The generation of chemically engineered essential oils(CEEOs)prepared from bi-heteroatomic reactions using ammonium thiocyanate as a source of bioactive compounds is described.The impact of the reaction on the chemica...The generation of chemically engineered essential oils(CEEOs)prepared from bi-heteroatomic reactions using ammonium thiocyanate as a source of bioactive compounds is described.The impact of the reaction on the chemical composition of the mixtures was qualitatively demonstrated through GC-MS,utilizing univariate and multivariate analysis.The reaction transformed most of the components in the natural mixtures,thereby expanding the chemical diversity of the mixtures.Changes in inhibition properties between natural and CEEOs were demonstrated through acetylcholinesterase TLC autography,resulting in a threefold increase in the number of positive events due to the modification process.The chemically engineered Origanum vulgare L.essential oil was subjected to bioguided fractionation,leading to the discovery of four new active compounds with similar or higher potency than eserine against the enzyme.The results suggest that the directed chemical transformation of essential oils can be a valuable strategy for discovering new acetylcholinesterase(AChE)inhibitors.展开更多
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.
High valent iron complexes Fe-X have been known to transfer their X group toward carbon radical species to form R–X bond.To utilize this capability of iron catalyst,novel photo-induced iron catalysis system had been ...High valent iron complexes Fe-X have been known to transfer their X group toward carbon radical species to form R–X bond.To utilize this capability of iron catalyst,novel photo-induced iron catalysis system had been developed in the difunctionalization of alkenes in the presence of radical initiator.However,the details of the reaction mechanism are still unclear,especially the transformations of the photocatalyst and the iron catalyst during the catalytic turnover.Herein,we expanded the photo-driven non-heme iron complex catalyzed thiocyanation of styrene substrate.This protocol exhibited broad substrate scope and high efficiency.Detailed mechanistic studies using various spectroscopies,such as UV-vis,mass spectrometry,transient absorption spectroscopy and X-ray absorption spectroscopy,revealed the transformations of photocatalyst[Ir^(Ⅲ)(ppy)_(3)]and group transfer catalyst[Fe^(Ⅱ)(bpmen)]^(2+).Real-time spectroscopies combined with mechanistic experiments demonstrated that[Ir^(Ⅳ)(ppy)_(3)]^(+)and[Fe^(Ⅲ)(bpmen)]^(3+)were the key intermediates involved in the reaction cycle.展开更多
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(NHP...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.展开更多
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 condition...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.展开更多
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...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.展开更多
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...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.展开更多
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 hi...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.展开更多
Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is...Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is attributed to the instability of Sn^(2+),which easily oxidizes to Sn^(4+),creating Sn vacancies and increasing the open-circuit voltage loss.In this work,we implemented tin thiocyanate(Sn(SCN)_(2))as an additive for passivating the bulk defects of a germanium-doped tin halide perovskite film.Adding Sn^(2+)and SCN-ions reduces the Sn and iodine vacancies,limiting non-radiative recombination and favoring longer charge-carrier dynamics.Moreover,the addition of Sn(SCN)_(2) induces a higher film crystallinity and preferential orientation of the(l00)planes parallel to the substrate.The passivated devices showed improved photovoltaic parameters with the best open-circuit voltage of 0.716 V and the best efficiency of 12.22%,compared to 0.647 V and 10.2%for the reference device.In addition,the passivated solar cell retains 88.7%of its initial efficiency after 80 min of illumination under 100 mW cm^(-2) and is substantially better than the control device,which reaches 82.6%of its initial power conversion efficiency only after 30 min.This work demonstrates the passivation potential of tin-based additives,which combined with different counterions give a relatively large space of choices for passivation of Sn-based perovskites.展开更多
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...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.展开更多
Semitransparent organic photovoltaics(STOPVs)have gained wide attention owing to their promising applications in building-integrated photovoltaics,agrivoltaics,and floating photovoltaics.Organic semiconductors with hi...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%.展开更多
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_(...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.展开更多
