Regioselective thexyldimethylsilylation of (1➔3)-glucans - Does the linkage type matter.

α- and ß-(1➔3)-linked polysaccharides dissolved in N,N-dimethyl acetamide (DMA) were subjected to conversion with thexyldimethylchlorosilane (TDMS-Cl) in presence of pyridine as base. A degree of substitution of TDMS groups (DSSi) between 0.7 and 1.0 was achieved indicating that the ß-(1➔3)-linked curdlan (DSSi 0.7) is less reactive than α-(1➔3)-linked glucans (DSSi ca. 1). The synthesis sequence of permethylation, desilylation, and acetylation afforded the corresponding acetyl-methyl derivatives, where unaffected OH groups were methylated and TDMS groups were replaced by acetyl moieties. NMR spectroscopic investigations revealed a highly selective silylation of the primary OH group at position 6 while leaving the secondary OH moieties unaffected. This pronounced selectivity was found to be distinctly higher compared to cellulose and starch. Conversion of (1➔4)-linked polysaccharides dissolved in DMA/LiCl with TDMS-Cl leads to products consisting of both 6-mono-O- and 2,6-di-O- silylated repeating units. Regioselective 6-mono-O-silylation requires the hazardous use of liquid ammonia.

Silylation of phosphorylated cellulosic fibers with an aminosilane.

In this work, phosphorylated cellulosic fibers were functionalized with an aminosilane ((3-aminopropyl)triethoxysilane, APTES) using a simple and economical method. Several characterization were performed to determine the types of bonds between phosphorylated fibers and grafted APTES. The thermal behavior, hydrophobicity and surface charge variation as a function of pH of the multifunctional cellulose fibers were determined. Results demonstrate that APTES should proceed through Si-O-C, and possibly Si-O-P, covalent bonds with cellulose although the dimerization of silane through Si-O-Si bonds has also been observed. The terminal amino groups are expected to be partially involved in hydrogen bonds with phosphate hydroxyl groups found at phosphorylated cellulose fiber surface, causing a pulling in the configuration of the grafted APTES. The two chemical modifications proposed in this work do not significantly modify the morphology of cellulose fibers. XRD analysis also shows that the crystal structure of the phosphorylated fibers did not change after functionalization with APTES. The silylated phosphorylated fibers show potential flame-retardant properties with improved hydrophobicity. Furthermore, the functionalization of phosphorylated fibers with APTES changes the pH of zero charge point from 3.2 to 9.4 and providing a zwitterionic structure suitable for the simultaneous adsorption of both cationic and anionic species.

Fabrication of a modified bacterial cellulose with different alkyl chains and its prevention of abdominal adhesion.

Abdominal hernia mesh is a common product which is used for prevention of abdominal adhesion and repairing abdominal wall defect. Currently, designing and preparing a novel bio-mesh material with prevention of adhesion, promoting repair and good biocompatibility simultaneously remain a great bottleneck. In this study, a novel siloxane-modified bacterial cellulose (BC) was designed and fabricated by chemical vapor deposition silylation, then the effects of different alkyl chains length of siloxane on surface properties and cell behaviors were explored. The effect of preventing of abdominal adhesion and repairing abdominal wall defect in rats with the siloxane-modified BC was evaluated. As the grafted alkyl chains become longer, the surface of the siloxane-modified BC can be transformed from super hydrophilic to hydrophobic. In vivo results showed that BC-C16 had good long-term anti-adhesion effect, good tissue adaptability and histocompatibility, which is expected to be used as a new anti-adhesion hernia repair material in clinic.

Strategies and mechanisms for improving the detection accuracy of nonextractable residues of polycyclic aromatic hydrocarbons in soils.

