Littérature scientifique sur le sujet « P-type chromophores »

Chromophore conformation and protein secondary structure of biliproteins from the butterfly, Pieris brassicae, and the moth, Cerura vinula, have been investigated by absorption, circular dichroism and fluorescence spectroscopy. The chromophore of the P. brassicae protein, biliverdin IXy, has probably a cyclic-helical structure similar to that of free bile pigments of the biliverdin type. Though achiral by structure the chromophore displays strong optical activity in the native protein-bound state, but becomes inactive after urea denaturation of the protein. A minor biliprotein from P. brassicae shows absorption, circular dichroism and fluorescence spectra identical to the main biliprotein. In the biliprotein from Cerura vinula the structure of the pigment is still unknown. It has a semi-open conformation intermediate between that of the Pieris proteins and that of the phycobiliprotein, C-phycocyanin, and it retains optical activity after urea denaturation. The band widths and the size of the Stokes shifts of the fluorescence spectra indicate a high degree of conformational flexibility of the chromophores in the two Pieris pigments, and a decreased flexibility in the one from Cerura. In the biliproteins from both insects the polypeptides are low in a-helix content compared to that of phycobiliproteins. From these and earlier data, insect and algal biliproteins seem to be related only distantly if at all, but there exist also considerable differences among insect biliproteins from different species

The optical absorption and photoluminescence properties of PPE-type p-conjugated oligomers that contain a 2,2-bipyridine-5,5¢-diyl metal coordinating unit have been examined. The spectra of the free oligomers are compared with those that contain ­Re(CO)3Cl and ­Ru(bpy)22+ chromophores chelated to the bpy-diyl unit.

Porphyrins have been widely utilized as biochemical and biological functional chromophores which can operate under visible-light irradiation. Water-soluble porphyrins have been used as the drug for photodynamic therapy (PDT) and photodynamic inactivation (PDI). Although usual water-solubilization of porphyrins has been achieved by an introduction of an ionic group such as ammonium, pyridinium, sulfonate, phosphonium, or carboxyl to porphyrin ring, we proposed the preparation of water-soluble P and Sb porphyrins by modification of axial ligands. Alkyl (type A), ethylenedioxy (type E), pyridinium (type P), and glucosyl groups (type G) were introduced to axial ligands of Sb and P porphyrins to achieve water-solubilization of Sb porphyrin and P porphyrins. Here, we review their water-soluble P and Sb porphyrins from the standpoints of preparation, bioaffinity, and photosensitized inactivation.

A donor–π–acceptor type series of Triphenylamine–dicyanovinylene-based chromophores ( DPMN1–DPMN11 ) was designed theoretically by the structural tailoring of π-linkers of experimentally synthesized molecules DTTh and DTTz to exploit changes in the optical properties and their nonlinear optical materials (NLO) behaviour. Density functional theory (DFT) computations were employed to understand the electronic structures, absorption spectra, charge transfer phenomena and the influence of these structural modifications on NLO properties. Interestingly, all investigated chromophores exhibited lower band gap (2.22–2.60 eV) with broad absorption spectra in the visible region, reflecting the remarkable NLO response. Furthermore, natural bond orbital (NBO) findings revealed a strong push–pull mechanism in DPMN1–DPMN11 as donor and π-conjugates exhibited positive, while all acceptors showed negative values. Examination of electronic transitions from donor to acceptor moieties via π-conjugated linkers revealed greater linear (〈 α 〉 = 526.536–641.756 a.u.) and nonlinear ( β tot = 51 313.8–314 412.661 a.u.) response. It was noted that the chromophores containing imidazole in the second p-linker expressed greater hyperpolarizability when compared with the ones containing pyrrole. This study reveals that by controlling the type of π-spacers, interesting metal-free NLO materials can be designed, which can be valuable for the hi-tech NLO applications.

Natural dyes and pigments offer incomparable diversity of structures and functionalities, making them an excellent source of inspiration for the design and development of synthetic chromophores with a myriad of emerging properties. Formed during maturation of red wines, pyranoanthocyanins are electron-deficient cationic pyranoflavylium dyes with broad absorption in the visible spectral region and pronounced chemical and photostability. Herein, we survey the optical and electrochemical properties of synthetic pyranoflavylium dyes functionalized with different electron-donating and electron-withdrawing groups, which vary their reduction potentials over a range of about 400 mV. Despite their highly electron-deficient cores, the exploration of pyranoflavyliums as photosensitizers has been limited to the “classical” n-type dye-sensitized solar cells (DSSCs) where they act as electron donors. In light of their electrochemical and spectroscopic properties, however, these biomimetic synthetic dyes should prove to be immensely beneficial as chromophores in p-type DSSCs, where their ability to act as photooxidants, along with their pronounced photostability, can benefit key advances in solar-energy science and engineering.

