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Artykuły w czasopismach na temat „Mixed metal thiolates”

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Data publikacji: 6 września 2023

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1

Alharthi, Nahed S., Haroon Khan, Fahad Jibran Siyal, Zahid Ali Shaikh, Shumaila Parveen Arain, Lienda Bashier Eltayeb i Altaf Ali Mangi. "Glutathione, Cysteine, and D-Penicillamine Role in Exchange of Silver Metal from the Albumin Metal Complex". BioMed Research International 2022 (8.08.2022): 1–10. http://dx.doi.org/10.1155/2022/3619308.

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The purpose of this study is to investigate the exchange reaction taking place among the bovine serum albumin (BSA), 5,5 ′ -dithiobis-(2-nitrobenzoic acid (ESSE), reduced glutathione, N-acetylcysteine, D-penicillamine (thiolates), and silver metal (AgI). For this purpose, stock solutions of BSA and Ellman’s reagent were prepared by dissolving 264 mg of BSA in 5 ml of reaction buffer (0.1 M KH2PO4 at pH 7.8) and 23.8 mg of ESSE in 1.0 ml of reaction buffer which were mixed together. Mixture of BSA-AgI was prepared in a separate procedure by dissolving 0.17 mg of silver nitrate in 1 ml of reaction buffer and then dissolving BSA (200 mg) in the same solution of silver nitrate. Blocking of Cys-34 of BSA with AgI was confirmed by treating different dilutions of BSA-AgI (500 μM) solutions with the solutions of ESSE (85 μM) and ES- (85 μM) and recording the spectra (300-450) with a UV-visible spectrophotometer. The chromatographed AgI-modified BSA ((BSA-S)AgI)) samples (typically 500 μM) were subsequently mixed with thiolates (reduced glutathione, N-acetylcysteine, and D-penicillamine). AgI and modified BSA (typically 500 μM each) were treated with these low molecular weight thiolates and allowed to react overnight followed by chromatographic separation (Sephadex G25). The redox reactions of AgI-modified BSA with various low molecular weight thiols revealed a mechanically important phenomenon. In the case of reduced glutathione and N-acetylcysteine, we observed the rapid release of a commensurate amount of Ellman’s anion, indicating that an exchange has taken place and low molecular weight thiols (RSH) substituted AgI species at the Cys-34 of BSA eventually forming disulfide (BSA-SSR) at Cys-34. It can be anticipated from the phase of study involving bovine serum albumin that low molecular weight thiolates (reduced glutathione and N-acetylcysteine) take off AgI which are attached to proteins elsewhere in the physiological system, making these toxic metals free for toxic action.

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2

Krüger, Thomas, Bernt Krebs i Gerald Henkel. "[Ni4(SC3H7)8Br] and[Ni4(SC3H7)8I]: Mixed Valent Nickel Thiolates with Integral and Nonintegral Metal Oxidation States". Angewandte Chemie International Edition in English 31, nr 1 (styczeń 1992): 54–56. http://dx.doi.org/10.1002/anie.199200541.

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3

R. S., Vishwanath, i Sakthivel Kandaiah. "Metal ion-containing C3N3S3coordination polymers chemisorbed to a copper surface as acid stable hydrogen evolution electrocatalysts". Journal of Materials Chemistry A 5, nr 5 (2017): 2052–65. http://dx.doi.org/10.1039/c6ta08469a.

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We present here the preparation of a novel chemically immobilized mixed-metal ion-containing triazine thiolate (C₃N₃S₃) polymer electrocatalyst (M–TCA) on a copper (Cu) surface.

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4

Seela, Jeffrey L., Kirsten Folting, Ru Ji Wang, John C. Huffman, George Christou, Hsiu Rong Chang i David N. Hendrickson. "Manganese(III) thiolate chemistry: new structural types, including the first mixed-valence metal thiolate". Inorganic Chemistry 24, nr 26 (grudzień 1985): 4454–56. http://dx.doi.org/10.1021/ic00220a005.

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5

Vazquez, F., i M. Vasák. "Comparative 113Cd-n.m.r. studies on rabbit 113Cd7-, (Zn1,Cd6)- and partially metal-depleted 113Cd6-metallothionein- 2a". Biochemical Journal 253, nr 2 (15.07.1988): 611–14. http://dx.doi.org/10.1042/bj2530611.

