A Versatile Route to Acyl (MIDA)Boronates.

A modular approach to highly functional acyl (MIDA)boronates is described. It involves the generation of the hitherto unknown radical derived from acetyl (MIDA)boronate and its capture by various alkenes, including electronically unbiased, unactivated alkenes. In contrast to the anion of acetyl (MIDA)boronate, which has not so far been employed in synthesis, the corresponding radical is well behaved and readily produced from the novel α-xanthyl acetyl (MIDA)boronate. This shelf-stable, easily prepared solid is a convenient acyl (MIDA)boronate transfer agent that provides a direct entry to numerous otherwise inaccessible structures, including latent 1,4-dicarbonyl derivatives that can be transformed into B(MIDA) substituted pyrroles and furans. A competition experiment indicated the acyl (MIDA)boronate substituted radical to be more stable than the all-carbon acetonyl radical but somewhat less reactive in additions to alkenes.

Patterning at the Resolution Limit of Commercial Electron Beam Lithography.

It has been long known that low molecular weight resists can achieve a very high resolution, theoretically close to the probe diameter of the electron beam lithography (EBL) system. Despite technological improvements in EBL systems, the advances in resists have lagged behind. Here we demonstrate that a low-molecular-mass single-source precursor resist (based on cadmium(II) ethylxanthate complexed with pyridine) is capable of a achieving resolution (4 nm) that closely matches the measured probe diameter (∼3.8 nm). Energetic electrons enable the top-down radiolysis of the resist, while they provide the energy to construct the functional material from the bottom-up─unit cell by unit cell. Since this occurs only within the volume of resist exposed to primary electrons, the minimum size of the patterned features is close to the beam diameter. We speculate that angstrom-scale patterning of functional materials is possible with single-source precursor resists using an aberration-corrected electron beam writer with a spot size of ∼1 Å.

Some Aspects of α-(Acyloxy)alkyl Radicals in Organic Synthesis.

The preparation and use of α-(acyloxy)alkyl xanthates to generate and capture α-(acyloxy)alkyl radicals is briefly reviewed. Their inter- and intramolecular additions to both activated and unactivated, electronically unbiased, alkenes, and to (hetero)aromatic rings, as well as their radical allylation and vinylation reactions are described. Application to the total synthesis of two 4-hydroxytetralone natural products is also presented.

A Modular Access to 1,2- and 1,3-Disubstituted Cyclobutylboronic Esters by Consecutive Radical Additions.

A modular approach to substituted cyclobutylboronic esters is described. It proceeds by successive intermolecular radical additions of xanthates to pinacolato 1-cyclobutenylboronate and to pinacolato bicyclo[1.1.0]but-1-ylboronate. Success hinges on tuning the stability of the α-boryl radical by exploiting the stabilizing influence of the trivalent boronic ester and the slightly destabilizing cyclobutane, which increases the σ-character of the radical. Reductive removal of the xanthate group finally provides a range of 1,2- and 1,3-disubstituted cyclobutylboronic esters. The contrast with cyclopropylboronic esters is striking, since the strong destabilization by the highly strained cyclopropane ring allows the first radical addition to take place but not the second. Furthermore, the first adducts are geminal xanthyl boronic esters that can be converted into cyclobutanones. This chemistry furnishes cyclobutylboronic esters that would be quite difficult to obtain otherwise and thus complements existing methods.

Grafting of Polymer Brushes from Xanthate-Functionalized Silica Particles.

Monodisperse silica particles (SiPs) were surface-modified with a newly designed silane coupling agent comprising a triethoxysilane and an alkyl halide, namely, 6-(triethoxysilyl)hexyl 2-bromopropionate, which was further treated with potassium O-ethyl dithiocarbonate (PEX) to immobilize xanthate molecules on the particle surfaces. Surface-initiated macromolecular design via interchange of xanthates (MADIX) polymerization of vinyl acetate (VAc) was conducted with the xanthate-functionalized SiPs. The polymerization was well controlled and produced SiPs coated with poly(vinyl acetate) (PVAc) with a well-defined target molar mass and a graft density of about 0.2 chains nm-2 . Dynamic light scattering and TEM measurements revealed that the hybrid particles were highly dispersible in good solvents without any aggregation. The PVAc brushes were hydrolyzed with hydrochloric acid to produce poly(vinyl alcohol) brushes on the SiP surfaces. In addition, the number of xanthate molecules introduced on the SiP surfaces could be successfully controlled by adjusting the concentration of PEX. Thus, the SiPs have two functionalities: xanthates able to act as a MADIX chain-transfer agent and alkyl bromide initiation sites for atom transfer radical polymerization (ATRP). By using these unique bifunctional particles, mixed polymer brushes were constructed on the SiPs by MADIX of VAc followed by ATRP of styrene or methyl methacrylate.

