Статті в журналах з теми "Control surface nano-functionalization"

This short communication presents a simple method of preparation of thin-metal nano-platelets utilizing metal sputtering and lift-off photolithography. The method offers complete control over size, shape and properties of nano-platelets of sub-micrometer thickness. Platelets with a thickness of 50–200 nm and with defined arbitrary shapes and sizes in the range of 15–300 μm were prepared from single or multiple metal layers by magnetron sputtering. Deposition of different metals in layers enabled fabrication of bi- or tri-metallic platelets with a magnetic core and differently composed surfaces. Highly reflective nano-platelets with a magnetic core allowed manipulation by magnetic fields, while different metallic surfaces served for functionalization by selected molecules. Submicron thin nano-platelets are extremely light (e.g., ~20 ng for a 100 μm × 100 μm × 0.1 μm gold nano-platelet) so that they can be attached to surfaces by only a few chemical bonds. At the same time their area is sufficiently large for simple optical recognition of their shape which is intended to label various characteristics depending on the specific surface functionalization of the given shape.

Trifluoropropyl-trichlorosilane reagents were used to tailor the surface chemistry of porous nano-structured thin films fabricated using glancing angle deposition (GLAD). GLAD produces high surface area films of isolated columnar structures and provides complete control over the film morphology. Here, the chemical tunability of these GLAD films was investigated using solution and vapor-phase surface functionalization methods. All films were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy and advancing aqueous contact angle measurements. Our results indicate that the surface chemistry of the GLAD films was effectively changed after functionalization by either approaches. We also note that vapor-phase functionalization provides more consistent results and eliminates the need for organic solvents, making it an ideal method for tailoring the surface properties of GLAD films for specific applications.

Cells are the smallest living units of a human body’s structure and function, and their behaviors should not be ignored in human physiological and pathological metabolic activities. Each cell has a different scale, and presents distinct responses to specific scales: Vascular endothelial cells may obtain a normal function when regulated by the 25 µm strips, but de-function if the scale is removed; stem cells can rapidly proliferate on the 30 nm scales nanotubes surface, but stop proliferating when the scale is changed to 100 nm. Therefore, micro and nano scales play a crucial role in directing cell behaviors on biomaterials surface. In recent years, a series of biomaterials surface with micro and/or nano scales, such as micro-patterns, nanotubes and nanoparticles, have been developed to control the target cell behavior, and further enhance the surface biocompatibility. This contribution will introduce the related research, and review the advances in the micro/nano scales for biomaterials surface functionalization.

DNA SAMs have received a lot of research interest recently as a suitable platform for modern biosensors. However, there are some shortcomings that remain to be addressed, such as uneven coverage of monolayer, or the spacing between the DNA strands that is hard to control. Here, we present DNA nanostructured cubes as an improved platform for DNA SAM based sensors. The DNA nano-cubes allow for a precise control of ssDNA spacing on the surface and have a great functionalization possibility. We have modified the nanostructures to include thiolated surface anchor and a fluorescence reporter. Cubes were deposited gold electrode via Au-S bonds and analyzed, using AFM and in-situ fluorescence microscopy.

Functionalization of a surface with biomimetic nano-/micro-scale roughness (wires) has attracted significant interests in surface science and engineering as well as has inspired many real-world applications including anti-fouling and superhydrophobic surfaces. Although methods relying on lithography include soft-lithography greatly increase our abilities in structuring hard surfaces with engineered nano-/micro-topologies mimicking real-world counterparts, such as lotus leaves, rose petals, and gecko toe pads, scalable tools enabling us to pattern polymeric substrates with the same structures are largely absent in literature. Here we present a robust and simple technique combining anodic aluminum oxide (AAO) templating and vacuum-assisted molding to fabricate nanowires over polymeric substrates. We have demonstrated the efficacy and robustness of the technique by successfully fabricating nanowires with large aspect ratios (>25) using several common soft materials including both cross-linking polymers and thermal plastics. Furthermore, a model is also developed to determine the length and molding time based on nanowires material properties (e.g., viscosity and interfacial tension) and operational parameters (e.g., pressure, vacuum, and AAO template dimension). Applying the technique, we have further demonstrated the confinement effects on polymeric crosslinking processes and shown substantial lengthening of the curing time.

Two-dimensional poly(dimethylsiloxane) (PDMS) films with wavy patterns were studied in order to investigate reversible and irreversible wetting effects. Pre-strained, surface oxidized layers of PDMS were used to form relieved wavy geometries, on which hydrophobic functionalization was carried out in order to produce irreversible wetting effects. Wavy-patterned PDMS films showed time-dependent reversible wetting effects. The degree of surface wettability could be tuned by the choice of wavy groove geometries. And the groove geometries were controlled via O2 plasma treatment and mechanical pre-straining. The pre-strained, buckled PDMS films were applied to the fabrication of hydrophobic polystyrene nano-patterns using colloidal self-assembly, where the colloids were arrayed in two-dimensional way. The wavy polystyrene films were found to be more hydrophobic relative to flat polystyrene films. The grooving methodology used in this study could be applied to enhancing the hydrophobicity of other types of polymeric thin films, eliminating the need for chemical treatment.

Texturing can be used to functionalize the surface of plastic parts and, in particular, to modify the interaction with fluids. Wetting functionalization can be used for microfluidics, medical devices, scaffolds, and more. In this research, hierarchical textures were generated on steel mold inserts using femtosecond laser ablation to transfer on plastic parts surface via injection molding. Different textures were designed to study the effects of various hierarchical geometries on the wetting behavior. The textures are designed to create wetting functionalization while avoiding high aspect ratio features, which are complex to replicate and difficult to manufacture at scale. Nano-scale ripples were generated over the micro-scale texture by creating laser-induced periodic surface structures. The textured molds were then replicated by micro-injection molding using polypropylene and poly(methyl methacrylate). The static wetting behavior was investigated on steel inserts and molded parts and compared to the theoretical values obtained from the Cassie–Baxter and Wenzel models. The experimental results showed correlations between texture design, injection molding replication, and wetting properties. The wetting behavior on the polypropylene parts followed the Cassie–Baxter model, while for PMMA, a composite wetting state of Cassie–Baxter and Wenzel was observed.

Dendrimers are novel three dimensional, hyperbranched globular nano polymeric architectures. Attractive features like nanoscopic size, narrow polydispersity index and excellent control over molecular structure afford dendrimers with ideal drug delivery ability through encapsulating drugs in their interior or covalently conjugating drugs on their surfaces. The adaptable surface functionalization ability enables covalent conjugation of various targeting molecules onto the surface of dendrimers, thereby allowing for generation of various multifunctional nanodevices for targeted drug delivery applications. Drug delivery researchers are especially enthusiastic about possible utility of dendrimers as drug delivery tool. However, to get the maximum benefits of these novel class macromolecules, a research by collaboration is very much essential. Finally, it is one of the youngest and exciting fields of polymer researches where all branches of science can take part and hence, deserves more intensive attention. Keywords: Dendrimers, Drug Delivery, Targeting, Dual Drug Loading, PAMAM

The large surface areas and interlayer gaps of 2D materials enable surface functionalization and intercalation as effective post-synthesis design knobs to tune the properties of 2D materials using ions, atoms, and organic molecules. For complete engineering control, detailed understanding of the interactions between the 2D materials and the molecules adsorbed on 2D materials surface or between the 2D materials and the intercalants is necessary. I will first discuss surface functionalization to tune the electrical properties of 2D materials. We developed an experimental approach to quantitatively measure the doping powers of organic electron donors (OEDs) to monolayer MoS2. Using novel and previously studied OEDs, we demonstrate experimentally that the measured doping power is a sensitive function of molecule’s reduction potential, size, surface coverage, and orientation to 2D materials [1, 2]. I will then discuss electrochemical intercalation into 2D materials to induce novel phases that were previously undetected and to study heterointerface effects on the intercalation induced phase transition [3, 4]. We discover new structural phases in Td-WTe2 and T’-MoTe2 with lithium intercalation and these new phases are semiconducting even though the initial WTe2 and MoTe2 are semimetallic and lithium ions donate electrons to the host materials. In the lithium intercalation-induced phase transition from the 2H to 1T’ phase of MoS2, we show that the nucleation of the 1T’ phase proceeds via heterogeneous nucleation where the nature of heterointerface dictates the thermodynamics of the phase transition. For these studies, multi-modal, in-situ probes were necessary to track the changes in the structure-property relation of the layered materials as a function of intercalation. [1] Advanced Electronic Materials 7, 2000873 (2021). [2] Nano Letters 22, p.4501 (2022). [3] ACS Applied Materials & Interfaces 13, p.10603-10611 (2021). [4] Advanced Materials 34, 2200861 (2022).

