NBS AND NCS APPLIED TO THIOCYANATION OF AROMATIC RINGS

Instead of Br_2 and Cl_2,NBS and NCS are applicable to the thiocyanation of o-nitroaniline and carbendazim.The results show that NBS and NCS are superior to Br_2 and Cl_2 due to their easier operation.

Decarboxylative cyanation and thiocyanation via catalytic electron donor-acceptor complex with copper catalysis

A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.

Thianthrene Radical Cation as a Transient SET Mediator:Photoinduced Thiocyanation and Selenocyanation of Arylthianthrenium Salts

Comprehensive Summary A novel transient SET mediator approach has been developed for the photoinduced radical-radical cross coupling reaction.Using the in-situ generated thianthrene radical cation as the transient SET mediator,the thiocyanation and selenocyanation of aryl thianthrenium salts have been realized under the mild conditions without the need for photocatalyst or single electron donor.In comparison with the photocatalyst enabled process,the protocol features mild conditions,simple manipulation,a broad substrate scope,excellent functional group and heterocycle tolerance.Due to the feasible accessibility of aryl thianthrenium salts,this method has also been applied in the efficient synthesis of a bioactive molecule,and the late-stage functionalization of complex arenes.

Catalytic Thiourea Promoted Electrophilic Thiocyanation of Indoles and Aromatic Amines with NCS/NH4SCN

A simple and efficient protocol for the electrophilic thiocyanation of indoles and aromatic amines with thiourea/NCS/NH4SCN system has been developed. The major features of the present procedure are the mild conditions, good yields, short reaction times, and the use of inexpensive and readily available organocatalyst. Moreover, N-chlorosueeinimide （NCS） was found to be indispensable, and thiourea could greatly promote the reaction.

Semitransparent organic photovoltaics enabled by transparent p-type inorganic semiconductor and near-infrared acceptor

Semitransparent organic photovoltaics(STOPVs)have gained wide attention owing to their promising applications in building-integrated photovoltaics,agrivoltaics,and floating photovoltaics.Organic semiconductors with high charge carrier mobility usually have planar and conjugated structures,thereby showing strong absorption in visible region.In this work,a new concept of incorporating transparent inorganic semiconductors is proposed for high-performance STOPVs.Copper(I)thiocyanate(CuSCN)is a visible-transparent inorganic semiconductor with an ionization potential of 5.45 eV and high hole mobility.The transparency of CuSCN benefits high average visible transmittance(AVT)of STOPVs.The energy levels of CuSCN as donor match those of near-infrared small molecule acceptor BTP-eC9,and the formed heterojunction exhibits an ability of exciton dissociation.High mobility of CuSCN contributes to a more favorable charge transport channel and suppresses charge recombination.The control STOPVs based on PM6/BTP-eC9 exhibit an AVT of 19.0%with a power conversion efficiency(PCE)of 12.7%.Partial replacement of PM6 with CuSCN leads to a 63%increase in transmittance,resulting in a higher AVT of 30.9%and a comparable PCE of 10.8%.

Synthesis,crystal structures,and antibacterial activities of two zinc(Ⅱ) complexes bearing 5⁃phenyl⁃1H⁃pyrazole group

A novel compound(H_(2)L)SCN(5⁃methyl⁃3⁃phenyl⁃2H⁃pyrazol⁃1⁃ium thiocyanate)has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol.Two zinccomplexes[Zn(HL)_(2)(NCS)(CH_(3)COO)](1)and[Zn_(2)(L)_(2)(HL)_(2)(NCS)_(2)]_(2)·2CH_(3)OH(2)have been synthesized by the coordination reactions of Zn(OAc)_(2)·2H_(2)O or ZnCl_(2)with(H_(2)L)SCN under reflux conditions.Elemental analyses and single⁃crystal X⁃ray diffraction have con⁃firmed the structures of the synthesized compounds.The(H_(2)L)SCN ligand and complex 1 pertain to the triclinic sys⁃tem with space group P1,while complex 2 belongs to the monoclinic system with space group P2_(1)/n.Additionally,the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bac⁃terial strains(Candida albicans,Staphylococcus aureus,and Escherichia coli).The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria,and the complexes possessed stronger antibac⁃terial activities against the same bacteria than the free ligand.CCDC:2190252,(H2L)SCN;2190253,1;2190256,2.