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Rabbit 113Cd7-metallothionein-2a (MT) contains two metal-thiolate clusters of three (cluster B) and four (cluster A) metal ions. The 113Cd-n.m.r. spectrum of 113Cd6-MT, isolated from 113Cd7-MT upon treatment with EDTA, is similar to that of 113Cd7-MT, but the cluster B resonances are lower in intensity, suggesting its co-operative metal depletion. (Zn1,113Cd6)-MT, formed upon addition of the Zn(II) ions to 113Cd6-MT, shows 113Cd-n.m.r. features characteristic of cluster B populations containing both Cd(II) and Zn(II) ions. The overall intensity gain of the mixed cluster B resonances per Cd as to those in 113Cd6- and 113Cd7-MT suggests a stabilization effect of the bound Zn(II) ions upon the previously established intramolecular 113Cd exchange within this cluster.

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6

Salorinne, Kirsi, Renee W. Y. Man, Paul A. Lummis, Maryam Sabooni Asre Hazer, Sami Malola, Jacky C. H. Yim, Alex J. Veinot i in. "Synthesis and properties of an Au6 cluster supported by a mixed N-heterocyclic carbene–thiolate ligand". Chemical Communications 56, nr 45 (2020): 6102–5. http://dx.doi.org/10.1039/d0cc01482f.

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7

Grützmacher, Hansjörg, Matthias Steiner, Hans Pritzkow, Laszlo Zsolnai, Gottfried Huttner i Angelika Sebald. "Mixed amide thiolate complexes of zinc with low coordination number at the metal atom". Chemische Berichte 125, nr 10 (październik 1992): 2199–207. http://dx.doi.org/10.1002/cber.19921251006.

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8

Sanambatla, Vanitha, Sathish Kumar Nara, Balaji Hari, Varada Reddy Ammireddy i Saritha Nimmakayala. "Antimicrobial and antioxidant studies of Schiff base, 2-(2-hydroxy-2-methyl-1-phenylpropylidene) hydrazine carbothioamide and its mixed ligand cd (II) complexes". Journal of medical pharmaceutical and allied sciences 11, nr 1 (30.01.2022): 4470–76. http://dx.doi.org/10.55522/jmpas.v11i1.2451.

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New mononuclear mixed ligand Cadmium(II) complexes of the type [Cd(L)(diimine)] (1,2) [where L = 2-(2-hydroxy-2-methyl-1-phenylpropylidene)hydrazinecarbothioamide; diimine = 2,2’-bipyridine (1), 1,10-phenanthroline (2)] have been synthesized and characterized by spectroscopic techniques such as FT-IR, UV-Visible, and1H and 13CNMR Spectroscopy. From the investigations of spectral data, it is evident that the heterocyclic bases (2,2’-bipyridine and 1,10-Phenanthroline) act as neutral bidentate ligand coordinating to the metal ion through two nitrogen donor atoms addition to azomethane nitrogen, thiolate Sulphur, and hydroxyl oxygen in the Schiff base ligand. The synthesized Schiff base metal chelates have been screened for their anti-microbial activities using the agar well diffusion method against different selected types of bacteria and fungi in addition to antioxidant activity. The prepared Schiff base ligand and its metal complexes exhibited good antimicrobial and antioxidant activities. The antibacterial and antifungal efficacy of Complex-1 was higher than that of all the prepared compounds. In the case of antioxidant activity, Complex-2 has stronger scavenging activity among them. Keywords: Cd (II) metal complexes, 2,2’-Bipyridine, 1,10-Phenanthroline, Antimicrobial activities.

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9

Dean, Philip A. W., Jagadese J. Vittal i Yuyang Wu. "Synthesis, multinuclear magnetic resonance spectra, and chemistry of some complexes [(μ-SR)6(MX)4]2− (R = alkyl; M = Zn or Cd; X = Cl, Br, or I) and the X-ray structural analysis of (Et4N)2[(μ-SPri)6(CdBr)4]". Canadian Journal of Chemistry 70, nr 3 (1.03.1992): 779–91. http://dx.doi.org/10.1139/v92-103.