The site-selective C–H thiocyanation of quinoline has potential application value but remains undeveloped.We report herein an electrochemical C3-thiocyanation of quinoline derivatives under external oxidant-free cond...The site-selective C–H thiocyanation of quinoline has potential application value but remains undeveloped.We report herein an electrochemical C3-thiocyanation of quinoline derivatives under external oxidant-free conditions.The key to success for this reaction is the in situ formation of activated silylquinolinium salts.This method exhibits mild reaction conditions,broad substrate scope,and excellent site-selectivity.The practicality of this protocol is further demonstrated by a scale-up reaction,follow-up transformations,and late-stage thiocyanation of quinoline-based bioactive molecules.展开更多
A convenient and efficient phosphine-free procedure for the one-pot conversion of primary,secondary and tertiary alcohols into the corresponding alkyl thiocyanates or alkyl isothiocyanates is described using trichloro...A convenient and efficient phosphine-free procedure for the one-pot conversion of primary,secondary and tertiary alcohols into the corresponding alkyl thiocyanates or alkyl isothiocyanates is described using trichloroisocyanuric acid/NHUSCN.展开更多
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 f...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.展开更多
Schwertmannite is an amorphous iron(III)-oxyhydroxysulfate that forms in acid mine drainage(AMD) environments. The characteristic of high heavy metal adsorption capability makes schwertmannite a potentially useful, en...Schwertmannite is an amorphous iron(III)-oxyhydroxysulfate that forms in acid mine drainage(AMD) environments. The characteristic of high heavy metal adsorption capability makes schwertmannite a potentially useful, environmentally friendly material in wastewater treatment. Unstable schwertmannite is prone to recrystallization.Understanding the mechanisms that induce schwertmannite labilization and affect its capacity to remove heavy metals are of great environmental and geochemical significance.Thiocyanate(SCNˉ) is a hazardous pseudohalide that is also normally found in AMD.However, little is known about the impact of Fe(III)-binding ligand SCNˉ on schwertmannite stability and its subsequent capacity to bind trace elements. Here, we investigated the adsorption of SCNˉ on schwertmannite and subsequent mineral transformation to characterize this little-known process. The appearance of Fe2+indicated that the interactions between schwertmannite and SCNˉ may involve complexation and reduction reactions. Results showed that the majority of the adsorbed-SCNˉ was immobilized on schwertmannite during the 60-days transformation. The transformation rates of schwertmannite increased with increasing concentrations of SCNˉ. Goethite was detected as the dominant transformation product with or without SCNˉ. The mechanisms of SCNˉ-promoted dissolution of schwertmannite can be described as follows:(1) formation of Fe(III)–NCS complexes on the schwertmannite surface and in solution, a process which increases the reactivity of solid phase Fe(III);(2) the extraction of Fe(III) from schwertmannite by SCNˉ and subsequent schwertmannite dissolution; and(3) the formation of secondary minerals from extracted Fe(III). These findings may improve AMD treatment strategies and provide insight into the use and potential reuse of schwertmannite as a trace element sorbent.展开更多
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 i...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.展开更多
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 sui...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.展开更多
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 thiocyanohyd...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.展开更多
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 param...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.展开更多
基金support by Universidad Nacional de Rosario(80020180300114UR and 80020180100128UR)CONICET(PIP No 11220200102423)and FONCYT(PICT2015-3574 and PICT2018-01554)for the development of this work.
文摘The generation of chemically engineered essential oils(CEEOs)prepared from bi-heteroatomic reactions using ammonium thiocyanate as a source of bioactive compounds is described.The impact of the reaction on the chemical composition of the mixtures was qualitatively demonstrated through GC-MS,utilizing univariate and multivariate analysis.The reaction transformed most of the components in the natural mixtures,thereby expanding the chemical diversity of the mixtures.Changes in inhibition properties between natural and CEEOs were demonstrated through acetylcholinesterase TLC autography,resulting in a threefold increase in the number of positive events due to the modification process.The chemically engineered Origanum vulgare L.essential oil was subjected to bioguided fractionation,leading to the discovery of four new active compounds with similar or higher potency than eserine against the enzyme.The results suggest that the directed chemical transformation of essential oils can be a valuable strategy for discovering new acetylcholinesterase(AChE)inhibitors.