Copper-Catalyzed Benzylic C–H Bond Thiocyanation: Enabling Late-Stage Diversifications

The rapid growth of using C–H bond as cross-coupling partners is reshaping the landscape of organic synthesis.C(sp3)–H functionalization via hydrogen atom transfer(HAT)represents the most compelling strategy in this avenue.Here,we demonstrate an efficient method for benzylic C–H bond thiocyanation via copper-catalyzed radical relay.The reaction exhibits broad substrate scope and exquisite benzylic selectivity with C–H substrates as limiting reagents.In addition,the benzyl thiocyanates are readily converted to other pharmaceutically important motifs,including isothiocyanate,thiourea,and others,highlighting the broad utility of this method.

PhlCl_(2)/NH_(4)SCN-Mediated Oxidative Regioselective Thiocyanation of Pyridin-2(1H)-ones

The reaction of pyridin-2(1H)·ones with PhlCl_(2) and NH_(4)SCN enables an efficient regioselective thiocyanation,leading to the synthesis of the biologically interesting C5 thiocyanated 2-pyridones in good to high yields.The mechanistic pathway of this metal-free approach is postulated to involve the formation of the reactive thiocyanogen chloride from the reaction of PhlCl_(2) and NH4SCN followed with the regioselective electrophilic thiocyanation of the pyridin-2(1H)-one ring.

Synthesis of 3-thiocyanated chromones via TCCA/NH_(4)SCN-mediated cyclization/thiocyanation of alkynyl aryl ketones

3-Thiocyanated chromones was conveniently synthesized from alkynyl aryl ketones using commercially available,inexpensive trichloroisocyanuric acid(TCCA)as oxidant and NH_(4)SCN as thiocyanato(SCN)source.This metalfree approach is postulated to first in situ generate thiocyanogen chloride(Cl-SCN)from the reaction of TCCA and NH_(4)SCN,followed by a rare efficient electrophilic thiocyano oxyfunctionalization of alkynes enabled by the reactive electrophilic species generated thereof.

Identification,structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors

During the analysis of benziamidazole-class irreversible proton pump inhibitors,an unusual mass spectral response with the mass-to-charge ratio at[Mt10]t intrigued us,as it couldn't be assigned to any literature known relevant structure,intermediate or adduct ion.Moreover,this mysterious mass pattern of[Mt10]t has been gradually observed by series of marketed proton pump inhibitors,viz.omeprazole,pantoprazole,lansoprazole and rabeprazole.All the previous attempts to isolate the corresponding component were unsuccessful.The investigation of present work addresses this kind of signal to a pyridinium thiocyanate mass spectral intermediate(10),which is the common fragment ion of series of labile aggregates.The origin of such aggregates can be traced to the reactive intermediates formed by acid-promoted degradation.These reactive intermediates tend to react with each other and give raise series of complicated aggregates systematically in a water/acetonitrile solution by electrospray ionization.The structure of the corresponding pyridinium thiocyanate species of omeprazole(10a)has been eventually characterized with the help of synthetic specimen(10a′).Our structural proposal as well as its origin was supported by in situ nuclear magnetic resonance,chemical derivatization and colorimetric experiments.

Potassium thiocyanate additive for PEDOT:PSS layer to fabricate efficient tin-based perovskite solar cells

The commercialized poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS)is usually used as hole transport layers(HTLs)in tin-based perovskite solar cells(TPSCs).However,the further development has been restricted due to the acidity that could damage the stability of TPSCs.Although the PEDOT:PSS solution can be diluted by water to decrease acidity and reduce the cost of device fabrication,the electrical conductivity will decrease obviously in diluted PEDOT:PSS solution.Herein,potassium thiocyanate(KSCN)is selected to regulate the properties of PEDOT:PSS HTLs from the diluted PEDOT:PSS aqueous solution by water with a volume ratio of 1:1 to prepare efficient TPSCs.The effect of KSCN addition on the structure and photoelectrical properties of PEDOT:PSS HTLs and TPSCs have been systematically studied.At the optimal KSCN concentration,the TPSCs based on KSCN-doped PEDOT:PSS HTLs(KSCN-PSCs)demonstrate the champion power conversion efficiency(PCE)of 8.39%,while the reference TPSCs only show a champioan PCE of 6.70%.The further analysis demonstrates that the KSCN additive increases the electrical conductivity of HTLs prepared by the diluted PEDOT:PSS solution,improves the microstructure of perovskite film,and inhibits carrier recombination in TPSCs,leading to the reduced hysteresis effect and enhanced PCE in KSCN-PSCs.This work gives a low-cost and practical strategy to develop a high-quality PEDOT:PSS HTLs from diluted PEDOT:PSS aqueous solution for efficient TPSCs.