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The self-assembly method has been used to prepare a wide range of new adamantane-like anions of the type [(μ-SR)6(MX)4]2− (M = Zn or Cd; R = alkyl or benzyl; X = Cl, Br, or I) as their Et4N+ salts. Metal (111 or 113Cd) NMR data have been measured for the cadmium complexes, and also for many of the possible mixed-metal complexes [(μ-SR)6(CdX)n(ZnX)4−n]2−. In the complexes with mixed metals, the effects of Zn substitution on the metal chemical shifts are generally larger for the alkyl- and benzyl-thiolate complexes than for related benzenethiolate complexes. However, for [(μ-SPri)6(CdX)n(CdX′)4−n]2− (X/X′ = Cl/Br, Cl/I, or Br/I), substituent effects are no larger than found in some PhS−-bridged complexes. The reaction of [(μ-SPri)6(CdX)4]2− (X = Cl, Br, or I) with E′8 (E′ = S or Se) in CH2Cl2 gives [Cd4(μ4-E′) (μ-SPri)12(CdX)4]2− as the major species detectable by metal, 13C, and, where applicable, 77Se NMR. However, the reaction does not occur stoichiometrically. The compound (Et4N)2[(μ-SPri)6(CdBr)4] crystallizes in the monoclinic space group P21/c with cell dimensions a = 24.079(3) Å, b = 11.365(2) Å, c = 22.561(3) Å, β = 113.89(1), and Z = 4. The structure was refined to R(Rw) = 0.0663(0.0703) with the use of 2669 unique data with I > 2.5σ(I). The anion contains an adamantane-type (μ2-S)6Cd4 cage composed of a nearly regular Cd4 tetrahedron and a distorted S6 octahedron, the irregularity of which is caused by 1,3-interactions of the substituent groups on the sulfur atoms. The axial or equatorial dispositions of the six alkyl groups in the four fused M3S3 rings are [aae, aae, aee, aee]. For the zinc-group elements, this is the first example of an adamantane-like (μ-Salkyl)6M4 cage that has been characterized crystallographically. Keywords: cadmium complex, cadmium-111/113 NMR, thiolate complex, X-ray analysis, zinc complex.

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10

Adams, H., N. A. Bailey, M. N. Bancroft, A. P. Bisson i M. J. Morris. "Phosphido-bridged dimolybdenum complexes with sulfide and thiolate ligands as precursors to mixed-metal clusters". Journal of Organometallic Chemistry 542, nr 1 (wrzesień 1997): 131–40. http://dx.doi.org/10.1016/s0022-328x(97)00297-0.

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11

Stephan, Hans-Oscar, Gerald Henkel i Mercouri G. Kanatzidis. "[Fe3Cu(SPri)6Cl3] 2−: a novel mixed-metal thiolate complex with a ‘truncated’ adamantane-like structure". Chemical Communications, nr 1 (1997): 67–68. http://dx.doi.org/10.1039/a606962b.

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12

Kuwata, Shigeki, Yasushi Mizobe i Masanobu Hidai. "Reactions of a diruthenium complex bridged by disulfide and thiolate ligands with zero-valent noble metal complexes. Syntheses of mixed metal-sulfide-thiolate clusters containing trinuclear PtRu2 and tetranuclear Pd2Ru2 cores". Journal of the American Chemical Society 115, nr 18 (wrzesień 1993): 8499–500. http://dx.doi.org/10.1021/ja00071a090.

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13

Müller, Arnd, i Gerald Henkel. "[Ni3Se(o-C6H4{CH2Se}2)3]2- und [Ni4(SeiC3H7)8], die ersten höherkernigen NickeI(II)-Komplexe mit vollständiger Selen-Ligandensphäre [Ni3Se(o-C6H4{CH2Se}2)3]2- and [Ni4(SeiC3H7)8], the First Polynuclear Nickel(II) Complexes with Complete Selenium Ligand Spheres". Zeitschrift für Naturforschung B 52, nr 12 (1.12.1997): 1501–9. http://dx.doi.org/10.1515/znb-1997-1211.

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Reaction of nickel(II) chloride with disodium ο-xylenediselenolate in methanol yields the trinuclear mixed selenide-selenolate complex anion [Ni3Se(ο-C6H4{CH2Se}2)3]2- (3) which was isolated both as tetramethylammonium and mixed sodium/tetraethylammonium salt of formula [Me4N]2[Ni3Se(ο-C6H4{CH2Se}2)3] · MeOH (1) and [Et4N]3Na[Ni3Se-(ο-C6H4{CH2Se}2)3]2- · 3MeOH · 3H2O (2), respectively. Crystals of 1 are triclinic, space group P1̄, a = 9.065(2), b = 13.281(3); c = 18.019(4) Å , α = 92.81(2), β = 97.55(2), γ = 105.09(2)° and Z = 2. 2 crystallizes in the rhom bohedral space group R3c with a = 20.305(5), c = 41.709(9) Å and Z = 6. The structures were refined to R = 0.0705 (1) and 0.0794 (2), respectively. Both compounds contain the complex anion [Ni3Se- (ο-C6H4{CH2Se}2)3]2- (3), which possesses the same principal structural features as the corresponding thiolato derivatives. Reaction of nickel(II) chloride with sodium iso-propane selenolate in methanol leads to the cyclic tetranuclear complex [Ni4(SeiC3H7)8] (4), which crystallizes in the monoclinic space group P2/n with a = 13.161(3), b = 10.464(2), c = 14.603(2) Å , β = 94.42(1)° and Z = 2. The structure refinement converged to R = 0.0541. 4 is isostructural with the corresponding thiolato compound. The introduction of selenium instead of sulfur ligands reduces the midpoint potential of the reversible metal-centered oxidation from +595 to +285 mV.