Auxiliary metabolic genes (AMG) are commonly found in the genomes of phages that infect cyanobacteria and increase the fitness of the cyanophage. AMGs are often homologs of host genes, and also typically related to photosynthesis. For example, the ΦcpeT gene in the cyanophage P-HM1 encodes a putative phycobiliprotein lyase related to cyanobacterial T-type lyases, which facilitate attachment of linear tetrapyrrole chromophores to Cys-155 of phycobiliprotein β-subunits, suggesting that ΦCpeT may also help assemble light-harvesting phycobiliproteins during infection. To investigate this possibility, we structurally and biochemically characterized recombinant ΦCpeT. The solved crystal structure of ΦCpeT at 1.8-Å resolution revealed that the protein adopts a similar fold as the cyanobacterial T-type lyase CpcT from Nostoc sp. PCC7120 but overall is more compact and smaller. ΦCpeT specifically binds phycoerythrobilin (PEB) in vitro leading to a tight complex that can also be formed in Escherichia coli when it is co-expressed with genes encoding PEB biosynthesis (i.e. ho1 and pebS). The formed ΦCpeT·PEB complex was very stable as the chromophore was not lost during chromatography and displayed a strong red fluorescence with a fluorescence quantum yield of ΦF = 0.3. This complex was not directly able to transfer PEB to the host phycobiliprotein β-subunit. However, it could assist the host lyase CpeS in its function by providing a pool of readily available PEB, a feature that might be important for fast phycobiliprotein assembly during phage infection.

New complexes of osmium(III) with para - and meta-substituted benzeneseleninic acids of the type XC6H4SeO2H (X = H, p- Cl , m- Cl , p-Br, m-Br, p-Me) are reported. The compounds, of the type Os(XC6H4SeO2)3, Os(XC6H4SeO2)2Y, Os(XC6H4SeO2)Y2 and Os2(XC6H4SeO2)3Y3 (Y = Cl , Br), have been studied through spectroscopic techniques ( i.r ., far- i.r .and electronic spectra), magnetic susceptibility measurements, thermogravimetric studies and conductivity measurements. The wavelengths of the principal electronic absorption peaks have been accounted for quantitatively in terms of the crystal-field theory; the nephelauxetic parameter is indicative of an appreciable metal- ligand covalency. It is worth noting that among the present complexes the highest q values are related to the Os(XC6H4SeO2)3 derivatives in which OsO6 chromophores are present; the Dq values decrease on passing to the 1 : 2, 1 : 1.5 and 1 : 1 metal/ ligand molar ratio complexes according to the presence of chlorine- and bromine-containing chromophores . The i.r . data point to a seleninato -O,O′ coordination for all the complexes; in particular, the presence of three SeO bands with the irreducible representation A2 + 2E in the i.r . spectra of the tris derivatives suggests an octahedral configuration with D3 symmetry. All the halo complexes are polymeric octahedral with bridging halide atoms. The magnetic moment values lie in the expected range for the trisbenzeneseleninato derivatives, and they decrease on passing to the halo complexes.