Aromatic Xanthates and Dithiocarbamates for the Polymerization of Ethylene through Reversible Addition-Fragmentation Chain Transfer (RAFT).

Aromatic xanthates and dithiocarbamates were used as chain-transfer agents (CTAs) in reversible addition-fragmentation chain-transfer (RAFT) polymerizations of ethylene under milder conditions (≤80 °C, ≤200 bar). While detrimental side fragmentation of the intermediate radical leading to loss of living chain-ends was observed before with alkyl xanthate CTAs, this was absent for the aromatic CTAs. The loss of living chain-ends was nevertheless detected for the aromatic xanthates via a different mechanism based on cross-termination. Narrow molar-mass distributions with dispersities between 1.2 and 1.3 were still obtained up to number average molar masses Mn of 1000 g mol-1 . The loss of chain-ends was minor for dithiocarbamates, yielding polyethylene up to Mn =3000 g mol-1 with dispersities between 1.4 and 1.8. While systems investigated showed significant rate retardation, the dithiocarbamates are the first CTAs giving polyethylene with a high livingness via RAFT polymerization.

Alternating Radical Stabilities: A Convergent Route to Terminal and Internal Boronates.

Pinacolato boronates (Bpin) with an empty p-orbital on boron stabilize an adjacent carbon radical, in contrast to diethanolamino boronates [B(DEA)] where the boron is sp3 -hybridized. By alternately placing a pinacol or diethanolamine moiety on the boron atom, thus stabilizing or not stabilizing the corresponding adjacent radical, it is possible to control the behavior of α-boronyl xanthates and construct a large variety of terminal or internal boronates in a modular fashion. The remarkable tolerance of polar groups and the ability to introduce quaternary centers are particularly noteworthy features of this process.

Multimeric xanthates as carbonic anhydrase inhibitors.

The field of multivalent inhibition of enzymes is growing exponentially from the first reported multivalent effect on a glycosidase enzyme. However, the investigations have generally remained restricted to carbohydrate-processing enzymes. Carbonic anhydrases are ubiquitous metallo-enzymes involved in many key biological processes, that catalyze the reversible hydration/dehydration of [Formula: see text]. This study reports the first synthesis of multimeric xanthates addressing the selectivity and potency of CA multivalent inhibition. Six multivalent compounds containing three, four, and six xanthate moieties were prepared and assayed against four relevant CA isoforms together with their monovalent analogues. Some of the multimers were stronger inhibitors than the monomeric species. For hCA I, the two best molecules 18 and 20 showed an improvement of the ligand affinity of 4.8 and 2.3 per xanthate units (valence-corrected values), respectively, which corresponds to a clear multivalent effect. Moreover, the biochemical assays demonstrated that the multimeric presentation of xanthates, also affected the selectivity of the relative inhibition among the four CAs assayed.

Selective and Quantitative Oxidation of Xanthate End-Groups of RAFT Poly(n-butyl acrylate) Latexes by Ozonolysis.

Although various successful strategies have been reported in the past for the postpolymerization modification of the reversible addition-fragmentation chain transfer (RAFT) terminal group in homogeneous media, no solution is proposed for the tedious case of aqueous polymer dispersions where most of the thiocarbonylthio terminal group is buried into the core of the polymer particle. In this work, ozone is proposed to tackle this important academic and industrial challenge. After preliminary model ozonolysis reactions performed on a xanthate RAFT agent and a derived low molar mass poly(n-butyl acrylate) (PBA) in dichloromethane solution, it is shown that the hydrophobic nature and strong oxidant properties of ozone are responsible for its efficient diffusion in aqueous PBA latex particles obtained by RAFT and selective and complete transformation of the xanthate terminal group into a thiocarbonate end-group. In addition to the beneficial total discoloration of the final product, this chemical treatment does not generate any volatile organic compound and leaves the colloidal stability of the polymer particles unaffected, provided that a PBA latex with a sufficiently high Mn of 5000 g mol(-1) is selected.