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14

Grisoli, Pietro, Lorenzo De Vita, Chiara Milanese, Angelo Taglietti, Yuri Diaz Fernandez, Margaux Bouzin, Laura D’Alfonso i in. "PVA Films with Mixed Silver Nanoparticles and Gold Nanostars for Intrinsic and Photothermal Antibacterial Action". Nanomaterials 11, nr 6 (25.05.2021): 1387. http://dx.doi.org/10.3390/nano11061387.

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PVA films with embedded either silver nanoparticles (AgNP), NIR-absorbing photothermal gold nanostars (GNS), or mixed AgNP+GNS were prepared in this research. The optimal conditions to obtain stable AgNP+GNS films with intact, long lasting photothermal GNS were obtained. These require coating of GNS with a thiolated polyethylene glycol (PEG) terminated with a carboxylic acid function, acting as reticulant in the film formation. In the mixed AgNP+GNS films, the total noble metal content is <0.15% w/w and in the Ag films < 0.025% w/w. The slow but prolonged Ag+ release from film-embedded AgNP (8–11% of total Ag released after 24 h, in the mixed films) results in a very strong microbicidal effect against planktonic Escherichia coli and Staphylococcus aureus bacterial strains (the release of Au from films is instead negligible). Beside this intrinsic effect, the mixed films also exert an on-demand, fast hyperthermal bactericidal action, switched on by NIR laser irradiation (800 nm, i.e., inside the biotransparent window) of the localized surface plasmon resonance (LSPR) absorption bands of GNS. Temperature increases of 30 °C are obtained using irradiances as low as 0.27 W/cm2. Moreover, 80–90% death on both strains was observed in bacteria in contact with the GNS-containing films, after 30 min of irradiation. Finally, the biocompatibility of all films was verified on human fibroblasts, finding negligible viability decrease in all cases.

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15

Joy, Md Tuhinur Rahman, Jagodish Chandra Sarker i Shariff Enamul Kabir. "The chemistry of rhenium and manganese carbonyl complexes bearing heterocyclic thiolate ligands: Mono‒, di‒, tri‒, and tetranuclear complexes". Journal of Bangladesh Academy of Sciences 47, nr 1 (27.06.2023): 1–21. http://dx.doi.org/10.3329/jbas.v47i1.66442.

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This article provides an overview of the rich chemistry of rhenium and manganese decacarbonyls, M2(CO)10 (M = Re, Mn) and their acetonitrile derivatives [M2(CO)8(NCMe)2] as precursors for synthesis of new di‒, tri‒ and tetranuclear complexes derived from a wide range of heterocyclic thiols such as pyridine-2-thiol, pyrimidine-2-thiol, tetrahydropyrimidine-2-thiol, 2-mercapto-1-methylimidazole, benzimidazole-2-thiol etc. A comparative study of the reactivities of these complexes with various mono and bidentate ligands is also the subject of this review. In some instances, the structural aspects of the complexes are also discussed. The applications of these complexes as precursors for the synthesis of a wide variety of mixed-metal cluster complexes are highlighted. J. Bangladesh Acad. Sci. 47(1); 1-21: June 2023

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16

Novara, Chiara, Alessandro Chiadò, Niccolò Paccotti, Silvia Catuogno, Carla Lucia Esposito, Gerolama Condorelli, Vittorio De Franciscis, Francesco Geobaldo, Paola Rivolo i Fabrizio Giorgis. "SERS-active metal-dielectric nanostructures integrated in microfluidic devices for label-free quantitative detection of miRNA". Faraday Discussions 205 (2017): 271–89. http://dx.doi.org/10.1039/c7fd00140a.