The methods that can accurately measure the concentrations of nonextractable residues (NERs) of hydrophobic organic contaminants (HOCs) in soil are still lacked in current studies. In this study, three methods, namely methanolic saponification treatment (MST), silylation treatment (ST), and acid deashing treatment (ADT), were investigated and then combined to extract the NERs of six types of polycyclic aromatic hydrocarbons (PAHs) from nine soil samples. The NER concentrations of PAHs obtained by ST (2.43-521.73 ng g-1) were comparable to or significantly higher than those obtained by MST (1.94-291.54 ng g-1), owing to the properties of soil and target compounds. Additionally, ADT could further release a considerable amount of PAH NERs (0.39-276.99 ng g-1) from the soils that had been treated with ST. The mechanism was that acid solution dissolved mineral components, significantly increasing the pore size of the soil matrices from 9.37-15.57 nm to 17.11-27.51 nm. The average percentage of each PAH obtained by ADT (the ratio of the amount obtained by ADT to the total NER content) exhibited a negative correlation with their ring numbers (R2 = 0.62, p < 0.05), whereas the percentage of targets recovered through ST increased linearly with their log KOW values (R2 = 0.75, p < 0.05). Moreover, there is a positive correlation (R2 = 0.73, p < 0.05) between the NER percentages of phenanthrene (obtained by ST-ADT) and the specific surface areas of soils, and the NER percentages of benzo(g,h,i)perylene is positively correlated to the content of total organic carbon (R2 = 0.62, p < 0.05). These results suggested that the amounts and locations of NERs were influenced by both the physicochemical characteristics of PAHs and soils. These findings provide some basic understandings of the entrapped mechanisms of PAH NERs, helping to establish strategies for improving their detection accuracy.

Mexican Coccoloba uvifera L. Leaf and Fruit Extracts: Identification of Pentacyclic Triterpenes and Volatile Profile by GC-MS.

Mexican Coccoloba uvifera fruit contains polyphenols, flavonoids, and anthocyanins, while in the leaves, lupeol, α- and ß-amyrin have been previously identified by HPLC. However, the low resolution by HPLC of pentacyclic triterpenes (PTs) is a limitation. Moreover, the volatile profile of C. uvifera fruit is still unknown. Therefore, this study aimed to identify PTs in C. uvifera leaf and fruit extracts by CG-MS analysis and to determine the volatile profile of C. uvifera pulp by headspace solid-phase microextraction. The results showed trimethylsilylated compounds of standards lupeol, α- and ß-amyrin, indicating that the silylation reaction was suitable. These trimethylsilylated compounds were identified in leaf and fruit extracts. The fruit volatile profile revealed the presence of 278 esters, 20 terpenes, 9 aldehydes, 5 alcohols, and 4 ketones. The fruit showed a high content of esters and terpenes. Due to their flavour properties, esters are essential for the food, cosmetics, and pharmaceutics industries. Moreover, terpenes in the fruit, such as menthone, ß-elemene, junipene, and ß-caryophyllene have the potential as anticancer and phytopathogen agents. The results indicated that GC-MS is an alternative to HPLC approaches for identifying PTs. Besides, identifying volatile compounds in the fruit will increase the value of this plant and expand its application. Identifying PTs and volatile compounds in Mexican C. uvifera leads to a better understanding of the potential benefits of this plant. This would increase the consumption of Mexican C. uvifera fresh or as functional ingredients in nutraceutical or pharmaceutical products.

Iron-Catalyzed Allylic C(sp3)-H Silylation: Spin-Crossover-Efficiency-Determined Chemoselectivity.

The nuanced role of spin effects remains a critical gap in designing proficient open-shell catalysts. This study elucidates an iron-catalyzed allylic C(sp3)-H silylation/alkyne hydrosilylation reaction, in which the spin state of the open-shell iron catalyst dictates the reaction kinetics and pathway. Specifically, spin crossover led to alkyne hydrosilylation, whereas spin conservation resulted in a novel allylic C(sp3)-H silylation reaction. This chemoselectivity, governed by the spin-crossover efficiency, reveals an unexpected dimension in spin effects and a first in the realm of transition-metal-catalyzed in situ silylation of allylic C(sp3)-H bonds, which had been previously inhibited by the heightened reactivity of alkenes in hydrosilylation reactions. Furthermore, this spin crossover can either accelerate or hinder the reaction at different stages within a single catalytic reaction, a phenomenon scarcely documented. Moreover, we identify a substrate-assisted C-H activation mechanism, a departure from known ligand-assisted processes, offering a fresh perspective on C-H activation strategies.