In general, nano-emulsions are submicron droplets composed of liquid oil phase dispersed in liquid aqueous bulk phase. They are stable and very powerful systems when it regards the encapsulation of lipophilic compounds and their dispersion in aqueous medium. On the other hand, when the properties of the nano-emulsions aim to be modified, e.g. for changing their surface properties, decorating the droplets with targeting ligands, or modifying the surface charge, the dynamic liquid / liquid interfaces make it relatively challenging. In this study, we have explored the development of nano-emulsions which were not anymore stabilized with a classical low-molecular weight surfactant, but instead, with an amphiphilic polymer based on poly(maleic anhydride-alt-1-octadecene) (PMAO) and Jeffamine®, a hydrophilic amino-terminated PPG/PEG copolymer. Using a polymer as stabilizer is a potential solution for the nano-emulsion functionalization, ensuring the droplet stabilization as well as being a platform for the droplet decoration with ligands (for instance after addition of function groups in the terminations of the chains). The main idea of the present work was to understand if the spontaneous emulsification –commonly performed with nonionic surfactants– can be transposed with amphiphilic polymers, and a secondary objective was to identify the main parameters impacting on the process. PMAO was modified with two different Jeffamine®, additionally different oils and different formulation conditions were evaluated. As a control, the parent monomer, octadecyl succinic anhydride (OSA) was also modified and studied in the similar way as that of polymer. The generated nano-emulsions were mainly studied by dynamic light scattering and electron microscopy, that allows discriminating the crucial parameters in the spontaneous process, originally conducted with polymers as only stabilizer.

Graphene is the prototype of two-dimensional (2D) materials, whose main feature is the extremely large surface-to-mass ratio. This property is interesting for a series of applications that involve interactions between particles and surfaces, such as, for instance, gas, fluid or charge storage, catalysis, and filtering. However, for most of these, a volumetric extension is needed, while preserving the large exposed surface. This proved to be rather a hard task, especially when specific structural features are also required (e.g., porosity or density given). Here we review the recent experimental realizations and theoretical/simulation studies of 3D materials based on graphene. Two main synthesis routes area available, both of which currently use (reduced) graphene oxide flakes as precursors. The first involves mixing and interlacing the flakes through various treatments (suspension, dehydration, reduction, activation, and others), leading to disordered nanoporous materials whose structure can be characterized a posteriori, but is difficult to control. With the aim of achieving a better control, a second path involves the functionalization of the flakes with pillars molecules, bringing a new class of materials with structure partially controlled by the size, shape, and chemical-physical properties of the pillars. We finally outline the first steps on a possible third road, which involves the construction of pillared multi-layers using epitaxial regularly nano-patterned graphene as precursor. While presenting a number of further difficulties, in principle this strategy would allow a complete control on the structural characteristics of the final 3D architecture.

An equilibrium study ofBacillus atrophaeus(B.a) spores on functionalized Single-Wall Carbon Nanotubes (SWCNTs) has been performed in order to characterize the adsorption properties of the spores/nanotubes complex. The carbon nanotubes here investigated were subjected to a two-step purification and functionalization treatment in order to introduce chemical groups on their basal planes. The inclusion of carboxyl functional groups on the nanotubes was corroborated by Raman and infrared spectroscopy. These carboxyl groups appear to enhance the nanotube-B.a.interaction by reacting with the proteinaceous pili appendages present on the spore surface. The adsorption data demonstrate that bacillus spores diffuse faster on functionalized carbon nanotubes than on as-received and purified nanomaterials. Transmission Electron Microscopy also shows that the chemically treated nanotubes resulted in a swollen nano-network which seems to further enhance the bacillus adsorption due to a more extensive spore-nanotube contact area.

Introduction: Silica nanoparticles (SNP) are extremely promising tools in nanotechnology and nano medicine. In most of applications such as capture and release of bacteriophage viruses the nano-structures of silica are coated by bio-compatible groups such as amine compounds. The presence of amino groups on the surface of the biosensors enables the installation of analyte receptors and antifouling agents such as oligo (ethylene oxide). Therefore, in this study, the electronic and structural properties of Core-Shell amino- Silica Nanoparticles are investigated.Material and Methods: In this investigation, we aim at obtaining the optimized structures and evaluate the geometries of the ground state for (SiO2) n (n=16, 20) nanoclusters. The electronic properties computed by density functional theory with GGA approximation and SCC-DFTB with hybrid Slater-Koster files are investigated and the effect of functionalization on such properties is discussed.Results: Solvolysis of studied structures is examined and it is shown that the highest occupied and lowest unoccupied molecular orbital states shift to obviously higher energy levels, which lead to more stable hydrogenated nanoclusters. The stability of nanoclusters rises by functionalization with amino and methylamine groups. Charge analysis of functionalized systems indicates the reactivity of nanoclusters. The results obtained in this paper are useful for chemical and biochemical applications of silica nanostructures.Conclusion: Results show that the length of amine hydrocarbon chain can control the electronic and magnetic properties of studied silica nanocluster (SNP) with different number of SiO2 unit. Pure ultra-small nanocluster shows the impressive spin splitting around the Fermi level, which is due to the spin splitting of outer silicon atoms. This feature of silica nanoclusters may be notable for applications in electronics.

Hydrothermally carbonized sugarcane bagasse (SCB) has exceptional surface properties. Looking at the huge amount of SCB produced, its biocompatible nature, cheap-cost for carbonization, and its easy functionalization can give impeccable nano-biomaterials for tissue engineering applications. Herein, sugarcane bagasse was converted into hydrochar (SCB-H) by hydrothermal carbonation. The SCB-H produced was further modified with iron oxide (Fe3O4) nanoparticles (denoted as SCB-H@Fe3O4). Facile synthesized nano-bio-composites were characterized by SEM, HR-TEM, XRD, FT-IR, XPS, TGA, and VSM analysis. Bare Fe3O4 nanoparticles (NPs), SCB-H, and SCB-H@Fe3O4 were tested for cytocompatibility and osteoconduction enhancement of human adipose tissue-derived mesenchymal stem cells (hADMSCs). The results confirmed the cytocompatible and nontoxic nature of SCB-H@Fe3O4. SCB-H did not show enhancement in osteoconduction, whilst on the other hand, Fe3O4 NPs exhibited a 0.5-fold increase in the osteoconduction of hADMSCs. However, SCB-H@Fe3O4 demonstrated an excellent enhancement in osteoconduction of a 3-fold increase over the control, and a 2.5-fold increase over the bare Fe3O4 NPs. Correspondingly, the expression patterns assessment of osteoconduction marker genes (ALP, OCN, and RUNX2) confirmed the osteoconductive enhancement by SCB-H@Fe3O4. In the proposed mechanism, the surface of SCB-H@Fe3O4 might provide a unique topology, and anchoring to receptors of hADMSCs leads to accelerated osteogenesis. In conclusion, agriculture waste-derived sustainable materials like “SCB-H@Fe3O44” can be potentially applied in highly valued medicinal applications of stem cell differentiation.

CDs are carbon fluorescent nanomaterials that have gained significant attention in recent years owing to their unique properties. In this work, we utilized a simple solution to produce CDs with func-tionalized amino groups via a one-step carbonization from a chitosan precursor. This simultaneous approach does not use special reagent for either the formation step or the amino-functionalization step of CDs. The as-prepared amino-functionalized CDs that possesses expected characteristics, such as nano-size distribution, monodispersible, high blue light emission, high absolute quantum yield of 5.52%, and functionalized amino groups on the surface. Furthermore, this work demonstrated the low cytotoxicity and high biocompatibility of the CDs, through the improvements in the astaxanthin production of alga Tetraselmis sp. (more than doubled (up to 0.044 mg/L), relative to the control). Thus, as-prepared CDs have promising properties not only for applications in bioimaging, drug delivery or sensors, but also as promoter in algal biorefinery

Surface functionalization with end-tethered weak polyelectrolytes (PE) is a versatile way to modify and control surface properties, given their ability to alter their degree of charge depending on external cues like pH and salt concentration. Weak PEs find usage in a wide range of applications, from colloidal stabilization, lubrication, adhesion, wetting to biomedical applications such as drug delivery and theranostics applications. They are also ubiquitous in many biological systems. Here, we present an overview of some of the main theoretical methods that we consider key in the field of weak PE at interfaces. Several applications involving engineered nanoparticles, synthetic and biological nanopores, as well as biological macromolecules are discussed to illustrate the salient features of systems involving weak PE near an interface or under (nano)confinement. The key feature is that by confining weak PEs near an interface the degree of charge is different from what would be expected in solution. This is the result of the strong coupling between structural organization of weak PE and its chemical state. The responsiveness of engineered and biological nanomaterials comprising weak PE combined with an adequate level of modeling can provide the keys to a rational design of smart nanosystems.