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In this work, SERS-based microfluidic PDMS chips integrating silver-coated porous silicon membranes were used for the detection and quantitation of microRNAs (miRNAs), which consist of short regulatory non-coding RNA sequences typically over- or under-expressed in connection with several diseases such as oncogenesis. In detail, metal–dielectric nanostructures which provide noticeable Raman enhancements were functionalized according to a biological protocol, adapted and optimized from an enzyme-linked immunosorbent assay (ELISA), for the detection of miR-222. Two sets of experiments based on different approaches were designed and performed, yielding a critical comparison. In the first one, the labelled target miRNA is revealed through hybridization to a complementary thiolated DNA probe, immobilized on the silver nanoparticles. In the second one, the probe is halved into shorter strands (half1 and half2) that interact with the complementary miRNA in two steps of hybridization. Such an approach, taking advantage of the Raman labelling of half2, provides a label-free analysis of the target. After suitable optimisation of the procedures, two calibration curves allowing quantitative measurements were obtained and compared on the basis of the SERS maps acquired on the samples loaded with several miRNA concentrations. The selectivity of the two-step assay was confirmed by the detection of target miR-222 mixed with different synthetic oligos, simulating the hybridization interference coming from similar sequences in real biological samples. Finally, that protocol was applied to the analysis of miR-222 in cellular extracts using an optofluidic multichamber biosensor, confirming the potentialities of SERS-based microfluidics for early-cancer diagnosis.

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17

Hossain, Md Munkir, Hsiu-Mei Lin i Shin-Guang Shyu. "Thiolate Ligand Transfer from Metallothiolates to Phosphido-Bridged Heterobimetallic Compounds: C−S Bond Cleavage in Benzenethiol and Formation of a Mixed-Metal Trinuclear Compound". Organometallics 22, nr 16 (sierpień 2003): 3262–70. http://dx.doi.org/10.1021/om030131j.

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18

Rosenhein, Laurence D., i John W. McDonald. "Synthesis of cis- and trans-Fe(CyNC)4(SPh)2: bis-thiolate precursors of the mixed-metal complex, (CyNC)4Fe(SPh)2Mo(CO)4". Journal of Organometallic Chemistry 345, nr 1-2 (maj 1988): 143–49. http://dx.doi.org/10.1016/0022-328x(88)80243-2.

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19

Pyrak, Edyta, Kacper Jędrzejewski, Aleksandra Szaniawska i Andrzej Kudelski. "Attachment of Single-Stranded DNA to Certain SERS-Active Gold and Silver Substrates: Selected Practical Tips". Molecules 26, nr 14 (13.07.2021): 4246. http://dx.doi.org/10.3390/molecules26144246.

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Layers formed from single-stranded DNA on nanostructured plasmonic metals can be applied as “working elements” in surface–enhanced Raman scattering (SERS) sensors used to sensitively and accurately identify specific DNA fragments in various biological samples (for example, in samples of blood). Therefore, the proper formation of the desired DNA layers on SERS substrates is of great practical importance, and many research groups are working to improve the process in forming such structures. In this work, we propose two modifications of a standard method used for depositing DNA with an attached linking thiol moiety on certain SERS-active structures; the modifications yield DNA layers that generate a stronger SERS signal. We propose: (i) freezing the sample when forming DNA layers on the nanoparticles, and (ii) when forming DNA layers on SERS-active macroscopic silver substrates, using ω-substituted alkanethiols with very short alkane chains (such as cysteamine or mercaptopropionic acid) to backfill the empty spaces on the metal surface unoccupied by DNA. When 6-mercapto-1-hexanol is used to fill the unoccupied places on a silver surface (as in experiments on standard gold substrates), a quick detachment of chemisorbed DNA from the silver surface is observed. Whereas, using ω-substituted alkanethiols with a shorter alkane chain makes it possible to easily form mixed DNA/backfilling thiol monolayers. Probably, the significantly lower desorption rate of the thiolated DNA induced by alkanethiols with shorter chains is due to the lower stabilization energy in monolayers formed from such compounds.

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20

Ciriano, Miguel A., Luis A. Oro, Jesús J. Pérez-Torrente, Antonio Tiripicchio i Marisa Tiripicchio-Camellini. "Synthesis of mixed-metal trinuclear complexes. X-Ray crystal structure of [(cod)2Rh2(µ3-C7H4NS2)2AgO2ClO2](cod = cyclo-octa-1,5-diene; C7H4NS2= benzothiazole-2-thiolate)". J. Chem. Soc., Chem. Commun., nr 23 (1986): 1737–38. http://dx.doi.org/10.1039/c39860001737.

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Pasynskii, A. A., I. V. Skabitsky, Yu V. Torubaev, S. G. Sakharov i S. S. Shapovalov. "Synthesis and structure of mixed-metal thiolate complex Cp′Cr(CO)2(μ-SBu)Pt(PPh3)2: Side-on-coordination of Cr–S double bond with platinum". Journal of Organometallic Chemistry 694, nr 21 (październik 2009): 3373–75. http://dx.doi.org/10.1016/j.jorganchem.2009.06.043.