Anti-Selective Carbosilylation: Nickel-Catalyzed Multicomponent Reaction of Solid Me3SiZnI.

The stereodefined and highly substituted vinylsilanes are essential building blocks for constructing complex organic molecules. Transition metal-mediated silylmetalation of alkynes was developed to overcome the limitations of conventional hydrosilylations; however, a very limited study was carried out to utilize transient vinylmetal species in cross-coupling reactions. Moreover, they produce syn-adduct, and the anti-selective cross-coupling is still unknown and highly desired. Silylzinc reagents are highly functional group tolerant, however, their synthesis from pyrophoric silyllithium and dissolved lithium salts hampers cross-coupling reactions. Our novel solid silylzinc reagents circumvent these constraints are employed in the anti-selective synthesis of vinylsilanes via a multi-component reaction involving Me3SiZnI, terminal alkynes, and activated alkyl halides. An intensive computational and experimental investigation of the mechanism reveals an equilibrium between the intermediate syn- and anti-adducts; the greater barrier at the single electron reduction of alkyl halides and the thermodynamic stability of the Ni(III) adduct determine the anti-selectivity.

Designable Synthesis of Layered Silicates and Tunable Interlayer Expanded to Zeolites.

Layered zeolitic silicates and corresponding interlayer-expanded porous materials exhibit attractive application potential in wide fields. Nonetheless, designable synthesis and structure analysis of layered silicates remain challenging. Herein, two kinds of layered silicates are synthesized using different di-quaternary ammonium-type organic structure-directing agents (OSDAs). Their crystal structures are analyzed and verified by 3D electron diffraction (3D ED) and high-resolution TEM imaging. The suitable configurations of OSDA can lead to desirable interlayer states. Additionally, two new zeolite structures both with 12-membered ring (MR) channels intersected by 8 MR channels and larger interlayer spaces are constructed from layered silicate precursors by interlayer silylation. The new zeolitic material exhibits potential application in adsorption of organic pollution and catalytic reaction. This study is expected to develop versatile ways for the design and synthesis of layered silicates even zeolites and provide references in characterizing layered materials and zeolites as well.

Enantioselective and Regiodivergent Synthesis of Propargyl- and Allenylsilanes through Catalytic Propargylic C-H Deprotonation.

We report a highly enantioselective intermolecular C-H bond silylation catalyzed by a phosphoramidite-ligated iridium catalyst. Under reagent-controlled protocols, propargylsilanes resulting from C(sp3)-H functionalization, as well the regioisomeric and synthetically versatile allenylsilanes, could be obtained with excellent levels of enantioselectivity and good to excellent control of propargyl/allenyl selectivity. In the case of unsymmetrical dialkyl acetylenes, good to excellent selectivity for functionalization at the less-hindered site was also observed. A variety of electrophilic silyl sources (R3SiOTf and R3SiNTf2), either commercial or in situ-generated, were used as the silylation reagents, and a broad range of simple and functionalized alkynes, including aryl alkyl acetylenes, dialkyl acetylenes, 1,3-enynes, and drug derivatives were successfully employed as substrates. Detailed mechanistic experiments and DFT calculations suggest that an η3-propargyl/allenyl Ir intermediate is generated upon π-complexation-assisted deprotonation and undergoes outer-sphere attack by the electrophilic silylating reagent to give propargylic silanes, with the latter step identified as the enantiodetermining step.