文摘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.
基金supported by the National Natural Science Foundation of China(22171216)the National Key R&D Program of China(2021YFA1500100).
文摘High valent iron complexes Fe-X have been known to transfer their X group toward carbon radical species to form R–X bond.To utilize this capability of iron catalyst,novel photo-induced iron catalysis system had been developed in the difunctionalization of alkenes in the presence of radical initiator.However,the details of the reaction mechanism are still unclear,especially the transformations of the photocatalyst and the iron catalyst during the catalytic turnover.Herein,we expanded the photo-driven non-heme iron complex catalyzed thiocyanation of styrene substrate.This protocol exhibited broad substrate scope and high efficiency.Detailed mechanistic studies using various spectroscopies,such as UV-vis,mass spectrometry,transient absorption spectroscopy and X-ray absorption spectroscopy,revealed the transformations of photocatalyst[Ir^(Ⅲ)(ppy)_(3)]and group transfer catalyst[Fe^(Ⅱ)(bpmen)]^(2+).Real-time spectroscopies combined with mechanistic experiments demonstrated that[Ir^(Ⅳ)(ppy)_(3)]^(+)and[Fe^(Ⅲ)(bpmen)]^(3+)were the key intermediates involved in the reaction cycle.
基金supported by the National Natural Science Foundation of China(22201087)the National Key R&D Program of China(2022YFA1503200)Guangdong Basic and Applied Basic Research Foundation(2022A1515012507)。
文摘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.
基金This project was financially supported by the National Natural Science Foundation of China （No. 21302014）.
文摘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.
基金We gratefully acknowledge National Natural Science Foundation of China(22101291,22171277,21821002)National Key R&D Program of China(2021YFA1500200)+1 种基金Shanghai Rising-Star Program(20QA1411400)Shanghai Institute of Organic Chemistry,and State Key Laboratory of Organometallic Chemistry for finan cial support.
文摘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.
基金support from the National Nature Science Foundation of China(nos.21532009,91956202,21821002,21790330,and 21761142010)the Science and Technology Commission of Shanghai Municipality(nos.19590750400 and 17JC1401200)+1 种基金the strategic Priority Research Program(no.XDB20000000),the Key Research Program of Frontier Science(no.QYZDJSSW-SLH055)the International Partnership Program(no.121731KYSB20190016)of the Chinese Academy of Sciences.P.C.also thanks the Youth Innovation Promotion Association CAS(no.2018292).
文摘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.
基金Y.Du acknowledges the National Natural Science Foundation of China(No.22071175)for financial support.
文摘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.
基金support from the Focus Group‘Next Generation Organic Photovoltaics’participating with the Dutch Institute for Fundamental Energy Research(DIFFER)(FOM130)Advanced Materials research program of the Zernike National Research Centre under the Bonus Incentive Scheme(BIS)of the Dutch Ministry for Education,Culture and Science.
文摘Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is attributed to the instability of Sn^(2+),which easily oxidizes to Sn^(4+),creating Sn vacancies and increasing the open-circuit voltage loss.In this work,we implemented tin thiocyanate(Sn(SCN)_(2))as an additive for passivating the bulk defects of a germanium-doped tin halide perovskite film.Adding Sn^(2+)and SCN-ions reduces the Sn and iodine vacancies,limiting non-radiative recombination and favoring longer charge-carrier dynamics.Moreover,the addition of Sn(SCN)_(2) induces a higher film crystallinity and preferential orientation of the(l00)planes parallel to the substrate.The passivated devices showed improved photovoltaic parameters with the best open-circuit voltage of 0.716 V and the best efficiency of 12.22%,compared to 0.647 V and 10.2%for the reference device.In addition,the passivated solar cell retains 88.7%of its initial efficiency after 80 min of illumination under 100 mW cm^(-2) and is substantially better than the control device,which reaches 82.6%of its initial power conversion efficiency only after 30 min.This work demonstrates the passivation potential of tin-based additives,which combined with different counterions give a relatively large space of choices for passivation of Sn-based perovskites.