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Sellmann, Dieter, Susanne Emig, Frank W. Heinemann i Falk Knoch. "Übergangsmetallkomplexe mit Schwefelliganden, CXXXIII [1]. Synthese, Struktur und Eigenschaften neuer FeII-Komplexe mit [FeN2S2]-Gerüsten / Transition Metal Complexes with Sulfur Ligands, CXXXIII [1]. Synthesis, Structure, and Properties of New FeII Complexes with [Fe2N2S2] Cores". Zeitschrift für Naturforschung B 53, nr 12 (1.12.1998): 1461–74. http://dx.doi.org/10.1515/znb-1998-1208.

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Abstract In order to obtain suitable precursors for iron complexes that model the reactivity of the active sites of nitrogenases, the coordination chemistry of the [Fe(′N2H2S2′)] fragment was systematically investigated(′N2H2S2′2- = 1,2-ethanediamine-N,N′-bis(2-benzenethiolate)(2-)). One-pot reactions of FeCl2 -4H2O with the tetradentate amine-thiolate ligand ′N2H2S2′2- and CO, PR3 or P(OR)3 yielded the complexes [Fe(CO)2(′N2H2S2′)] (1), [Fe(CO)(PR3)(′N2H2S2′)] (R = Et (2), Pr (3), Bu (4)), [Fe(PMe3)2 (′N2H2S2′)] (7), [Fe(dppe)(′N2H2S2′)] (8 , dppe = 1,2- bis(diphenylphosphine)ethane), and [Fe(P(ÖR)3)2(′N2H2S2′)l (R = Me (9), Pr (10)). Mixed phosphane/phosphite complexes [Fe(PMe3)(P(OR)3)(′N2H2S2′)] (R = Me (11), Pr (12)) were synthesized by PMe3/P(OPr)3 exchange of the labile complexes [Fe(PMe3 )2(′N2H2S2′)] (7) and [Fe(P(OPr)3)2(′N2H2S2′)] (10). The [Fe(CO)(PR3)(′N2H2S2′)l complexes 3 and 4 also resulted from 1 and PR3 by photochemical CO substitution. They exhibit characteristic low-frequency v (CO) bands ( ≈1925 cm-1), and their remaining CO ligand proved photolytically inert. Reaction of 3 or 4 with NOBF4 yielded the dinuclear NO complex [Fe(NO)(′N2HS2′)]2 (6 ) which contains two amide functions. Contrary to expectations, [Fe(PR3)2(′N2H2S2′)l complexes could not be obtained with monodentate phosphanes other than PMe3. The corresponding N-methylated ligand ′N2Me2S2,2- yielded only the complexes [Fe(CO)2 (′N2Me2S2′)] (15) and [Fe(′N2Me2S2′)] (16). X-ray structure analyses of complexes 7, 8 -MeOH, 3, [Fe(CO)(dppm)(′N2H2S2 ′)]·0,5 THF (5 ·0,5THF, dppm = bis(diphenylphosphino)methane), and 12·0,5′N2 H2S2 ′-H2 confirm the pseudo-octahedral coordination of the Fe centers by two trans-S and two cis-N donors and two c/s-coligands. The structural data further suggest that the unexpected instability of the [Fe(PR3)2 (′N1H2S2′)] complexes is not caused by steric but by electronic effects. The cyclic voltammograms and the reactivity of the [Fe(L)(L′)(′N2H2S2′)] complexes corroborate this assumption. The oxidation behaviour of the [Fe(L)(L′)(′N2H2S2′)] complexes depends critically on the coligands L and L′. Reaction of 1 with dioxygen leads to oxidative dehydrogenation of the ′N2H2S2′2- ligand and yields the dinuclear Schiff-Base complex [Fe(′gma′ )]2 (′gma′2- = glyoxal-bis(2- mercaptoanil)(2-)). In contrast, oxidation of [Fe(CO)(PR3)(′N2H2S2′)], [Fe(PR3)2 (′N2H2S2′)] and [Fe(P(OR)3)2 (′N2H2S2)] complexes by dioxygen occurs metal-centered and gives the Fe(IV) complexes [Fe(PR3)(′N2S2′)] (R = Me, Pr), [Fe(P(OR)3)(′N2S2′)] (R = Me) and [Fe(′N2S2′)]2 that contain the tetraanionic thiolate-amide ligand ′N2S2′4-.

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Börner, Martin, Laura Blömer, Marcus Kischel, Peter Richter, Georgeta Salvan, Dietrich R. T. Zahn, Pablo F. Siles i in. "Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands". Beilstein Journal of Nanotechnology 8 (5.07.2017): 1375–87. http://dx.doi.org/10.3762/bjnano.8.139.