One-step double covalent functionalization of reduced graphene oxide with xanthates and peroxides.

Radical functionalization of reduced graphene oxide has been achieved by reaction with a xanthate in the presence of peroxide as a radical initiator. X-ray photoelectron spectroscopy, bulk elemental analyses, and thermogravimetric analyses showed that the xanthate grafting is covalent and efficient. The synthesis and use of seven xanthates and three peroxides showed that the highest grafting yield is obtained when xanthate and peroxide are introduced in stoichiometric amounts. It also revealed that the peroxide used as radical initiator is grafted at the graphenic surface during the functionalization. The method presented in this contribution therefore allows bifunctionalized reduced graphene oxide samples to be easily obtained in one single step. This method leads to undamaged graphene sheets with higher dispersibility than the pristine sample.

Theoretical studies of Zn2+ complexes with alkyl xanthate ligands: a thermochemical, electronic energy decomposition, and natural bond orbital analysis.

CONTEXT: Xanthates are organic compounds that present great interest for coordination chemistry, because they can bond in different ways to the metal ion. Thus, these compounds have several applications, being best known for their environmental application. In fact, xanthates are recognized for their application as heavy metal collector agents in aqueous environments. In view of this application, this study is aimed at showing the thermochemical and electronic parameters obtained for the reactions of substitution water molecules in the aqua zinc complexes, by xanthate ligands (n-propyl, n-butyl, and n-pentyl xanthates). In addition to their environmental application, xanthates have shown biological properties, such as anti-bacterial and anti-cancer. In recent years, xanthates have also been used in the technological area, where it participates as a precursor of sulfides for the manufacture of thin films. Our results showed complexes with distorted octahedral geometries and with negative values of enthalpy and Gibbs free energy, indicating exothermic and spontaneous processes. For all the complexes, it was observed that Zn2+ complexes have both an ionic and covalent character. However, the monosubstituted complexes showed a predominance of the ionic character. In addition, high donor-acceptor interaction energies were obtained, indicating a good superposition between the s and p orbitals involved in the Zn-S bond. METHODS: This work consists in theoretical studies of Zn2+ complexes with alkyl xanthate ligands, with different structures, where optimization and normal modes calculations were performed at different DFT levels: M06L, M06-2X, wB97XD, and B3LYP/6-311++G**+LANL2TZ, with Gaussian09 program. The process of substitution of two aqua by two xanthate ligands was analyzed in stages, forming cationic and neutral complexes, in the first and second stages, respectively. In addition, electronic energy decomposition (EDA) and natural bond orbital (NBO) analysis were performed at level M06L/6-311++G**+LANL2TZ with Gamess program.

Microbial community structures and their driving factors in a typical gathering area of antimony mining and smelting in South China.

This study investigated soil microbial community in a typical gathering area of antimony mining and smelting in South China. The physical and chemical properties of different soils (mining waste dumps, flotation tailings, and smelting slag) and depths (0-20 cm, 40-60 cm, and 80-100 cm) were compared. The results showed that antimony (Sb) and arsenic (As) were the main pollutants, and their concentrations were 5524.7 mg/kg and 3433.7 mg/kg, respectively. Xanthates were found in the flotation tailings and smelting slag, and the highest concentration was 585.1 mg/kg. The microbial communities were analyzed by high-throughput sequencing, and it was shown that Proteobacteria, Acidobacteria, Chlorobacterium, Bacteroides, and Actinomycetes were the dominant taxa at the phylum level. There were obvious differences in microbial community structure in different sites. The dominant microorganism in the mining site was Chujaibacter. Subgroup_2_unclassified and Gemmatimonadaceae_unclassified were the prevalent microorganisms in the flotation and smelting sites, respectively. As, Sb, and xanthates were the main factors affecting the diversity and composition of bacteria in the flotation tailings and smelting slag areas. Therefore, this study provides experimental guidance and a theoretical basis for soil antimony pollution quality assessment, biological treatment, and environmental remediation.

Dithiocarbamates as Effective Reversible Addition-Fragmentation Chain Transfer Agents for Controlled Radical Polymerization of 1-Vinyl-1,2,4-triazole.