Ruthenium-Catalyzed Dehydrogenative Intermolecular O-H/Si-H/C-H Silylation: Synthesis of (E)-Alkenyl Silyl-Ether and Silyl-Ether Heterocycle.

Selective dehydrogenative silylation is one of the most valuable tools for synthesizing organosilicon compounds. In this study, a regio- and stereoselective ruthenium-catalyzed dehydrogenative intermolecular silylation was firstly developed to access (E)-alkenyl silyl-ether derivatives and silyl-ether heterocycles with good functional group tolerance. Furthermore, two pathways for RuH2(CO)(PPh3)3/NBE-catalyzed dehydrogenative intermolecular silylation of alcohols and alkenes as well as intermolecular silylation of naphthol derivatives were investigated with H2SiEt2 as the hydrosilane reagent.

Recent Progress in the Synthesis of Silaspiranes.

Silaspiranes bearing a spiro-silicon center are promising ring frameworks for the synthesis of novel spirocyclic molecules possessing unique properties. Development of efficient methods towards these ring structures has therefore attracted considerable attentions of synthetic chemists. This minireview highlights the representative advances in the field, and is categorized into four parts according to the ring formation strategies: cyclization, annulation, ring expansion and cycloaddition.

Access to Enantiomerically Pure P-Chiral 1-Phosphanorbornane Silyl Ethers.

Sulfur-protected enantiopure P-chiral 1-phosphanorbornane silyl ethers 5a,b are obtained in high yields via the reaction of the hydroxy group of P-chiral 1-phosphanorbornane alcohol 4 with tert-butyldimethylsilyl chloride (TBDMSCl) and triphenylsilyl chloride (TPSCl). The corresponding optically pure silyl ethers 5a,b are purified via crystallization and fully structurally characterized. Desulfurization with excess Raney nickel gives access to bulky monodentate enantiopure phosphorus(III) 1-phosphanorbornane silyl ethers 6a,b which are subsequently applied as ligands in iridium-catalyzed asymmetric hydrogenation of a prochiral ketone and enamide. Better activity and selectivity were observed in the latter case.

A green deep eutectic solvent based dispersive liquid-liquid microextraction for the quantitative analysis of 21 polychlorinated biphenyl metabolites in food of animal origin using injector port silylation-gas chromatography-tandem mass spectrometry.

An analytical method was developed for the quantitative determination of 21 polychlorinated biphenyls (PCBs) metabolites (17 were -OH, 1 -MeO, and 3 were MeSO2) in foods of animal origin using deep eutectic solvent (DES) based dispersive liquid-liquid microextraction followed by injector port silylation-gas chromatography-tandem mass spectrometry. The type of DES (thymol: camphor, 1:1 molar ratio) and optimum volume of DES (300 µL), pH (7.0), and disperser solvent (acetonitrile) were optimized to attain the maximum extraction efficiency. The limit of detection, limit of quantification, and percent recovery were found to be in the range of 0.12-0.23 ng/mL, 0.40-0.76 ng/mL, and 80.1-111.4%, respectively. The expanded uncertainty was observed to be in the range of 7.2-22.8% for the targeted analytes. The proposed method was applied to real food samples (milk, meat, fish, and egg) and the levels were found to be in the range of 0.64-32.14 ng/g. This is first of its kind method using green solvent based method for the analysis of PCB metabolites (-OH, MeO, and MeSO2) and will find extensive application in routine testing for foods of animal origin.

Chiral PSiSi-Ligand Enabled Iridium-Catalyzed Atroposelective Intermolecular C-H Silylation.

Catalytic enantioselective intermolecular C-H silylation offers an efficient approach for the rapid construction of chiral organosilicon compounds, but remains a significant challenge. Herein, a new type of chiral silyl ligand is developed, which enables the first iridium-catalyzed atroposelective intermolecular C-H silylation reaction of 2-arylisoquinolines. This protocol features mild reaction conditions, high atom economy, and remarkable yield with excellent stereoselectivity (up to 99 % yield, 99 % ee), delivering enantioenriched axially chiral silane platform molecules with facile convertibility. Key to the success of this unprecedented transformation relies on a novel chiral PSiSi-ligand, which facilitates the intermolecular C-H silylation process with perfect chem-, regio- and stereo-control via a multi-coordinated silyl iridium complex.