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The chemisorption of magnetically bistable transition metal complexes on planar surfaces has recently attracted increased scientific interest due to its potential application in various fields, including molecular spintronics. In this work, the synthesis of mixed-ligand complexes of the type [NiII 2L(L’)](ClO4), where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand and L’ is a ω-mercapto-carboxylato ligand (L’ = HS(CH2)5CO2 − (6), HS(CH2)10CO2 − (7), or HS(C6H4)2CO2 − (8)), and their ability to adsorb on gold surfaces is reported. Besides elemental analysis, IR spectroscopy, electrospray ionization mass spectrometry (ESIMS), UV–vis spectroscopy, and X-ray crystallography (for 6 and 7), the compounds were also studied by temperature-dependent magnetic susceptibility measurements (for 7 and 8) and (broken symmetry) density functional theory (DFT) calculations. An S = 2 ground state is demonstrated by temperature-dependent susceptibility and magnetization measurements, achieved by ferromagnetic coupling between the spins of the Ni(II) ions in 7 (J = +22.3 cm−1) and 8 (J = +20.8 cm−1; H = −2JS1S2). The reactivity of complexes 6–8 is reminiscent of that of pure thiolato ligands, which readily chemisorb on Au surfaces as verified by contact angle, atomic force microscopy (AFM) and spectroscopic ellipsometry measurements. The large [Ni2L] tail groups, however, prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported.

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Adams, Harry, Neil A. Bailey, Sally R. Gay, Louise J. Gill, Trevor Hamilton i Michael J. Morris. "Dimolybdenum complexes with sulfide and thiolate ligands as precursors to mixed-metal clusters: crystal structure of [Mo2Ru2(µ3-S)2(µ-SPri)2(CO)4(η-C5H5)2]". J. Chem. Soc., Dalton Trans., nr 12 (1996): 2403–7. http://dx.doi.org/10.1039/dt9960002403.

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Grzedowski, Adrian, i Dan Bizzotto. "(Invited) Towards a FRET Based DNA SAM Biosensor for Detection of Nucleic Acids". ECS Meeting Abstracts MA2022-01, nr 45 (7.07.2022): 1882. http://dx.doi.org/10.1149/ma2022-01451882mtgabs.

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Rapid and sensitive detection of nucleic acids is an essential tool in many medical and clinical settings, that allows for fast diagnosis of bacterial and viral infections. Here, we present a DNA FRET-based biosensor to detect a hybridization event on a DNA SAM on gold surface. The monolayer was prepared by a potential assisted thiol exchange deposition, which provides better control over the surface coverage and its uniformity1. Our approach relies on a change in FRET (Förster Resonance Energy Transfer) signal caused by variations in distance between fluorophores. FRET imaging is a well-known, very sensitive technique, used commonly in many areas of chemistry and microbiology. FRET signal depends strongly on the distance between an acceptor and a donor fluorophore. It is an excellent tool to analyze small changes in DNA distance between adjacent strands and the surface2. Metal quenching also plays a major role, since fluorescence is strongly dependent on the distance from the metal surface3, which is an efficient quencher. Fluorophores, both acceptor and donor, are quenched significantly by the gold surface, this however, decreases substantially as the distance increases between the surface and fluorophore. As DNA is binding its complementary strands, the distance between the surface and the fluorophore labelled end increases. Using a self-assembly property of thiols on gold surface, we show that mixed ssDNA SAM composed of two strands of thiolated ssDNA, each labelled with a different FRET fluorophore, gives an 8-to-10-fold signal enhancement, upon DNA hybridization (see figure 1). Binding of a complementary strand rigidifies the adsorbed DNA structure, and as a result we observe the increase in signal due to weaker gold quenching and shorter distance between FRET participating fluorophores. Moreover, by utilizing a single crystal electrode, we can study different surface concentration regimes and fluorescence signal increases, based on surface crystallography and the electrode potential. (1) Leung, K. K.; Gaxiola, A. D.; Yu, H.-Z.; Bizzotto, D. Tailoring the DNA SAM Surface Density on Different Surface Crystallographic Features Using Potential Assisted Thiol Exchange. Electrochim. Acta 2018, 261, 188–197. https://doi.org/https://doi.org/10.1016/j.electacta.2017.12.114. (2) Verhaven, A.; Doneux, T.; Bizzotto, D. Application of FRET Microscopy to the Study of the Local Environment and Dynamics of DNA SAMs on Au Electrodes. Langmuir 2018, 34 (49), 14802–14810. https://doi.org/10.1021/acs.langmuir.8b02131. (3) Casanova-Moreno, J.; Yu, Z. L.; Massey-Allard, J.; Ditchburn, B.; Young, J. F.; Bizzotto, D. Luminescence in Electrochemistry; Springer International Publishing: Cham, 2017; pp 21– 77. Figure 1