Narrow dispersed poly(1-vinyl-1,2,4-triazole) (PVT) was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of 1-vinyl-1,2,4-triazole (VT). AIBN as the initiator and dithiocarbamates, xanthates, and trithiocarbonates as the chain transfer agents (CTA) were used. Dithiocarbamates proved to be the most efficient in VT polymerization. Gel permeation chromatography was used to determine the molecular weight distribution and polydispersity of the synthesized polymers. The presence of the CTA stabilizing and leaving groups in the PVT was confirmed by 1H and 13C NMR spectroscopy. The linear dependence of the degree of polymerization on time confirms the conduct of radical polymerization in a controlled mode. The VT conversion was over 98% and the PVT number average molecular weight ranged from 11 to 61 kDa. The polydispersity of the synthesized polymers reached 1.16. The occurrence of the controlled radical polymerization was confirmed by monitoring the degree of polymerization over time.

Room-Temperature Patterning of Nanoscale MoS2 under an Electron Beam.

Molybdenum disulfide (MoS2) is traditionally grown at a high temperature and subsequently patterned to study its electronic properties or make devices. This method imposes severe limitations on the shape and size of MoS2 crystals that can be patterned precisely at required positions. Here, we describe a method of direct nanoscale patterning of MoS2 at room temperature by exposing a molybdenum thiocubane single-source precursor to a beam of electrons. Molybdenum thiocubanes with various alkylxanthate moieties [Mo4S4(ROCS2)6, where R = alkyl] were prepared using a "self-assembly" approach. Micro-Raman and micro-FTIR spectroscopic studies suggest that exposure to a relatively smaller dose of electrons results in the breakdown of xanthate moieties, leading to the formation of MoS2. High-resolution transmission electron micrographs suggest that the growth of MoS2 most likely happens along (100) planes. An electron-beam-induced chemical transformation of a molybdenum thiocubane resist was exploited to fabricate sub-10 nm MoS2 lines and dense dots as small as 13 nm with a pitch of 33 nm. Since this technique does not require the liftoff and etching steps, patterning of MoS2 with interesting shapes, sizes, and thicknesses potentially leading to tunable band gap is possible.

Multi-layered nanoscale cellulose/CuInS2 sandwich type thin films.

A generic procedure for the manufacturing of cellulose-metal sulfide multilayered sandwich type thin films is demonstrated at the example of copper indium sulfide. These multilayers were created by alternate spin coating steps of precursors, followed by their conversion using either acidic vapors, or heat treatment. As precursors, cellulose xanthate, a widely available cellulose derivative employed in viscose fiber manufacturing and commercial copper and indium xanthates were used. After conversion of the single layers into cellulose and copper indium sulfide, the film properties (structure, thickness, photoelectric activity) of the single and multilayer systems consisting of alternate layers of cellulose and copper indium sulfide were studied. For the proof of concept, up to five layers were built up, showing a clear separation of the cellulose and the metal sulfide layers as demonstrated using cross sectional analysis using ion slope beam cutting and SEM imaging. Finally, the conversion of xanthates was performed using UV light and a mask, allowing for the creation of 2D patterns.

Direct Patterning of Zinc Sulfide on a Sub-10 Nanometer Scale via Electron Beam Lithography.

Nanostructures of metal sulfides are conventionally prepared via chemical techniques and patterned using self-assembly. This poses a considerable amount of challenge when arbitrary shapes and sizes of nanostructures are desired to be placed at precise locations. Here, we describe an alternative approach of nanoscale patterning of zinc sulfide (ZnS) directly using a spin-coatable and electron beam sensitive zinc butylxanthate resist without the lift-off or etching step. Time-resolved electron beam damage studies using micro-Raman and micro-FTIR spectroscopies suggest that exposure to a beam of electrons leads to quick disappearance of xanthate moieties most likely via the Chugaev elimination, and further increase of electron dose results in the appearance of ZnS, thereby making the exposed resist insoluble in organic solvents. Formation of ZnS nanocrystals was confirmed by high-resolution transmission electron microscopy and selected area electron diffraction. This property was exploited for the fabrication of ZnS lines as small as 6 nm and also enabled patterning of 10 nm dots with pitches as close as 22 nm. The ZnS patterns fabricated by this technique showed defect-induced photoluminescence related to sub-band-gap optical transitions. This method offers an easy way to generate an ensemble of functional ZnS nanostructures that can be arbitrarily patterned and placed in a precise way. Such an approach may enable programmable design of functional chalcogenide nanostructures.