In the first part, we will focus on the principles of self-assembled molecular network formation at the liquid-solid interface on surfaces such as graphite, MoS2, and graphene. Then we will discuss how lateral confinement, induced by covalent functionalization of graphite and graphene, affects self-assembly. Several strategies will be demonstrated to realize two-dimensional lateral confinement, all based on the covalent modification of the surface, making use of bottom-up approaches or a combination of bottom-up and top-down approaches. The impact of these various types of confinement on the formation of self-assembled molecular networks will be discussed, including aspects such as nucleation and growth, directional self-assembly, on-surface chirality, polymorphism, and reactivity. In a second part, we will focus on the formation of porous two-dimensional covalent organic frameworks at the liquid-solid interface, and reveal various interesting aspects at the molecular level such as nucleation and growth mechanisms, and the impact local electric fields may have on (de)polymerization processes. The relevance and importance of scanning probe microscopes to investigate (and control) self-assembly and reactivity on surfaces will be illustrated. C. Rodríguez González, A. Leonhardt, H. Stadler, S. Eyley, W. Thielemans, S. De Gendt, K. S. Mali, S. De Feyter, ACS Nano, 2021, 15, 10618–10627 Verstraete, S. De Feyter, Chem. Soc. Rev., Chemical Society Reviews, 2021, 50, 5884–5897 Bragança, A. Minoia, R. Steeno, J. Seibel, B. E. Hirsch, L. Verstraete, O. Ivasenko, K. Müllen, K. S. Mali, R. Lazzaroni, S. De Feyter, J. Am. Chem. Soc., 2021, 143, 11080–11087 Tahara, Y. Kubo, S. Hashimoto, T. Ishikawa, H. Kaneko, A. Brown, B. E. Hirsch, S. De Feyter, Y. Tobe, J. Am. Chem. Soc., 2020, 142, 7699–7708 Zhan, Z.-F. Cai, M. Martínez-Abadía, A. Mateo-Alonso, S. De Feyter, J. Am. Chem. Soc. 2020, 142, 5964–5968

Today, MXenes with fascinating electronic, thermal, optical, and mechanical features have been broadly studied for biomedical applications, such as drug/gene delivery, photothermal/photodynamic therapy, antimicrobials/antivirals, sensing, tissue engineering, and regenerative medicine. In this context, various MXene-polymer composites have been designed to improve the characteristics such as physiological stability, sustained/controlled release behaviors, biodegradability, biocompatibility, selectivity/sensitivity, and functionality. Chitosan with advantages of ease of modification, biodegradability, antibacterial activities, non-toxicity, and biocompatibility can be considered as attractive materials for designing hybridized composites together with MXenes. These hybrid composites ought to be further explored for biomedical applications because of their unique properties such as high photothermal conversion efficiency, improved stability, selectivity/sensitivity, stimuli-responsiveness behaviors, and superior antibacterial features. These unique structural, functional, and biological attributes indicate that MXene-chitosan composites are attractive alternatives in biomedical engineering. However, several crucial aspects regarding the surface functionalization/modification, hybridization, nanotoxicological analyses, long-term biosafety assessments, biocompatibility, in vitro/in vivo evaluations, identification of optimization conditions, implementation of environmentally-benign synthesis techniques, and clinical translation studies are still need to be examined by researchers. Although very limited studies have revealed the great potentials of MXene-chitosan hybrids in biomedicine, the next steps should be toward the extensive research and detailed analyses in optimizing their properties and improving their functionality with a clinical and industrial outlook. Herein, recent developments in the use of MXene-chitosan composites with biomedical potentials are deliberated, with a focus on important challenges and future perspectives. In view of the fascinating properties and multifunctionality of MXene-chitosan composites, these hybrid materials can open significant new opportunities in the future for bio- and nano-medicine arena.

The COronaVIrus Disease (COVID-19) is a newly emerging viral disease caused by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Rapid increase in the number of COVID-19 cases worldwide led the WHO to declare a pandemic within a few months after the first case of infection. Due to the lack of a prophylactic measure to control the virus infection and spread, early diagnosis and quarantining of infected as well as the asymptomatic individuals are necessary for the containment of this pandemic. However, the current methods for SARS-CoV-2 diagnosis are expensive and time consuming, although some promising and inexpensive technologies are becoming available for emergency use. In this work, we report the synthesis of a cheap, yet highly sensitive, cobalt-functionalized TiO2 nanotubes (Co-TNTs)-based electrochemical sensor for rapid detection of SARS-CoV-2 through sensing the spike (receptor binding domain (RBD)) present on the surface of the virus. A simple, low-cost, and one-step electrochemical anodization route was used for synthesizing TNTs, followed by an incipient wetting method for cobalt functionalization of the TNTs platform, which was connected to a potentiostat for data collection. This sensor specifically detected the S-RBD protein of SARS-CoV-2 even at very low concentration (range of 14 to 1400 nM (nano molar)). Additionally, our sensor showed a linear response in the detection of viral protein over the concentration range. Thus, our Co-TNT sensor is highly effective in detecting SARS-CoV-2 S-RBD protein in approximately 30 s, which can be explored for developing a point of care diagnostics for rapid detection of SARS-CoV-2 in nasal secretions and saliva samples.

Background: Over the last decades, synthetic polymer-based electrospun nano/microfibers have emerged as potent materials in crucial biomedical applications such as tissue engineering, drug delivery and diagnostics. This is mainly attributed to versatility and reproducibility of the electrospinning (ES) process, as well as the high surface- to-volume ratio of the generated nanostructures. Appropriate functionalization with dedicated biomolecules (i.e. cell adhesive peptides, therapeutic molecules, bio-probes) is a critical requirement for the performances of such materials in their related application. Methods: We report on the different chemical methodologies for preparing biofunctionalized synthetic polymer fibers, on the basis of two main approaches: biomolecule introduction after ES process (post-ES) and before ES (pre-ES). We then focused on the latest implications of such materials in areas of tissue engineering, drug delivery and diagnostics. Results: This review describes the numerous immobilization strategies (either covalent or non-covalent) developed for designing biofunctionalized fibers, as well as their impact on their properties in dedicated application. The inputs of advanced conjugation tools (“clickable” chemistries, PEG linkers) for biofunctionalization are also highlighted. In the light of the literature, it appears that increasing research efforts are now devoted to multifunctional character and fiber combination with other materials (hydrogels, inorganic particles, microfluidic devices) for improved and tunable performances. Conclusion: Owing to flexibility and robustness of ES process as well as advances in conjugation and polymer/material engineering, high degree of control over biofunctionalization can now be achieved, to fit as best as possible the requirements of the targeted application. The performances reached up to now augur well for the future of such class of materials.

Graphene field-effect transistors (G-FETs) constitute an emerging platform for biosensing applications. Most genomic applications with G-FETs use single-stranded DNA (ssDNA) as probes in order to capture a specific target DNA sequence and to detect the corresponding change in the electrical response of the sensor1. Controlling the distribution of DNA probes on the graphene surface is crucial to the sensitivity, selectivity and reproducibility of the sensors1. The most popular immobilization approach uses a non-covalent linker molecule named 1-pyrenebutanoic acid succinimidyl ester (PBASE)1. This bifunctional molecule binds to the graphene surface through non-covalent π-π interactions via its aromatic pyrene group, and on the other end, its succinimidyl ester group can form a covalent bond with amine groups added to the terminal end of ssDNA probes. However, the adsorption process of PBASE molecules is not well controlled, which represents a limitation in the optimization of G-FET biosensors. Here, we present an investigation of the kinetics of the non-covalent adsorption of PBASE on graphene, in order to control the density of ssDNA probes for biosensing applications with G-FETs. We fabricated G-FET sensor arrays using CVD-grown graphene and photolithography techniques, as described previously2. First, we investigated the effect of incubation time on PBASE coverage on graphene, using electrical curves as well as Raman hyperspectral imaging (RIMA). We report a significative and reproducible electrical signature for the PBASE compared to the control without PBASE. We find that this electrical signature appears and saturates quickly compared to the timescales usually reported in the literature. Corroborating results were obtained with RIMA spectroscopy, showing a rapid response of the graphene modes following PBASE incubation. Next, we studied the effect of PBASE accumulation on the assembly of ssDNA probes. We will discuss the combined effect of PBASE accumulation and screening effects in saline buffer on the electrical signature of ssDNA probes. Our results will enable a better control on the non-covalent functionalization of graphene with PBASE for the assembly of various biomolecular probes for biosensing applications. 1. Béraud A, Sauvage M, Bazan CM, Tie M, Bencherif A, Bouilly D. Graphene field-effect transistors as bioanalytical sensors: design, operation and performance. Analyst. 2021;(146):403-428. 2.Bazan CM, Béraud A, Nguyen M, Bencherif A, Martel R and Bouilly D. Dynamic Gate controlled of Aryldiazonium chemistry on Graphene field-effect transistors. Nano Lett. 2022;22(7):2635-2642.

A new, innovative approach in the search for an effective and cheap carbon dioxide sorbent, in line with the circular economy and sustainable development principles, directs the attention of researchers to various types of waste ashes generated as a result of biomass combustion. In addition to the use of environmentally safe materials that have been experimentally identified, and that, in some way, have adjustable sorption capacity, it is also possible to rationally develop a widely applicable, simple, and inexpensive technology based on large amounts of this type of post-industrial waste, which is also an equally important issue for the natural environment (reducing the need for ash storage and accumulation). Even the lower sorption capacity can be successfully compensated for by their common availability and very low cost. Thus, the CO2 adsorption capability of the ashes from the combustion of straw biomass was experimentally investigated with the use of a high-pressure adsorption stand. The presented original technological concept has been positively verified on a laboratory scale, thus a functionalization-based approach to the combustion of substrate mixtures with nano-structural additives (raw, dried, calcined halloysite, kaolinite), introduced to improve the performance of straw biomass combustion and bottom ash formation in power boilers, clearly increased the CO2 adsorption capacity of the modified ashes. This allows for an advantageous synergy effect in the extra side-production of useful adsorbents in the closed-loop “cascade” scheme of the CE process. The addition of 4 wt.% kaolinite to straw biomass caused an over 2.5-fold increase in the CO2 adsorption capacity in relation to ash from the combustion of pure straw biomass (with a CO2 adsorption capacity of 0.132 mmol/g). In the case of addition of 4 wt.% nano-structured species to the straw combustion process, the best effects (ash adsorption capacity) were obtained in the following order: kaolinite (0.321 mmol/g), raw halloysite (0.310 mmol/g), calcined halloysite (0.298 mmol/g), and dried halloysite (0.288 mmol/g). Increasing the dose (in relation to all four tested substances) of the straw biomass additive from 2 to 4 wt.%, not only increase the adsorption capacity of the obtained ash, thus enriched with nano-structural additives, but also a showed a significant reduction in the differences between the maximum adsorption capacity of each ash is observed. The experimental results were analyzed using five models of adsorption isotherms: Freundlich, Langmuir, Jovanović, Temkin, and Hill. Moreover, selected samples of each ash were subjected to porosimetry tests and identification of the surface morphology (SEM). The obtained results can be used in the design of PSA processes or as permanent CO2 adsorbents, based on the environmentally beneficial option of using ashes from biomass combustion with appropriately selected additives.