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Tremel, Wolfgang, Bernt Krebs, Klaus Greiwe, Wolfgang Simon, Hans-Oscar Stephan i Gerald Henkel. "[Mn(SPh)3Cl]2-, [Mn(SPh)3Br]2-, [Mn(SePh)4]2-, [Mn(TePh)4]2-, and [Co4(SPh)6Cl4]2-: New Mixed Halide/Thiolate and Chalcogenolate Complexes of Manganese and Cobalt". Zeitschrift für Naturforschung B 47, nr 11 (1.11.1992): 1580–92. http://dx.doi.org/10.1515/znb-1992-1112.

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The reactions of 1:1:1 molar ratio mixtures of NaSPh/MnCl2/Et4NBr and NaSPh/CoCl2/ Et4NCl in methanol afford the compounds [Et4N]4[Mn(SPh)3Br][Mn(SPh)3Cl] (1) and [Et4N]2[Co4(SPh)6Cl4] · MeCN (2), respectively, with the following crystal data: a = 14.408(5), b = 13.788(4), c = 17.984(5) Å, β = 90.16(2)°, space group P21/c and Ζ = 4 for 1, and a = 21.976(4), b = 13.081(2), c = 22.012(4) Å, β = 105.48(1)°, space group P 21/c for 2. The structures were refined to R values of 0.049 and 0.037, respectively. Crystals of 1 contain both of the paramagnetic (S = 5/2) mononuclear anions [Mn(SPh)3Br]2- (3 a) and [Mn(SPh)3Cl]2- (3b). The anions 3 a and 3 b are superimposed in an averaged unit cell and thus occupy crystallographically equivalent sites, the positions of the chlorine and bromine atoms being unresolved. The monohalide species are distributed statistically over 93% of the total anion positions. The remaining 7% are occupied by the dihalide species [Mn(SPh)2Br2]2- (4a) and [Mn(SPh)2BrCl]2- (4b) in equal amounts. In all these cases the metal atoms exhibit a distorted tetrahedral stereochemistry. In crystals of 2 [Co4(SPh)6Cl4]2- anions (5) are observed which feature a {Co4S6Cl4} core consisting of a distorted (D2d) Co4 tetrahedron inscribed in a moderately irregular S6 octahedron defined by bridging S atoms of an adamantane type cage. The four chlorine atoms each bind to different Co atoms and define an outer Cl4 tetrahedron, such that the overall symmetry of the {Co4S6Cl4} core comes close to Td. The results presented show that [M3(SPh)3Hal6]3- type species reported for M = Fe are not as readily formed for M = Mn and Co in methanolic solution, where other species are found instead. Physical properties such as solid state susceptibilities and 1H NMR spectra confirm the identity of 1 and 2. Reactions of 4:1:2 molar ratio mixtures of NaSePh/MnCl2/Et4NCl and NaTePh/MnCl2/Et4NCl in methanol lead to [Et4N]2[Mn(SePh)4] (6) and [Et4N]2[Mn(TePh)4] (7). Both compounds crystallize in the monoclinic space group P21/n with a = 16.162(4), b = 15.323(4), c = 16.949(4) Å, β = 91.28(2)°, Z = 4 for 6, and a = 16.367(6), b = 15.641(7), c = 17.220(7) Å, β = 92.00(3)°, Z = 4 for 7. Their structures were refined to R = 0.077 and 0.026, respectively. Four benzeneselenolate and benzenetellurolate ligands provide a slightly distorted tetrahedral coordination about the Mn(II) center for 6 and 7, respectively. The Mn–Se and Mn–Te distances average 2.567 and 2.742 Å, the Se– Mn– Se and Te–Mn–Te angles range from 99.1(1) to 124.2(1) and from 94.7(1) to 127.0(1)°, respectively.

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SEELA, J. L., K. FOLTING, R. J. WANG, J. C. HUFFMAN, G. CHRISTOU, H. R. CHANG i D. N. HENDRICKSON. "ChemInform Abstract: Manganese(III) Thiolate Chemistry: New Structural Types, Including the First Mixed-Valence Metal Thiolate." Chemischer Informationsdienst 17, nr 16 (22.04.1986). http://dx.doi.org/10.1002/chin.198616286.

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