Adsorption removal of thiocyanate from aqueous solution by calcined hydrotalcite

A hydrotalcite with Mg/AI molar ratio 2 was prepared by co-precipitation method and was characterized by XRD, TG/DTA, Zeta potential and BET surface area. The hydrotalcite was calcined at 500℃, with the dehydration from interlayer, the dehydroxilation from the brucite-like layer and the decomposition of carbonate successively, transformed into the mixed oxide type. The removal of thiocyanate from aqueous solution by using the original hydrotalcite and calcined hydrotalcite （HTC-500） was investigated. The results showed that the thiocyanate adsorption capacity of calcined hydrotalcite was much higher than that of the original form. Calcined hydrotalcite was particularly effective at removing thiocyanate, and that the effective range of pH for the thiocyanate removal are between 5.5-10.0. The experimental data of thiocyanate removal fit nicely with Langmuir isotherm, and the saturated adsorption uptake was 96.2 mg SCN-/g HTC-500. The adsorption of thiocyanate by calcined hydrotalcite follows first-order kinetics. And the intercalation to the structure recovery for calcined hydrotalcite. But the presence of additional anions could affect the adsorption behavior of thiocyanate.

A facile and convenient method for synthesis of alkyl thiocyanates under homogeneous phase transfer catalyst conditions

A simple and environmentally friendly method is described for the efficient conversion of alkyl halide to alkyl thiocyanate using tetrabutylammonium bromide （TBAB） as a phase transfer catalyst. The reactions occur in water and furnish the corresponding alkyl thiocyanate in high yields. No evidence for the formation of isothiocyanates as by-product of the reaction was observed and the products were obtained in pure form without further purification.

Comparison of Three Different Techniques of Human Sperm DNA Isolation for Methylation Assay

Summary： Human sperm DNA is an important genetic and epigenetic material, whose chromatin structure differs from that of somatic cells. As such, conventional methods for DNA extraction of somatic cells may not be suitable for obtaining sperm DNA. In this study, we evaluated and compared three sperm DNA extraction techniques, namely, modified guanidinium thiocyanate method （method A）, traditional phenol-chloroform method （method B）, and TianGen kit method （method C）. Spectrophotometry and agarose gel electrophoresis analyses showed that method A produced DNA with higher quantity and purity than those of methods B and C （P〈0.01）. PCR results revealed that method A was more reliable in amplifying DEAD-box polypeptide 4 （DDX4） and copy number variations （CNVs） than methods B and C, which generated false-positive errors. The results of sperm DNA methylation assay further indicated that methods A and B were effective, and the former yielded higher quantitative accuracy. In conclusion, the modified guanidinium thiocyanate method provided high quality and reli- able results and could be an optimal technique for extracting sperm DNA for methylation assay.

Regioselective ring opening of epoxides using NH_4SCN/silica sulfuric acid:An efficient approach for the synthesis of β-hydroxy thiocyanate under solvent-free conditions

Silica sulfuric acid was developed as a stable and efficient heterogeneous catalyst in organic synthesis. This solid acid catalyzed the regioselective ring opening of epoxides by thiocyanate anion to give thiocyanohydrins as key intermediates in agricultural and pharmaceutical chemistry in high yields under solvent-free conditions.