Polymer membranes are used extensively in water purification to filter and remove particulate and molecular contaminants. Ideally, these membranes should exhibit high permeance, selectivity, and fouling resistance, but these attributes are rarely achieved simultaneously. One approach to improve membrane performance is to modify the polymer using reactive chemical vapors to impart the desired physiochemical properties. In this presentation, I will describe recent work at Argonne using atomic layer deposition (ALD), sequential infiltration synthesis (SIS), and vapor-phase grafting to modify polymer membranes used for ultra- and nano-filtration in water treatment. These techniques rely on self-limiting chemical reactions between gaseous precursors and a solid surface to grow material in an atomically controlled fashion. We have used ALD to produce ultrathin and conformal inorganic layers allowing the membrane pore size and pore wall composition to be precisely tuned, SIS for the bulk modification of polymers by creating an organic-inorganic hybrid material, and vapor-phase grafting of small molecules to achieve additional control over the membrane surface properties. Our studies employ a suite of in-situ and in-operando measurements to elucidate the surface chemistry for these processes and extensive ex-situ characterization and testing to understand the effects of chemical vapor treatment on polymers and how they impact membrane performance.

Bioactive secondary metabolites derived from herbs are examined for their suitability of conversion into nanoforms having flexible morphological controls, surface stabilizations and surface functionalization. This can lead to stable chemical conjugations based on molecular recognition for their possible applications in the form of smart pharmaceuticals, nutraceuticals, cosmaceuticals and many other related areas of human healthcare using green chemistry routes. Using the principles of nanoscience and technology in association with genomics and proteomics, an attempt has been made to decipher whether a suitable form of drug discovery and targeted drug delivery like schemes arefeasible in case of such nano phytochemicals using various kinds of nanosize carriers and labelling molecules already identified in the course of investigations of contemporary single molecule drug developments. Additional efforts can clarify whether such species will be successful in the early detection of diseases based on marker molecules. Once identified, these green phytochemicals will certainly replace many hazardous chemical compounds by their environmentally friendly and sustainable forms in times to come.

Bioactive secondary metabolites derived from herbs are examined for their suitability of conversion into nanoforms having flexible morphological controls, surface stabilizations and surface functionalization. This can lead to stable chemical conjugations based on molecular recognition for their possible applications in the form of smart pharmaceuticals, nutraceuticals, cosmaceuticals and many other related areas of human healthcare using green chemistry routes. Using the principles of nanoscience and technology in association with genomics and proteomics, an attempt has been made to decipher whether a suitable form of drug discovery and targeted drug delivery like schemes are feasible in case of such nano phytochemicals using various kinds of nanosize carriers and labelling molecules already identified in the course of investigations of contemporary single molecule drug developments. Additional efforts can clarify whether such species will be successful in the early detection of diseases based on marker molecules. Once identified, these green phytochemicals will certainly replace many hazardous chemical compounds by their environmentally friendly and sustainable forms in times to come.

Titanium (Ti) nanotopography modulates the osteogenic response to exogenous bone morphogenetic protein 7 (BMP-7) in vitro, supporting enhanced alkaline phosphatase mRNA expression and activity, as well as higher osteopontin (OPN) mRNA and protein levels. As the biological effects of OPN protein are modulated by its proteolytic cleavage by serum proteases, this in vitro study evaluated the effects on osteogenic cells in the presence of a physiological blood clot previously formed on a BMP-7-coated nanostructured Ti surface obtained by chemical etching (Nano-Ti). Pre-osteoblastic MC3T3-E1 cells were cultured during 5 days on recombinant mouse (rm) BMP-7-coated Nano-Ti after it was implanted in adult female C57BI/6 mouse dorsal dermal tissue for 18 h. Nano-Ti without blood clot or with blood clot at time 0 were used as the controls. The presence of blood clots tended to inhibit the expression of key osteoblast markers, except for Opn, and rmBMP-7 functionalization resulted in a tendency towards relatively greater osteoblastic differentiation, which was corroborated by runt-related transcription factor 2 (RUNX2) amounts. Undetectable levels of OPN and phosphorylated suppressor of mothers against decapentaplegic (SMAD) 1/5/9 were noted in these groups, and the cleaved form of OPN was only detected in the blood clot immediately prior to cell plating. In conclusion, the strategy to mimic in vitro the initial interfacial in vivo events by forming a blood clot on a Ti nanoporous surface resulted in the inhibition of pre-osteoblastic differentiation, which was minimally reverted with an rmBMP-7 coating.

Silane-coating strategy has been used to bind biological compounds to the titanium surface, thereby making implant devices biologically active. However, it has not been determined if the presence of the silane coating itself is biocompatible to osseointegration. The aim of the present study was to evaluate if silane-coating affects bone formation on titanium using a rabbit model. For this, titanium screw implants (3.75 by 6 mm) were hydroxylated in a solution of H2SO4/30% H2O2 for 4 h before silane-coating with 3-aminopropyltriethoxysilane (APTES). A parallel set of titanium screws underwent only the hydroxylation process to present similar acid-etched topography as a control. The presence of the silane on the surface was checked by x-ray photoelectron spectroscopy (XPS), with scanning electron microscopy (SEM) and atomic force microscopy (AFM). A total of 40 titanium screws were implanted in the tibia of ten New Zealand rabbits in order to evaluate bone-to-implant contact (BIC) after 3 weeks and 6 weeks of healing. Silane-coated surface presented higher nitrogen content in the XPS analysis, while micro- and nano-topography of the surface remained unaffected. No difference between the groups was observed after 3 and 6 weeks of healing (p > 0.05, independent t-test), although an increase in BIC occurred over time. These results indicate that silanization of a titanium surface with APTES did not impair the bone formation, indicating that this can be a reliable tool to anchor osteogenic molecules on the surface of implant devices.

Abstract Synthetic materials displaying multi-modal ligands with exact chemiophysical properties for immune modulation are valuable research tools and a promising therapeutic platform. However, precise chemical conjugation of multiple proteins on biomaterial surfaces is challenging. Through DNA hybridization-mediated biomolecule loading, we achieved high density and precise ratiometric control of multiple ligands on nano-/micro-particles. We found increasing ratios of anti-CD3 to anti-CD28, 1:5, 1:3, 1:1, 3:1 to 5:1, on microparticles yielded a linear increase of ex vivo expansion of primary human CD4+ and CD8+ T cells until reaching a plateau at 3:1 ratio. For CD8+ T cells, the ratio of 3:1 resulted in the highest percentage of central memory cells, 51.4 ± 7.2% vs. 14.4 ± 7.6% for 1:5 ratio (n = 5 donors). Particle surface presentation of IL-2 using an anti-IL-2 antibody (in trans to CD3/28 particles) yielded ~3 fold more ex vivo expansion of CD4+ and CD8+ T cells in 14 days when compared to the equivalent dose of soluble IL-2. Using intratumoral injection of microparticles presenting a ligand for a synthetic Notch receptor, we locally induced chimeric antigen receptor (CAR) expression on systemically infused engineered T cells and observed CAR T cell killing of the injected tumors, while sparing the uninjected identical tumors in the contralateral flank. These results highlight the potential of this platform in achieving better control of therapeutic cell manufacture and local tuning of immunotherapies. Ongoing work is using DNA origami-mediated patterning to dissect spatial requirements of various T cell activating ligands to better understand critical parameters of T cell activation with the goal to improve the design of immunotherapies.

Gold nanoparticles (Au NPs) have received great attention owing to their biocompatible nature, environmental, and widespread biomedical applications. Au NPs are known as capable to regulate inflammatory responses in several tissues and organs; interestingly, lower toxicity in conjunction with anti-inflammatory effects was reported to occur with Au NPs treatment. Several variables drive this benefit-risk balance, including Au NPs physicochemical properties such as their morphology, surface chemistry, and charge. In our research we prepared hybrid Au@LCC nanocolloids by the Pulsed Laser Ablation, which emerged as a suitable chemically clean technique to produce ligand-free or functionalized nanomaterials, with tight control on their properties (product purity, crystal structure selectivity, particle size distribution). Here, for the first time to our knowledge, we have investigated the bioproperties of Au@LCCs. When tested in vitro on intestinal epithelial cells exposed to TNF-α, Au@LCCs sample at the ratio of 2.6:1 showed a significantly reduced TNF gene expression and induced antioxidant heme oxygenase-1 gene expression better than the 1:1 dispersion. Although deeper investigations are needed, these findings indicate that the functionalization with LCCs allows a better interaction of Au NPs with targets involved in the cell redox status and inflammatory signaling.