Photocatalytic and Electrochemical Borylation and Silylation Reactions.

Due to their high versatility borylated and silylated compounds are inevitable synthons for organic chemists. To escape the classical hydroboration/hydrosilylation paradigm, chemists turned their attention to more modern and green methods such as photoredox chemistry and electrosynthesis. This account focuses on novel methods for the generation of boryl and silyl radicals to forge C-B and C-Si bonds from our group.

Improved Assessment of Soil Nonextractable Residues of the Pyrethroid Insecticide Cyphenothrin.

The metabolic fate of pyrethroid insecticide cyphenothrin (1) [(RS)-α-cyano-3-phenoxybenzyl (1RS)-cis-trans-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate] in soils was investigated using 14C-labeled (1R)-cis/trans isomers at the cyclopropane ring. Both isomers degraded with half-lives of 19.0-47.4 days, and 48.9-56.0% and 27.5-38.7% of the applied radioactivity (AR) were mineralized to CO2 and incorporated into nonextractable residues (NER), respectively, after 120 days at 20 °C. NER analyses revealed 37.5-42.2% (cis-1) and 44.9-54.1% (trans-1) of each residue at 30/120 days were comprised of 14C-amino acids (AAs) as microbial products. Assuming that 50% of microbial biomass is AAs, it was estimated that 11.3-22.9%AR (cis-1, 75.0-84.4% of NER) and 13.9-30.4%AR (trans-1, 89.8-108.2% of NER) were nonhazardous biogenic NER (bio-NER), while type I/II xenobiotic NER (xeno-NER) characterized by silylation was insignificant at 0.9-1.0%/2.8-3.3%AR (cis-1). Detailed 14C-AA quantitation indicated a high relevance of the tricarboxylic acid cycle and pyruvate pathway during bio-NER formation, offering new insights into the microbial assimilation of the chrysanthemic moiety.

Organopotassium-Catalyzed Silylation of Benzylic C(sp3 )-H Bonds.

Benzylsilanes have found increasing applications in organic synthesis as bench-stable synthetic intermediates, yet are mostly produced by stoichiometric procedures. Catalytic alternatives based on the atom-economical silylation of benzylic C(sp3 )-H bonds remain scarcely available as specialized directing groups and catalytic systems are needed to outcompete the kinetically-favored silylation of C(sp2 )-H bonds. Herein, we describe the first general and catalytic-in-metal undirected silylation of benzylic C(sp3 )-H bonds under ambient, transition metal-free conditions using stable tert-butyl-substituted silyldiazenes (tBu-N=N-SiR3 ) as silicon source. The high activity and selectivity of the catalytic system, exemplified by the preparation of various mono- or gem-bis benzyl(di)silanes, originates from the facile generation of organopotassium reagents, including tert-butylpotassium.

GC-EI-MS datasets of trimethylsilyl (TMS) and tert-butyl dimethyl silyl (TBDMS) derivatives for development of machine learning-based compound identification approaches.