基金We acknowledge the National Natural Science Foundation of China(No.22071175)for financial supportX.B.Wang thanks the financial support from the National Natural Science Foundation of China(Nos.21908018,22078174),and Qi Lu Young Scholar Start-up Foundation of Shandong University.
文摘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.
基金financially supported by the Sichuan Science and Technology Program (2023YFH0086, 2023YFH0085, 2023YFH0087 and 2023NSFSC0990)the State Key Laboratory of Polymer Materials Engineering (sklpme2022-3-02 and sklpme2023-2-11)the Tibet Foreign Experts Program (2022wz002)
文摘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%.
文摘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.
基金We thank the Natural Science Foundation of Shandong Province(ZR202oMB005)the Youth Innovation Science and Technology Plan of Colleges and Universities in Shandong Province(2021KJ076)for financial support.
文摘The site-selective C–H thiocyanation of quinoline has potential application value but remains undeveloped.We report herein an electrochemical C3-thiocyanation of quinoline derivatives under external oxidant-free conditions.The key to success for this reaction is the in situ formation of activated silylquinolinium salts.This method exhibits mild reaction conditions,broad substrate scope,and excellent site-selectivity.The practicality of this protocol is further demonstrated by a scale-up reaction,follow-up transformations,and late-stage thiocyanation of quinoline-based bioactive molecules.
基金Shahid Chamran University Research Council,Ahvaz,for financial support of this investigation
文摘A convenient and efficient phosphine-free procedure for the one-pot conversion of primary,secondary and tertiary alcohols into the corresponding alkyl thiocyanates or alkyl isothiocyanates is described using trichloroisocyanuric acid/NHUSCN.
文摘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.
基金supported by the National Natural Science Foundation of China (Nos. 41330639 and 41720104004)the National Key Research and Development Program of China (No. 2017YFD0801000)
文摘Schwertmannite is an amorphous iron(III)-oxyhydroxysulfate that forms in acid mine drainage(AMD) environments. The characteristic of high heavy metal adsorption capability makes schwertmannite a potentially useful, environmentally friendly material in wastewater treatment. Unstable schwertmannite is prone to recrystallization.Understanding the mechanisms that induce schwertmannite labilization and affect its capacity to remove heavy metals are of great environmental and geochemical significance.Thiocyanate(SCNˉ) is a hazardous pseudohalide that is also normally found in AMD.However, little is known about the impact of Fe(III)-binding ligand SCNˉ on schwertmannite stability and its subsequent capacity to bind trace elements. Here, we investigated the adsorption of SCNˉ on schwertmannite and subsequent mineral transformation to characterize this little-known process. The appearance of Fe2+indicated that the interactions between schwertmannite and SCNˉ may involve complexation and reduction reactions. Results showed that the majority of the adsorbed-SCNˉ was immobilized on schwertmannite during the 60-days transformation. The transformation rates of schwertmannite increased with increasing concentrations of SCNˉ. Goethite was detected as the dominant transformation product with or without SCNˉ. The mechanisms of SCNˉ-promoted dissolution of schwertmannite can be described as follows:(1) formation of Fe(III)–NCS complexes on the schwertmannite surface and in solution, a process which increases the reactivity of solid phase Fe(III);(2) the extraction of Fe(III) from schwertmannite by SCNˉ and subsequent schwertmannite dissolution; and(3) the formation of secondary minerals from extracted Fe(III). These findings may improve AMD treatment strategies and provide insight into the use and potential reuse of schwertmannite as a trace element sorbent.
基金Partial support for this work by Chamran University Research Council is gratefully acknowledged.
文摘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.
基金supported by the National Natural Science Foundation of China(No.81370755)
文摘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.
文摘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.
基金Supported by the Nature Science Fund Project of Hubei Province
文摘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.