Arg-Gly-Asp (RGD)-binding integrins, e.g., αvβ3, αvβ1, αvβ5 integrins, are currently regarded as privileged targets for the delivery of diagnostic and theranostic agents, especially in cancer treatment. In contrast, scarce attention has been paid so far to the diagnostic opportunities promised by integrins that recognize other peptide motifs. In particular, α4β1 integrin is involved in inflammatory, allergic, and autoimmune diseases, therefore, it represents an interesting therapeutic target. Aiming at obtaining simple, highly stable ligands of α4β1 integrin, we designed hybrid α/β peptidomimetics carrying linkable side chains for the expedient functionalization of biomaterials, nano- and microparticles. We identified the prototypic ligands MPUPA-(R)-isoAsp(NHPr)-Gly-OH (12) and MPUPA-Dap(Ac)-Gly-OH (13) (MPUPA, methylphenylureaphenylacetic acid; Dap, 2,3-diamino propionic acid). Modification of 12 and 13 by introduction of flexible linkers at isoAsp or Dap gave 49 and 50, respectively, which allowed for coating with monolayers (ML) of flat zeolite crystals. The resulting peptide–zeolite MLs were able to capture selectively α4β1 integrin-expressing cells. In perspective, the α4β1 integrin ligands identified in this study can find applications for preparing biofunctionalized surfaces and diagnostic devices to control the progression of α4β1 integrin-correlated diseases.

Abstract Nanoformulations of high-Z elements can improve therapeutic outcome in radiotherapy-based treatment of tumors, but current nanomedicine implementations in radiotherapy still need biocompatible, non-toxic nano-agents exhibiting low polydispersity and high colloidal stability. Here, we elaborate methods of femtosecond (fs) laser ablation in water and organic solvents to fabricate stable aqueous colloidal solutions of ultrapure elemental Bi nanoparticles (NPs) and characterize them. We show that fs laser ablation of Bi target leads to the formation of spherical elemental Bi NPs having 25 nm mean size and wide size-dispersion. NPs prepared in water undergo fast conversion into 400-500 nm flake-like nanosheets, while NPs prepared in acetone demonstrate a high colloidal stability. We then employ methods of fs laser fragmentation to control mean size and size dispersion of Bi NPs. Stable aqueous solution of Bi NPs suitable for biomedical applications can be obtained by coating with Pluronic® F-127. We finally show that surface modification of Bi NPs increases its colloidal stability in phosphate buffer saline (PBS) solution by more than 6 fold. Exempt of any toxic synthetic by-products, laser-ablated Bi NPs present a novel appealing nanoplatform for image-guided combination photo- and radiotherapy.