In the field of environment and health studies, recent trends have focused on the identification of contaminants of emerging concern (CEC). This is a complex, challenging task, as resources, such as compound databases (DBs) and mass spectral libraries (MSLs) concerning these compounds are very poor. This is particularly true for semi polar organic contaminants that have to be derivatized prior to gas chromatography-mass spectrometry (GC-MS) analysis with electron impact ionization (EI), for which it is barely possible to find any records. In particular, there is a severe lack of datasets of GC-EI-MS spectra generated and made publicly available for the purpose of development, validation and performance evaluation of cheminformatics-assisted compound structure identification (CSI) approaches, including novel cutting-edge machine learning (ML)-based approaches [1]. We set out to fill this gap and support the machine learning-assisted compound identification, thus aiding cheminformatics-assisted identification of silylated derivatives in GC-MS laboratories working in the field of environment and health. To this end, we have generated 12 datasets of GC-EI-MS spectra, six of which contain GC-EI-MS spectra of trimethylsilyl (TMS) and six GC-EI-MS spectra of tert-butyldimethylsilyl (TBDMS) derivatives. Four of these datasets, named testing datasets, contain mass spectra acquired by the authors. They are available in full, together with corresponding metadata. Eight datasets, named training datasets, were derived from mass spectra in the NIST 17 Mass Spectral Library. For these, we have only made the metadata publicly available, due to licensing reasons. For each type of derivative, two testing datasets are generated by acquiring and processing GC-EI-MS spectra, such that they include raw and processed GC-EI-MS spectra of TMS and TBDMS derivatives of CECs, along with their corresponding metadata. The metadata contains IUPAC name, exact mass, molecular formula, InChI, InChIKey, SMILES and PubChemID, of each CEC and CEC-TMS or CEC-TBDMS derivative, where available. Eight GC-EI-MS training datasets are generated by using the National Institute of Standards and Technology (NIST)/U.S. Environmental Protection Agency (EPA)/National Institute of Health (NIH) 17 Mass Spectral Library. For each derivative type (TMS and TBDMS), four datasets are given, each corresponding to an original dataset obtained from NIST/EPA/NIH 17 and three variants thereof, obtained after each of the filtering steps of the procedure described below. Only the metadata about the training datasets are available, describing the corresponding NIST/EPA/NIH 17 entires: These include the compound name, CAS Registry number, InChIKey, exact mass, Mw, NIST number and ID number. The datasets we present here were used to train and test predictive models for identification of silylated derivatives built with ML approaches [4]. The models were built by using data curated from the NIST Mass Spectral Library 17 [2] and the machine learning approach of CSI:Output Kernel Regression (CSI:OKR) [2]. Data from the NIST Mass Spectral Library 17 are commercially available from the National Institute of Standards and Technology (NIST)/U.S. Environmental Protection Agency (EPA)/National Institute of Health (NIH) and thus cannot be made publicly available. This highlights the need for publicly available GC-EI-MS spectra, which we address by releasing in full the four testing datasets.

Thioethers as Dichotomous Electrophiles for Site-Selective Silylation via C-S Bond Cleavage.

The development of aryl alkyl sulfides as dichotomous electrophiles for site-selective silylation via C-S bond cleavage has been achieved. Iron-catalyzed selective cleavage of C(aryl)-S bonds can occur in the presence of ß-diketimine ligands, and the cleavage of C(alkyl)-S bonds can be achieved by t-BuONa without the use of transition metals, resulting in the corresponding silylated products in moderate to excellent yields. Mechanistic studies suggest that Fe-Si species may undergo metathesis reactions during the cleavage of C(aryl)-S bonds, while silyl radicals are involved during the cleavage of C(alkyl)-S bonds.

Rhodium-Catalyzed Trans-Bis-Silylation Reactions of 2-Ethynyl-3-pentamethyldisilanylpyridines.

Rhodium-catalyzed reactions of 2-ethynyl-3-pentamethyldisilanylpyridine derivatives (1 and 2) are reported. The reactions of compounds 1 and 2 in the presence of catalytic amounts of rhodium complexes at 110 °C gave the corresponding pyridine-fused siloles (3) and (4) through intramolecular trans-bis-silylation cyclization. The reaction of 2-bromo-3-(1,1,2,2,2-pentamethyldisilanyl)pyridine with 3-phenyl-1-propyne in the presence of PdCl2(PPh3)2-CuI catalysts afforded 1:2 bis-silylation adduct 6. DFT calculations were also performed to understand the reaction mechanism for the production of compound 3 from compound 1.