Determination of Trace Thiocyanate by a Chitosan-Modified Glassy Carbon Electrode

A chitosan modified glassy carbon electrode(CMGCE) was employed for the determination of thiocyanate. The measurement was carried out by means of anodic stripping voltammetry. The effects of several experimental parameters, such as pH, the amount of modifier, deposition potential and deposition time were studied for analytical application, respectively. A liner response was obtained in the concentration range of 3 5×10 -8 - 9.3×10 -7 g/mL of SCN -. The detection limit was found to be 1.9×10 -8 g/mL. The method was satisfactorily used to detect SCN - in saliva.

Resonance Light Scattering Spectra of Silver Thiocyanate System and its Application in Analysis

A novel determination method of Ag^＋ was established. In acetic acid-sodium acetate buffer （pH 5.0） medium, Ag^＋ reacts with SCN^- to form AgSCN in the presence of TritonX-100,which results in an increase of resonance light scattering （RLS）and giving a new RLS spectrum.The maximum RLS peak was at 585 nm,The enhancement of resonance light scattering at 585 nm was proportional to the concentration of Ag^＋ ranging from 0.0045-4.00μg mL^-1 （r=9991）,and the detection limit was 1.37 ng mL^-1 with the recovery of 97.70%- 104.80%。

Simple Modifications to Standard TRIzol®Protocol Allow High-Yield RNA Extraction from Cells on Resorbable Materials

Resorbable bioceramics are attractive for medical applications such as bone substitution. Biochemical analysis on cells cultured on these biomaterials is vital to predict the impact of the materials in vivo and RNA extraction is an essential step in gene expression study using RT-qPCR. In this study, we describe simple modifications to the TRIzol? RNA extraction protocol widely used in biology and these allow high-yield extraction of RNA from cells on resorbable calcium phosphates. Without the modifications, RNA is trapped in the co-precipitated calcium compounds, rendering TRIzol? extraction method infeasible. Among the modifications, the use of extra TRIzol? to dilute the lysate before the RNA precipitation step is critical for extraction of RNA from porous ?-tricalcium phosphate (?-TCP) discs. We also investigate the rationale behind the undesirable precipitation so as to provide clues about the modifications required for other resorbable materials with high application potential in bone tissue engineering.

Thiocyanate Oxidation by Coculture from a Coke Wastewater Treatment Plant

Bacterial strains in an activated sludge aerobic reactor from a coke wastewater were found to be able to utilize thiocyanate as carbon source when the thiocyanate-containing wastewater was deprived of carbon source. This study showed that three thiocyanate-oxidizing bacterial strains, Burkholderia sp., Chryseobacterium sp., and Ralstonia sp. were isolated from the activated sludge of a coke wastewater treatment plant as evidenced by the fact that complete decomposition of thiocyanate was achieved either by coculture or individual pure culture. The thiocyanate biodegradation by the coculture occurred with an optimal pH range between 6.5 and 8.5 and an optimal temperature range between 30°C and 40°C. The biodegradation kinetics of thiocyanate was well fitted with the Andrew-Haldane model, which demonstrated a distinct substrate concentration-inhibited bacterial growth pattern. The effects of different types of additional carbon, nitrogen or sulfur sources on thiocyanate biodegradation were also investigated. Analysis of the end-products indicated that thiocyanate degradation by these strains should proceed via two pathways.

Synthesis and Crystal Structure of Co(DMSO)_2(H_2O)_2(SCN)_2 with One-dimensional Hydrogen-bonded Structure (DMSO = Dimethylsulfoxide)

The title complex Co（DMSO）2（H2O）2（SCN）2 has been prepared and structurally characterized. It crystallizes in monoclinic, space group P21/n with a= 5.1981（9）, b = 11.944（2）, c = 12.646（2） A,β = 98.686（2）°, V = 776.2（2） A^3, C6H16CoN2O4S4, Mr = 367.38, Z = 2, De = 1.572 g/cm^3, F（000） = 378 and μ（MoKa） = 1.646 mm^-1. The structure was refined to R= 0.0232 and wR = 0.0645 for 1241 observed reflections with I 〉 2σ（I）. In the title complex, each Co（II） atom is octahedrally coordinated by four O atoms from two DMSO ligands and two water molecules as well as two N atoms from SCN^- ions. The title molecules are connected to each other through intermolecular hydrogen bonds to form a 1-D structure extended by eight-membered Co2O4H2 rings.