This article provides the review of the medical use of pH- and temperature-sensitive polymer hydrogels. Such polymers are characterised by their thermal and pH sensitivity in aqueous solutions at the functioning temperature of living organisms and can react to the slightest changes in environmental conditions. Due to these properties, they are called stimuli-sensitive polymers. This response to an external stimulus occurs due to the amphiphilicity (diphilicity) of these (co)polymers. The term hydrogels includes several concepts of macrogels and microgels. Microgels, unlike macrogels, are polymer particles dispersed in a liquid and are nano- or micro-objects. The review presents studies reflecting the main methods of obtainingsuch polymeric materials, including precipitation polymerisation, as the main, simplest, and most accessible method for mini-emulsion polymerisation, microfluidics, and layer-by-layer adsorption of polyelectrolytes. Such systems will undoubtedly be promising for use in biotechnology and medicine due to the fact that they are liquid-swollen particles capable of binding and carrying various low to high molecular weight substances. It is also important that slight heating and cooling or a slight change in the pH of the medium shifts the system from a homogeneous to a heterogeneous state and vice versa. This providesthe opportunity to use these polymers as a means of targeted drug delivery, thereby reducing the negative effect of toxic substances used for treatment on the entire body and directing the action to a specific point. In addition, such polymers can be used to create smart coatings of implanted materials, as well as an artificial matrix for cell and tissue regeneration, contributing to a significant increase in the survival rate and regeneration rate of cells and tissues. References 1. Gisser K. R. C., Geselbracht M. J., Cappellari A.,Hunsberger L., Ellis A. B., Perepezko J., et al. Nickeltitaniummemory metal: A "Smart" material exhibitinga solid-state phase change and superelasticity. Journalof Chemical Education. 1994;71(4): 334. DOI: https://doi.org/10.1021/ed071p3342. Erman B., Flory P.J.. Critical phenomena andtransitions in swollen polymer networks and in linearmacromolecules. Macromolecules. 1986;19(9): 2342–2353. DOI: https://doi.org/10.1021/ma00163a0033. Tanaka T., Fillmore D., Sun S.-T., Nishio I.,Swislow G., Shah A. Phase transitions in ionic gels.Physical Review Letters. 1980;45(20): 1636–1639. DOI:https://doi.org/10.1103/physrevlett.45.16364. Polymer Gels. DeRossi D., Kajiwara K., Osada Y.,Yamauchi A. (eds.). Boston, MA: Springer US; 1991.354 p. DOI: https://doi.org/10.1007/978-1-4684-5892‑35. Ilmain F., Tanaka T., Kokufuta E. Volumetransition in a gel driven by hydrogen bonding. Nature.1991;349(6308): 400–401. DOI: https://doi.org/10.1038/349400a06. Kuhn W., Hargitay B., Katchalsky A., EisenbergH. Reversible dilation and contraction by changing thestate of ionization of high-polymer acid networks.Nature. 1950;165(4196): 514–516. DOI: https://doi.org/10.1038/165514a07. Steinberg I. Z., Oplatka A., Katchalsky A.Mechanochemical engines. Nature. 1966;210(5036):568-571. DOI: https://doi.org/10.1038/210568a08. Tian H., Tang Z., Zhuang X., Chen X., Jing X.Biodegradable synthetic polymers: Preparation,functionalization and biomedical application. Progressin Polymer Science. 2012;37(2): 237–280. DOI: https://doi.org/10.1016/j.progpolymsci.2011.06.0049. Gonçalves C., Pereira P., Gama M. Self-Assembledhydrogel nanoparticles for drug delivery applications.Materials. 2010;3(2): 1420–1460. DOI: https://doi.org/10.3390/ma302142010. Pangburn T. O., Petersen M. A., Waybrant B.,Adil M. M., Kokkoli E. Peptide- and Aptamer-functionalizednanovectors for targeted delivery of therapeutics.Journal of Biomechanical Engineering. 2009;131(7):074005. DOI: https://doi.org/10.1115/1.316076311. Caldorera-Moore M. E., Liechty W. B., PeppasN. A. Responsive theranostic systems: integrationof diagnostic imaging agents and responsive controlledrelease drug delivery carriers. Accounts of ChemicalResearch. 2011;44(10): 1061–1070. DOI: https://doi.org/10.1021/ar200177712. Das M., Sanson N., Fava D., Kumacheva E.Microgels loaded with gold nanorods: photothermallytriggered volume transitions under physiologicalconditions†’. Langmuir. 2007;23(1): 196–201. DOI:https://doi.org/10.1021/la061596s13. Oh J. K., Lee D. I., Park J. M. Biopolymer-basedmicrogels/nanogels for drug delivery applications.Progress in Polymer Science. 2009;34(12): 1261–1282.DOI: https://doi.org/10.1016/j.progpolymsci.2009.08.00114. Oh J. K., Drumright R., Siegwart D. J.,Matyjaszewski K. The development of microgels/nanogels for drug delivery applications. Progress inPolymer Science. 2008;33(4): 448–477. DOI: https://doi.org/10.1016/j.progpolymsci.2008.01.00215. Talelli M., Hennink W. E. Thermosensitivepolymeric micelles for targeted drug delivery.Nanomedicine. 2011;6(7): 1245–1255. DOI: https://doi.org/10.2217/nnm.11.9116. Bromberg L., Temchenko M., Hatton T. A. Smartmicrogel studies. Polyelectrolyte and drug-absorbingproperties of microgels from polyether-modifiedpoly(acrylic acid). Langmuir. 2003;19(21): 8675–8684.DOI: https://doi.org/10.1021/la030187i17. Vinogradov S. V. Polymeric nanogel formulationsof nucleoside analogs. Expert Opinion on Drug Delivery.2007;4(1): 5–17. DOI: https://doi.org/10.1517/17425247.4.1.518. Vinogradov S. V. Colloidal microgels in drugdelivery applications. Current Pharmaceutical Design.2006;12(36): 4703–4712. DOI: https://doi.org/10.2174/13816120677902625419. Kabanov A. V., Vinogradov S. V. Nanogels aspharmaceutical carriers: finite networks of infinitecapabilities. Angewandte Chemie International Edition.2009;48(30): 5418–5429. DOI: https://doi.org/10.1002/anie.20090044120. Lee E. S., Gao Z., Bae Y. H. Recent progress intumor pH targeting nanotechnology. Journal ofControlled Release. 2008;132(3): 164–170. DOI: https://doi.org/10.1016/j.jconrel.2008.05.00321. Dong H., Mantha V., Matyjaszewski K.Thermally responsive PM(EO)2MA magnetic microgelsvia activators generated by electron transfer atomtransfer radical polymerization in miniemulsion.Chemistry of Materials. 2009;21(17): 3965–3972. DOI:https://doi.org/10.1021/cm901143e22. Nayak S., Lyon L. A. Soft nanotechnology withsoft nanoparticles. Angewandte Chemie InternationalEdition. 2005;44(47): 7686–7708. DOI: https://doi.org/10.1002/anie.20050132123. Hennink W. E., van Nostrum C. F. Novelcrosslinking methods to design hydrogels. AdvancedDrug Delivery Reviews. 2012;64: 223–236. DOI: https://doi.org/10.1016/j.addr.2012.09.00924. Motornov M., Roiter Y., Tokarev I., Minko S.Stimuli-responsive nanoparticles, nanogels and capsulesfor integrated multifunctional intelligent systems.Progress in Polymer Science. 2010;35(1-2): 174–211. DOI:https://doi.org/10.1016/j.progpolymsci.2009.10.00425. Saunders B. R., Laajam N., Daly E., Teow S.,Hu X., Stepto R. Microgels: From responsive polymercolloids to biomaterials. Advances in Colloid andInterface Science. 2009;147-148: 251–262. DOI: https://doi.org/10.1016/j.cis.2008.08.00826. Landfester K. Miniemulsion polymerizationand the structure of polymer and hybrid nanoparticles.chemInform. 2009;40(33). DOI: https://doi.org/10.1002/chin.20093327927. Seo M., Nie Z., Xu S., Mok M., Lewis P.C.,Graham R., et al. Continuous microfluidic reactors forpolymer particles. Langmuir. 2005;21(25): 11614–11622. DOI: https://doi.org/10.1021/la050519e28. Nie Z., Li W., Seo M., Xu S., Kumacheva E. Janusand ternary particles generated by microfluidicsynthesis: design, synthesis, and self-assembly. Journalof the American Chemical Society. 2006;128(29): 9408–9412. DOI: https://doi.org/10.1021/ja060882n29. Seiffert S., Thiele J., Abate A. R., Weitz D. A.Smart microgel capsules from macromolecularprecursors. Journal of the American Chemical Society.2010;132(18): 6606–6609. DOI: https://doi.org/10.1021/ja102156h30. Rossow T., Heyman J. A., Ehrlicher A. J.,Langhoff A., Weitz D. A., Haag R., et al. Controlledsynthesis of cell-Laden Microgels by Radical-FreeGelation in Droplet Microfluidics. Journal of theAmerican Chemical Society. 2012;134(10): 4983–4989.DOI: https://doi.org/10.1021/ja300460p31. Perry J. L., Herlihy K. P., Napier M. E.,DeSimone J. M. PRINT: A novel platform toward shapeand size specific nanoparticle theranostics. Accountsof Chemical Research. 2011;44(10): 990–998. DOI:https://doi.org/10.1021/ar200031532. Caruso F., Sukhorukov G. Coated Colloids:Preparation, characterization, assembly and utilization.In: Decher G., Schlenoff J. B., editors. MultilayerThin Films. Weinheim, FRG: Wiley-VCH Verlag GmbH& Co. KGaA; 2002. p. 331-362.33. Sauzedde F., Elaïssari A., Pichot C. Hydrophilicmagnetic polymer latexes. 2. Encapsulation ofadsorbed iron oxide nanoparticles. Colloid & PolymerScience. 1999;277(11): 1041–1050. DOI: https://doi.org/10.1007/s00396005048834. Sauzedde F., Elaïssari A., Pichot C. Hydrophilicmagnetic polymer latexes. 1. Adsorption of magneticiron oxide nanoparticles onto various cationic latexes.Colloid & Polymer Science. 1999;277(9): 846–855. DOI:https://doi.org/10.1007/s00396005046135. Pich A., Richtering W. Microgels by PrecipitationPolymerization: Synthesis, Characterization, andFunctionalization. In: Pich A., Richtering W. (eds.)Chemical Design of Responsive Microgels. SpringerHeidelberg Dordrecht London New York; 2011. p. 1–37.DOI: https://doi.org/10.1007/978-3-642-16379-136. Yamada N., Okano T., Sakai H., Karikusa F.,Sawasaki Y., Sakurai Y. Thermo-responsive polymericsurfaces; control of attachment and detachment ofcultured cells. Die Makromolekulare Chemie, RapidCommunications. 1990;11(11): 571–576. DOI: https://doi.org/10.1002/marc.1990.03011110937. Kushida A., Yamato M., Konno C., Kikuchi A.,Sakurai Y., Okano T. Decrease in culture temperaturereleases monolayer endothelial cell sheets togetherwith deposited fibronectin matrix from temperatureresponsiveculture surfaces. Journal of BiomedicalMaterials Research. 1999;45(4): 355–362. DOI: https://doi.org/10.1002/(sici)1097-4636(19990615)45:4<355::aid-jbm10>3.0.co;2-738. Sekine H., Shimizu T., Dobashi I., Matsuura K.,Hagiwara N., Takahashi M., et al. Cardiac cell sheettransplantation improves damaged heart function viasuperior cell survival in comparison with dissociatedcell injection. Tissue Engineering Part A. 2011;17(23-24): 2973–2980. DOI: https://doi.org/10.1089/ten.tea.2010.065939. Nishida K., Yamato M., Hayashida Y.,Watanabe K., Yamamoto K., Adachi E., et al. Corneal reconstruction with tissue-engineered cell sheetscomposed of autologous oral mucosal epithelium. TheNew England Journal of Medicine. 2004;351(12): 1187–1196. DOI: https://doi.org/10.1056/nejmoa04045540. Kanzaki M., Yamato M., Yang J., Sekine H.,Kohno C., Takagi R., et al. Dynamic sealing of lungair leaks by the transplantation of tissue engineeredcell sheets. Biomaterials. 2007;28(29): 4294–4302.DOI: https://doi.org/10.1016/j.biomaterials.2007.06.00941. Iwata T., Yamato M., Tsuchioka H., Takagi R.,Mukobata S., Washio K., et al. Periodontal regenerationwith multi-layered periodontal ligament-derived cellsheets in a canine model. Biomaterials. 2009;30(14):2716–2723. DOI: https://doi.org/10.1016/j.biomaterials.2009.01.03242. Sawa Y., Miyagawa S., Sakaguchi T., Fujita T.,Matsuyama A., Saito A., et al. Tissue engineeredmyoblast sheets improved cardiac function sufficientlyto discontinue LVAS in a patient with DCM: report ofa case. Surgery Today. 2012;42(2): 181–184. DOI:https://doi.org/10.1007/s00595-011-0106-443. Ohki T., Yamato M., Ota M., Takagi R.,Murakami D., Kondo M., et al. Prevention of esophagealstricture after endoscopic submucosal dissection usingtissue-engineered cell sheets. Gastroenterology.2012;143(3): 582–588. DOI: https://doi.org/10.1053/j.gastro.2012.04.05044. Ebihara G., Sato M., Yamato M., Mitani G.,Kutsuna T., Nagai T., et al. Cartilage repair intransplanted scaffold-free chondrocyte sheets usinga minipig model. Biomaterials. 2012;33(15): 3846–3851. DOI: https://doi.org/10.1016/j.biomaterials.2012.01.05645. Sato M., Yamato M., Hamahashi K., Okano T.,Mochida J. Articular cartilage regeneration using cellsheet technology. The Anatomical Record. 2014;297(1):36–43. DOI: https://doi.org/10.1002/ar.2282946. Kuramoto G., Takagi S., Ishitani K., Shimizu T.,Okano T., Matsui H. Preventive effect of oral mucosalepithelial cell sheets on intrauterine adhesions. HumanReproduction. 2014;30(2): 406–416. DOI: https://doi.org/10.1093/humrep/deu32647. Yamamoto K., Yamato M., Morino T.,Sugiyama H., Takagi R., Yaguchi Y., et al. Middle earmucosal regeneration by tissue-engineered cell sheettransplantation. NPJ Regenerative Medicine. 2017;2(1):6. DOI: https://doi.org/10.1038/s41536-017-0010-748. Gan D., Lyon L. A. Synthesis and Proteinadsorption resistance of PEG-modified poly(Nisopropylacrylamide) core/shell microgels.Macromolecules. 2002;35(26): 9634–9639. DOI: https://doi.org/10.1021/ma021186k49. Veronese F. M., Mero A. The impact ofPEGylation on biological therapies. BioDrugs.2008;22(5): 315–329. DOI: https://doi.org/10.2165/00063030-200822050-0000450. Sahay G., Alakhova D. Y., Kabanov A. V.Endocytosis of nanomedicines. Journal of ControlledRelease. 2010;145(3): 182–195. DOI: https://doi.org/10.1016/j.jconrel.2010.01.03651. Nolan C. M., Reyes C. D., Debord J. D.,García A. J., Lyon L. A. Phase transition behavior,protein adsorption, and cell adhesion resistance ofpoly(ethylene glycol) cross-linked microgel particles.Biomacromolecules. 2005;6(4): 2032–2039. DOI:https://doi.org/10.1021/bm050008752. Scott E. A., Nichols M. D., Cordova L. H., GeorgeB. J., Jun Y.-S., Elbert D. L. Protein adsorption and celladhesion on nanoscale bioactive coatings formed frompoly(ethylene glycol) and albumin microgels.Biomaterials. 2008;29(34): 4481–4493. DOI: https://doi.org/10.1016/j.biomaterials.2008.08.00353. South A. B., Whitmire R. E., García A. J.,Lyon L. A. Centrifugal deposition of microgels for therapid assembly of nonfouling thin films. ACS AppliedMaterials & Interfaces. 2009;1(12): 2747–2754. DOI:https://doi.org/10.1021/am900543554. Wang Q., Uzunoglu E., Wu Y., Libera M. Selfassembledpoly(ethylene glycol)-co-acrylic acidmicrogels to inhibit bacterial colonization of syntheticsurfaces. ACS Applied Materials & Interfaces. 2012;4(5):2498–2506. DOI: https://doi.org/10.1021/am300197m55. Wang Q., Libera M. Microgel-modified surfacesenhance short-term osteoblast response. Colloids andSurfaces B: Biointerfaces. 2014;118: 202–209. DOI:https://doi.org/10.1016/j.colsurfb.2014.04.00256. Tsai H.-Y., Vats K., Yates M. Z., Benoit D. S. W.Two-dimensional patterns of poly(N-isopropylacrylamide)microgels to spatially control fibroblastadhesion and temperature-responsive detachment.Langmuir. 2013;29(39): 12183–12193. DOI: https://doi.org/10.1021/la400971g57. Lynch I. , Miller I. , Gallagher W. M. ,Dawson K. A. Novel method to prepare morphologicallyrich polymeric surfaces for biomedical applicationsvia phase separation and arrest of microgel particles.The Journal of Physical Chemistry B. 2006;110(30):14581–14589. DOI: https://doi.org/10.1021/jp061166a58. Li Y., Chen P., Wang Y., Yan S., Feng X., Du W.,et al. Rapid assembly of heterogeneous 3D cellmicroenvironments in a microgel array. AdvancedMaterials. 2016;28(18): 3543–3548. DOI: https://doi.org/10.1002/adma.20160024759. Bridges A. W., Singh N., Burns K. L., BabenseeJ. E., Andrew Lyon L., García A. J. Reduced acuteinflammatory responses to microgel conformalcoatings. Biomaterials. 2008;29(35): 4605–4615. DOI:https://doi.org/10.1016/j.biomaterials.2008.08.01560. Bridges A. W., Whitmire R. E., Singh N.,Templeman K. L., Babensee J. E., Lyon L. A., et al.Chronic inflammatory responses to microgel-basedimplant coatings. Journal of Biomedical Materials Research Part A. 2010;94A(1): 252–258. DOI: https://doi.org/10.1002/jbm.a.3266961. Gutowski S. M., Templeman K. L., South A. B.,Gaulding J. C., Shoemaker J. T., LaPlaca M. C., et al.Host response to microgel coatings on neuralelectrodes implanted in the brain. Journal of BiomedicalMaterials Research Part A. 2014;102(5): 1486–1499.DOI: https://doi.org/10.1002/jbm.a.3479962. da Silva R. M. P., Mano J. F., Reis R. L. Smartthermoresponsive coatings and surfaces for tissueengineering: switching cell-material boundaries.Trends in Biotechnology. 2007;25(12): 577–583. DOI:https://doi.org/10.1016/j.tibtech.2007.08.01463. Schmidt S., Zeiser M., Hellweg T., Duschl C.,Fery A., Möhwald H. Adhesion and mechanicalproperties of PNIPAM microgel films and theirpotential use as switchable cell culture substrates.Advanced Functional Materials. 2010;20(19): 3235–3243. DOI: https://doi.org/10.1002/adfm.20100073064. Uhlig K., Wegener T., He J., Zeiser M., BookholdJ., Dewald I., et al. Patterned thermoresponsivemicrogel coatings for noninvasive processing ofadherent cells. Biomacromolecules. 2016;17(3): 1110–1116. DOI: https://doi.org/10.1021/acs.biomac.5b01728