With the increasing demand for reliable and efficient devices with minimal environmental impact, novel organic materials gain extreme interest in the research community and industry. In this work we present synthetic strategies towards new organic compounds as promising materials for dye sensitized solar cells (DSCs) and low-cost integrated optics along with the investigation of these materials in devices. Despite the recent hype in the research community around DSCs, increasing efficiency of DSCs is still a challenge. In principle, one promising way to obtain DSCs with significantly enhanced efficiency lies in connecting an n-type photoelectrode (i.e. n-Dye/TiO2) with a p-type one (i.e. p-Dye/NiO) leading to a tandem cell composed by two serially connected photoactive electrodes, each contributing with its own photovoltage to the total photovoltage delivered by the cell. Applying such concept could theoretically lead to organic photovoltaic devices with up to 40% overall conversion yield. One of the main limitations in p-type systems, commonly based on NiO, arises from fast charge recombination between the photoinjected hole in NiO, and the reduced dye. Therefore it is crucially important to develop p-type chromophores which could produce a long-lived charge separated state and minimize back recombination. We were thus triggered to explore new organic structures for potentially efficient chromophores for p-type devices, by considering that the intramolecular charge transfer, at the basis of efficient charge separation in donor-acceptor dyes, is strongly dependent on the electron-withdrawing ability of the acceptor. Herein we present charge separators based on organic push-pull systems of tryphenylamine donors and branched electron acceptors (SK2-3-4) based either on Dalton (SK2) or benzothidaziole acceptor groups (SK3-4) which were synthesized and characterized by steady state spectroscopic, electrochemical and computational means. All the dyes exhibit strong charge transfer bands in the visible regions with ground and excited state energetics which are favourable to the sensitization of NiO electrodes. The computational investigation revealed a clear directionality of the lowest excited state exhibiting a marked charge transfer character, shifting the electron density to the acceptor branches, an electronic situation which is favourable to the hole injection in p-type semiconductors. When tested in p-type DSCs the SK series was found capable to sensitize NiO electrodes. The charge recombination kinetics, probed by considering the charge transfer resistance at the NiO/electrolyte interface at a comparable chemical capacitance, showed that the dyes behaved similarly and that the higher Voc observed with the SK4 dye is ostensibly due to a positive shift of the valence band edge, consistent with the shift in the anodic current threshold observed in dark conditions. The second part of this work is dedicated to synthesis and characterisation of metallo-organic materials for optoelectronic devices. Optical amplification plays crucial role in the transmission and manipulation of optical signals in modern telecomunications. Nowadays amplifiers, which rely on erbium ions in a glass matrix, suffer from difficulties in fabrication and the need of high pump power densities to produce gain. Here we show a newly synthesised series of organic fully halogenated optical amplifier materials. We will compare the ability of materials with different halogen atoms in complexes with transition metals to provide population of triplets which together with the lack of CH or OH oscillators in the molecule, can be potentially used as an efficient chromophore to sensitise the erbium ions in a long-lifetime erbium complex. Finally by doping Er(FTPIP)3 with newly designed Zn and Co complexes, we aim to find differences in the lifetime emission from erbium at the important telecommunication wavelength of 1.5 μm.

Potential advances in sensing can be made by conjugated polymers includes poly(p-phenylene), poly(p-phenylene vinylene), polyfluorene, and poly(thiophene). Among the most important classes of polymers are heterocyclic polymers, such as polyimides, because polyimide nanocomposites possess exceptional mechanical strength as well as chemical, mechanical and temperature resistance. Polyimide offers the potential of providing efficient sensors through its ability to work actively. There is evidence that fluorescent polyimide is efficient at detecting hazardous pollutants. Chemical modifications of the polyimide backbone gave rise to an improved luminescence efficiency of polyimide by incorporating fluorescent chromophores. An overview of recent developments in fluorescent polyimide in sensing applications is presented in this chapter. Some of the fluorescent polyimide materials prepared from different types with surface modification (type-1: perylene tetracarboxylic dianhydride and oxydianiline) (type-2: Tetra (4-aminophenyl) porphyrin and perylenetracarboxylic dianhydride) and (type-3 2-(4,4′-diamino-4′′-triphenylamine)-5-(4-dimethylaminophenyl)-1,3,4-oxadiazole) etc. In the following section, the methods and sensing mechanism of fluorescent polyimide are described.

The bacterial reaction center of Rhodobacter Sphaeroides contains six pigments, arranged within a protein environment. These pigments act in a very concerted way to generate a remarkably efficient charge transfer which initiates the process of photosynthesis.1 The structure of the reaction center is well known, consisting of two strongly interacting bacteriochlorophyll (BChl) molecules known as the special pair (P), two accessory BChls, and two bacteriopheophytins (H) arranged in approximately C2 symmetry.2,3,4 Upon excitation of P, either directly (light absorption) or through energy transfer from the light harvesting antennae, an electron is transferred to H within about 3 ps. Although much work has been done on these types of systems, many issues remain unresolved: (1) what is the role of the accessory bacteriochlorophyll (B) in the electron transfer, (2) what is the influence of the upper excitonic state of P (Py+), (3) what is the spectrum of fluctuations (frequencies, couplings…) that describes the interaction of the reaction center chromophores with the protein environment?