Xanthates As Useful Probes for Testing the Active Sites of Cytochromes P450 4A11 and 2E1.

Xanthates (alkyl or aryl derivatives of dithiocarbonic acid) have been shown to be selective mechanism-based inactivators of cytochromes P450 2B1/2B6 and 2E1 due to covalent binding of a reactive intermediate to apoprotein after double hydrogen abstraction at α-carbon atom, suggesting interaction of the xanthate dithiocarbonic head with the enzyme heme. The structures of xanthates with a long alkyl chain are similar to the fatty acids. Saturated fatty acids (FA) such as lauric acid (LA), are metabolized by different cytochrome P450 isoforms to ω- and (ω-1)-hydroxy products, in humans done by CYP4A11 and CYP2E1, respectively. In the present study we aimed at elucidating the possible interactions of xanthates with two cytochrome P450 isoforms CYP4A11 and CYP2E1 involved in the metabolism of the FA. Our experiments showed that LA-ω-hydroxylation by CYP4A11 is inhibited in a competitive manner by xanthates with long alkyl chain (C12-xanthate being the most potent inhibitor). On the other hand LA-(ω-1)-hydroxylation reaction by purified CYP2E1 is inactivated by a mechanism-based type. The suggested differences in the interactions of C12-xanthate with the two cytochrome P450 isoforms were investigated by molecular modeling using docking approach. The results suggested that in CYP2E1 active site C12-xanthate coordinates to the heme with its most vulnerable dithiocarbonic head leading to a mechanism-based inactivation. In CYP4A11 xanthate alkyl chain is exposed to the heme, thus, a potenial ω-hydroxylated xanthate product could be formed, which could inhibit in a competitive manner the hydroxylation of LA. The observed differences of xanthates interactions with the active sites of the two similar cytochrome P450 isoforms (CYP4A11 and CYP2E1) involved in the metabolism of FA, which lead to different changes in the enzyme activity, suggest that xanthates can be used as probing tools for analyzing enzyme active sites when exploring useful and selective compounds influencing FA homeostasis.

Capacidad de adsorción de plomo con intercambiadores catiónicos de carbón xantado / Adsorption capacity of lead with cationics exchangers of xanted coal

En este estudio, se describe la adsorción de plomo (Pb2+) en soluciones acuosas, a partir de carbón modificado, mediante tratamiento con CS2 y NaOH, empleando una relación 16,6:1 NaOH/Carbón p/p y 4,08:1 CS2/carbón p/p. Se realizaron pruebas de pH, cinéticas e isotermas de adsorción, para evaluar la capacidad de adsorción del carbón xantado y carbón no xantado. Los grupos azufre en el carbón xantado fueron identificados por espectroscopia infrarroja de reflectancia difusa (FTIR) y comparados con los espectros del carbón no xantado. Los resultados muestran que la mejor remoción de plomo en la solución con una concentración de 100mg de Pb2+/L y dosis de 50mg de adsorbente/10mL, respectivamente, fue a un valor de pH 5,0, logrando un porcentaje de adsorción de 98%. Los estudios cinéticos indican que el proceso de adsorción puede alcanzar el equilibrio alrededor de 120min, siguiendo una cinética de pseudo-segundo orden, para ambos materiales. El estudio de las isotermas indica que el carbón se ajusta mejor a una isoterma de tipo Langmuir y cuando se somete a la xantación, se ajusta a una isoterma de tipo Freundlich.

This study describes the adsorption of lead (Pb2+) in aqueous solutions of modified coal by treatment with CS2 and NaOH, using a ratio of 16,6:1 NaOH/coal (w/w) and 4,08 CS2/coal (w/w). Different tests such as acidity, kinetic and adsorption isotherms were carried out in order to assess the adsorption capacity of xanted and non-xanted coal. The sulfur groups presented in the xanted coal were identified by infrared spectroscopy(FTIR) and they were compared with non-xanted coal spectrum. The results show that the best lead removal in the solution (with a concentration of 100mg Pb2+/L and 50mg of adsorbent) was obtained at pH 5.0 for both coal (xanted and non-xanted) with an adsorption percentage of 98%. The kinetic studies indicate that the adsorption process can reach the equilibrium in about 120 minutes, following a pseudo-second order kinetics for both materials. The isotherms study indicates that the coal fits best to a Langmuir-type isotherm, however when the coal is xanted, it fits best to a Freundlich-type isotherm.