AbstractControllable fabrication of surface micro/nano structures is the key to realizing surface functionalization for various applications. As a versatile approach, ultrafast laser ablation has been widely studied for surface micro/nano structuring. Increasing research efforts in this field have been devoted to gaining more control over the fabrication processes to meet the increasing need for creation of complex structures. In this paper, we focus on the in-situ deposition process following the plasma formation under ultrafast laser ablation. From an overview perspective, we firstly summarize the different roles that plasma plumes, from pulsed laser ablation of solids, play in different laser processing approaches. Then, the distinctive in-situ deposition process within surface micro/nano structuring is highlighted. Our experimental work demonstrated that the in-situ deposition during ultrafast laser surface structuring can be controlled as a localized micro-additive process to pile up secondary ordered structures, through which a unique kind of hierarchical structure with fort-like bodies sitting on top of micro cone arrays were fabricated as a showcase. The revealed laser-matter interaction mechanism can be inspiring for the development of new ultrafast laser fabrication approaches, adding a new dimension and more flexibility in controlling the fabrication of functional surface micro/nano structures. Graphical Abstract

AbstractVirus-like particles are an emerging class of nano-biotechnology with the Tobacco Mosaic Virus (TMV) having found a wide range of applications in imaging, drug delivery, and vaccine development. TMV is typically produced in planta, and, as an RNA virus, is highly susceptible to natural mutation that may impact its properties. Over the course of 2 years, from 2018 until 2020, our laboratory followed a spontaneous point mutation in the TMV coat protein—first observed as a 30 Da difference in electrospray ionization mass spectrometry (ESI–MS). The mutation would have been difficult to notice by electrophoretic mobility in agarose or SDS-PAGE and does not alter viral morphology as assessed by transmission electron microscopy. The mutation responsible for the 30 Da difference between the wild-type (wTMV) and mutant (mTMV) coat proteins was identified by a bottom-up proteomic approach as a change from glycine to serine at position 155 based on collision-induced dissociation data. Since residue 155 is located on the outer surface of the TMV rod, it is feasible that the mutation alters TMV surface chemistry. However, enzyme-linked immunosorbent assays found no difference in binding between mTMV and wTMV. Functionalization of a nearby residue, tyrosine 139, with diazonium salt, also appears unaffected. Overall, this study highlights the necessity of standard workflows to quality-control viral stocks. We suggest that ESI–MS is a straightforward and low-cost way to identify emerging mutants in coat proteins.

AbstractThe cornerstone of nanomaterial-based sensing systems is the synthesis of nanoparticles with appropriate surface functionalization that ensures their stability and determines their reactivity with organic or inorganic analytes. To accomplish these requirements, various compounds are used as additives or growth factors to regulate the properties of the synthesized nanoparticles and their reactivity with the target analytes. A different rationale is to use the target analytes as additives or growth agents to control the formation and properties of nanoparticles. The main difference is that the analyte recognition event occurs before or during the formation of nanoparticles and it is based on the reactivity of the analytes with the precursor materials of the nanoparticles (e.g., metal ions, reducing agents, and coatings). The transition from the ionic (or molecular) state of the precursor materials to ordered nanostructured assemblies is used for sensing and signal transduction for the qualitative detection and the quantitative determination of the target analytes, respectively. This review focuses on assays that are based on analyte-mediated regulation of nanoparticles’ formation and differentiate them from standard nanoparticle-based assays which rely on pre-synthesized nanoparticles. Firstly, the principles of analyte-mediated nanomaterial sensors are described and then they are discussed with emphasis on the sensing strategies, the signal transduction mechanisms, and their applications. Finally, the main advantages, as well as the limitations of this approach, are discussed and compared with assays that rely on pre-synthesized nanoparticles in order to highlight the major advances accomplished with this type of nano-sensors and elucidate challenges and opportunities for further evolving new nano-sensing strategies. Graphical abstract

Abstract Study question Re-establish the cell-cell communication of isolated oocyte and granulosa cells (GCs) to mimic the follicle microenvironment and promote the success rate of in-vitro maturation (IVM). Summary answer The Metal-phenolic network (MPN) nanoparticles-mediated cell membrane modification system was used to achieve self-assembly of GCs on the oocyte membrane and re-establishing the Oocyte-GCs communication. What is known already How to preserve the fertility of female patients of childbearing age is an important problem faced by reproductive medicine. IVM of oocytes is an important means for female fertility preservation, but the problem of oocyte maturation rate needs to be solved urgently. The Oocyte-GCs interaction determines the key events in the oocyte development and maturation. Biological materials are gradually used for IVM, but there are still significant disadvantages. MPN has been widely used for the functionalization of bacteria and cell surface due to its unique nano-network structure and good biocompatibility. Study design, size, duration The MPN nanoparticles are respectively modified on GCs and oocytes, and the GCs can be self-assembled on the surface of the oocytes to re-establish cell communication. Then explore the biosafety and cytotoxicity of MPN nanoparticles on GCs and oocytes to rule out potential impact on the secretory function of GCs, reveal the formation of gap junction and substance exchange of Oocyte-GCs, and evaluate the effects of this technology on oocyte maturation, fertilization and embryo development. Participants/materials, setting, methods The oocyte-GCs assembly could be achieved through the MPN(EGCG-Zn2+). Then MPN@GCs and MPN@Oocytes were characterized by fluorescent protein, Zeta, SEM and TEM; the cytotoxicity was assessed by Live/Dead staining, CCK-8 and flow cytometry assays. Gap junction was observed by TEM; the expression levels changes of signaling pathways for assembled oocyte and GCs were detected by single-cell RNA-seq, RT-qPCR and WB. The oocyte and embryo developmental potential were also analyzed. Main results and the role of chance We confirmed the formation of a nano-network surrounding GCs and oocytes and achieved the assembly of GCs on the surface of oocytes. Furthermore, we illustrated that MPN was non- cytotoxicity for GCs and oocytes and have no negative effect on the secretion function of GCs, indicating high biocompatibility of MPN and shows the potential application on the re-establishment of oocyte-GCs communication. Gap junctions formation and substance exchange establishment between GCs and oocytes were also proved in the study. The single-cell RNA-seq uncovered key pathways involved in oocyte-GCs interactions after the oocyte-GCs assembly. In detail, the SUMO1 ubiquitination modification of PTEN was inhibited after re-establishing cell-cell communication and decreased the localization of PTEN at the GCs membrane, which weakened its inhibition on PI3K. Higher PI3K level further up-regulated AKT level and stimulated its activation by increasing phosphorylation modification, finally improved the developmental potential and maturation rate of oocytes. The re-establishment of cell communication significantly down-regulated the P38/MAPK pathway in oocytes, including inhibited P38/MAPK expression, thereby reducing the phosphorylation of MSK1 and the activation of ATF-1, and effectively weakened the apoptosis controlled by P38/MAPK. Finally, a significantly higher fertilization and blastocyst formation rate were observed as compared to the control group. Limitations, reasons for caution Although this study has achieved promising results, there is still gap between basic research and applications, and more fundamental research should be conducted to make it a powerful tool for clinical application in the future. Wider implications of the findings This study not only provided a promising tool for establishing oocyte-GCs communication and improving oocyte maturation rate for IVM, but also showed a versatile and powerful cell-cell assembly platform for regenerative medicine including tissue engineering and organoid studies. Trial registration number not applicable

Abstract Regenerative medicine is aimed at restoring normal tissue function and can benefit from the application of tissue engineering and nano-therapeutics. In order for regenerative therapies to be effective, the spatiotemporal integration of tissue-engineered scaffolds by the native tissue, and the binding/release of therapeutic payloads by nano-materials, must be tightly controlled at the nanoscale in order to direct cell fate. However, due to a lack of insight regarding cell–material interactions at the nanoscale and subsequent downstream signaling, the clinical translation of regenerative therapies is limited due to poor material integration, rapid clearance, and complications such as graft-versus-host disease. This review paper is intended to outline our current understanding of cell–material interactions with the aim of highlighting potential areas for knowledge advancement or application in the field of regenerative medicine. This is achieved by reviewing the nanoscale organization of key cell surface receptors, the current techniques used to control the presentation of cell-interactive molecules on material surfaces, and the most advanced techniques for characterizing the interactions that occur between cell surface receptors and materials intended for use in regenerative medicine. Lay Summary The combination of biology, chemistry, materials science, and imaging technology affords exciting opportunities to better diagnose and treat a wide range of diseases. Recent advances in imaging technologies have enabled better understanding of the specific interactions that occur between human cells and their immediate surroundings in both health and disease. This biological understanding can be used to design smart therapies and tissue replacements that better mimic native tissue. Here, we discuss the advances in molecular biology and technologies that can be employed to functionalize materials and characterize their interaction with biological entities to facilitate the design of more sophisticated medical therapies.

AbstractThis highlight presents a recent technique of “Light Vaccine” for COVID-19 pandemic control. Though this technique has the germicidal advantage to SARS-CoV-2, its shortcomings will limit the wide and in-depth application. We make a perspective of real nano light vaccine, which will play an important role in the prevention and control of COVID-19. Briefly, This flow chart described the MWCNT was fabricated with strong acid and base conditional mixture in order to achieve the p-WCNT (chemical process); then modified with RNA layse and receptor binding domain (RBD) by covalent conjugation and physical absorption to get f-WCNT (functionalization); thereafter, f-WCNT was used in the multi-cell culture system interacting with SARS-CoV-2 to identify the special affinity of f-WCNT to ACE2 labeled alveolar type II cells and the inhibition capacity to SARS-CoV-2. This design, is different from the so called “light vaccine”, has the real function to against SARS-CoV-2 by local cellular temperature-rising through photothermal conversion under the near infrared (NIR) light irradiation, according to the physical and chemical nature of carbon nanotubes, and initiates the immune response consequently.

While the optical properties of localized surface plasmon resonance (LSPR) and the relaxation processes of excited hot electrons in gold nanoparticles (AuNPs) have been well understood, the phenomena that occur when AuNPs relax on solid surfaces of semiconductors or insulators remain largely unknown. Thermal energy diffusion and electron transfer are relatively simple physical processes, but the phenomena they induce are interesting because of a variety of new application developments. In this article, we introduce the fundamental aspects as well as advanced applications of several new physical phenomena induced by AuNPs-based hybrid materials with oxides or 2D materials. Localized heat can induce a great force on the surrounding medium to control mass transport, and plasmon-induced charge transfer reactions are expected to have applications in photocatalysis and solar cells. We also review increasing reports on the development of nano-optical sensors, transistors, and nano-light sources based on precisely controlled device structures utilizing AuNPs.

AbstractThe performance of Stimulated Emission Depletion (STED) microscopy depends critically on the fluorescent probe. Ultrasmall Au nanoclusters (Au NCs) exhibit large Stokes shift, and good stimulated emission response, which are potentially useful for STED imaging. However, Au NCs are polydispersed in size, sensitive to the surrounding environment, and difficult to control surface functional group stoichiometry, which results in reduced density and high heterogeneity in the labeling of biological structures. Here, this limitation is overcome by developing a method to encapsulate ultrasmall Au NCs with DNA cages, which yielded monodispersed, and monofunctionalized Au NCs that are long‐term stable. Moreover, the DNA‐caging also greatly improved the fluorescence quantum yield and photostability of Au NCs. In STED imaging, the DNA‐caged Au NCs yielded ≈40 nm spatial resolution and are able to resolve microtubule line shapes with good labeling density and homogeneity. In contrast, without caging, the Au NCs‐DNA conjugates only achieved ≈55 nm resolution and yielded spotted, poorly resolved microtubule structures, due to the presence of aggregates. Overall, a method is developed to achieve precise surface functionalization and greatly improve the monodispersity, stability, as well as optical properties of Au NCs, providing a promising class of fluorescent probes for STED imaging.

Viral diseases are considered as a global burden. The eradication of viral diseases is always a challenging task in medical research due to the high infectivity and mutation capability of the virus. The ongoing COVID-19 pandemic is still not under control even after several months of the first reported case and global spread. Neither a specific drug nor a vaccine is available for public use yet. In the pursuit of a promising strategy, carbon dots could be considered as potential nanostructure against this viral pandemic. This review explores the possibility of carbon nano-dots to combat COVID-19 based on some reported studies. Carbon dots are photoluminescent carbon nanoparticles, smaller than 10 nm in dimension with a very attractive photostable and biocompatible properties which can be surfaced modified or functionalized. These photoluminescent tiny particles have captured much attention owing to their functionalization property and biocompatibility. In response to this pandemic outbreak, this review attempts to summarize the potential use of carbon dots in antiviral therapy with particular emphasis on their probable role in the battlefront against COVID-19 including their possible biosensing applications.

To improve the mechanical and durability properties of ordinary Portland cement (OPC) mortar and paste, the incorporation of multi walled Carbon nanotubes (MWCNTs) and their dispersion procedures, functionalization, and ultra sonication have been intensively implemented. Most of the studies showed significant enhancements in the mechanical properties of OPC mortar or paste; however, others showed impairments. The recent studies regarding the implementation of MWCNTs and Glass Fibres on the mechanical properties of OPC paste and mortar were reviewed and these properties include compressive, tensile, flexural strengths, and elastic modulus. A statistical study was conducted to evaluate the mechanical properties of concrete by dispersion of MWCNT’s and Glass Fibres in the cement paste. In these composites, the percentage of MWCNTs was fixed at 0.75% by weight of cement, while the percentage of Glass Fibers was fixed at 0.25% by weight of cement. The samples were cured in tap water for 28 days at 25 + 2?C.Composite specimens were tested for compression and flexure in order to evaluate their mechanical properties such as compressive strength, flexural strength, toughness and ductility and compared with the results of plain cement control beams. The maximum deflection was found to be 0.5mm with a maximum load of 500N. The flexural strength was observed to be 1250.50 N/mm2 as per ASTM D 790 which is 20% more than the flexural strength obtained with Plain Cement+MWCNT’s and 60 to 70% more than that obtained with Plain Cement + Glass Fibres. The flexural modulus as per deflection criteria is 535.94 N/mm2 which is 10 to 20% more than that obtained of Plain Cement+MWCNT’s and Plain Cement+ Glass Fibres. The compressive strength of Plain Cement+0.75% MWCNT’s+0.25% Glass fibres was found to be 65 N/mm2 which is greater than Plain cement and Plain cement+MWCNT’s. Surface morphology by Scanning Electron microscopy of the specimens infers the clustering of glass fibres and demonstr