An efficient new method has been developed to synthesize N2‐alkyl 1,2,3‐triazole products by tol‐uenesulfonic acid （TsOH） catalyzed addition of N1‐Ts substituted 1,2,3‐triazoles to olefins. The reac‐tions of m...An efficient new method has been developed to synthesize N2‐alkyl 1,2,3‐triazole products by tol‐uenesulfonic acid （TsOH） catalyzed addition of N1‐Ts substituted 1,2,3‐triazoles to olefins. The reac‐tions of monosubstituted and unsubstituted triazole substrates with various olefins, including vinyl esters, are explored.展开更多
To explore the denitration mechanism of iron-vanadium/activated carbon(Fe-V/AC)catalysts in ammonia-selective catalytic reduction(NH_(3)-SCR),the physicochemical properties of Fe-V/AC catalysts were characterized.The ...To explore the denitration mechanism of iron-vanadium/activated carbon(Fe-V/AC)catalysts in ammonia-selective catalytic reduction(NH_(3)-SCR),the physicochemical properties of Fe-V/AC catalysts were characterized.The denitration activities of the Fe-V/AC catalysts in the range of 150-300℃ were evaluated.The increase in denitration temperature leads to the highest and fastest recovery rate of NO conversion in the 10Fe-15V/AC catalyst.However,more metal oxides were attached to the catalyst surface as the V loading increased,and the accumulation occurred.The surface-active components are FeO,Fe_(2)O_(3),Fe_(3)O_(4),VO_(2),and V_(2)O_(5).In addition,the increase in the V loading induced a series of modification effects.A large amount of Fe^(3+)was reduced to Fe^(2+),and a large amount of V^(4+)was oxidized to V^(5+).The surface oxygen species(O_(α))were transformed into lattice oxygen(O_(β)).The presence of a large amount of V species deteriorated the pore-structure parameters and destroyed the oxygen-containing functional groups.Increasing the V loading can effectively increase the Lewis acid sites,thereby promoting NH_(3) adsorption and NO reduction and increasing the stretching vibration of weakly adsorbed ammonia species on the catalyst.The NH_(3) adsorption process produces a notable increase in the concentration of monodentate nitrite(NH_(4)^(+)).The NH_(3)-SCR denitration mechanism of the Fe-V/AC catalyst includes reaction gas adsorption,catalytic denitration of metal active components,and gas desorption.展开更多
A copper-catalyzedα-selective C–H trifluoromethylation of acrylamides with TMSCF3 is described.A wide range of arenes and heteroarenes at theβ-position of acrylamides are compatible with the reaction,affording the ...A copper-catalyzedα-selective C–H trifluoromethylation of acrylamides with TMSCF3 is described.A wide range of arenes and heteroarenes at theβ-position of acrylamides are compatible with the reaction,affording the corresponding(E)-trifluoromethylated products in moderate to good yields.The reaction proceeded fast and can be completed within 30 min.展开更多
Polymerization of 2-(4-halophenyl)-1,3-butadiene(2-XPB) and their copolymerization with isoprene using a yttrium catalyst have been examined. The β-diketiminato yttrium bis(alkyl) complex(1) activated by [Ph_3 C][B(C...Polymerization of 2-(4-halophenyl)-1,3-butadiene(2-XPB) and their copolymerization with isoprene using a yttrium catalyst have been examined. The β-diketiminato yttrium bis(alkyl) complex(1) activated by [Ph_3 C][B(C_(6) F_(5))_(4)] and Ali Bu3 shows high cis-1,4-selectivity(>98%) for the polymerization of 2-XPB(2-XPB = 2-FPB, 2-Cl PB and 2-Br PB) to afford halogenated plastic poly(dienes) with glass transition temperatures of30–55 ℃. Moreover, the copolymerization of 2-XPB with isoprene(IP) has also been achieved by this catalyst, and the insertion ratios of 2-XPB can be facilely tuned in a full range of 0%–100% simply by changing the 2-XPB-to-IP ratio. Quantitative hydrogenation of cis-1,4-poly(2-XPB) results in perfect alternating ethylene-halostyrene copolymers, and an alternating copolymer of 4-vinylbenzoic acid with ethylene is obtained by a consecutive reaction of ethylene-4-bromostyrene copolymer with ^(n)Bu Li, CO_(2) and HCl.展开更多
Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost target...Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost targets for CO2 capture. This study attempts to develop membranes with multiple permselective mechanisms in order to enhance CO2 separation performance of fixed carder membrane. In this study, a novel membrane with multiplepermselective mechanisms of solubility selectivity and reaction selectivity was developed by incorporating CO2-selective adsorptive silica nanoparticles in situ into the tertiary amine containing polyamide membrane formed by interfacial polymerization （IP）. Various techniques were employed to characterize the polyamide and polyam-ide-silica composite membranes. The TGA result shows that nanocomposite membranes exhlbit superior-thermal stability than pure polyamide membranes. In addition, gas permeation experiments show that both nanocomposite membranes have larger CO2 permeance than pure polyamide membranes. The enhanced CO2/N2 separation performance for nanocomposite membranes is mainly due to the thin film thickness, and multiple permselective mechanisms of solubility selectivity and reaction selectivity.展开更多
Based on poly(vinyl chloride) membranes, a novel miniaturized screen-printed all-solid-state copper(II)-selective electrode has been developed for applications in environmental monitoring. Performance and applicabilit...Based on poly(vinyl chloride) membranes, a novel miniaturized screen-printed all-solid-state copper(II)-selective electrode has been developed for applications in environmental monitoring. Performance and applicability of the ion-selective electrode (ISE) have been proved by potentiometric investigations. Conducting polymers were used as intermediate layers and as solid contacts between the ion-selective membrane and the graphite transducer. The ion-complexing reagent 2-mercapto-benzoxazole was incorporated into poly(vinyl chloride) membranes. In the concentration range 10<sup>-6</sup> - 10<sup>-2</sup> mol/L, the ISE exhibited a linear Nernstian potential response to copper(II) with an average slope value of 28 mV/decade. The detection limit was 3 × 10<sup>-7</sup> mol/L. The electrode exhibits a short response time (<10 s) and can be used in the range of pH = 3 - 7. Selectivity coefficents against certain interfering ions are investigated. The life time of the electrode under laboratory conditions was approximately 12-month. The electrode was applied in the investigation of different aqueous environmental samples and the electrode characteristics were described. The copper(II) ASS electrode has also successfully been used in potentiometric, complexometric titrations with ethylenediaminetetraacetic acid.展开更多
Tetra(amino)azacalix[4]arene skeleton was functionalized at the bridging NH sites using various aromatic aldehydes via formation of imidazobenzimidazole fused heterocycles.X-ray single crystal analysis revealed distor...Tetra(amino)azacalix[4]arene skeleton was functionalized at the bridging NH sites using various aromatic aldehydes via formation of imidazobenzimidazole fused heterocycles.X-ray single crystal analysis revealed distorted 1,3-alternate conformations for the resulting macrocycles.Anthracenyl and pyrenyl modified imidazobenzimidazole fused aza-calix[4]arenes existed as dimers in the solid state,associated mainly through-stacking interactions between the planar polycyclic fluorophores.The tetrapyrenyl modified product was further used as a Zn^(2+)-selective sensor,which showed naked-eye detected color change and enhanced excimer emission.The stoichiometry between the sensor and Zn2+was determined to be 1:1 and the association constant was 1.1×10^(5)L/mol.The sensing process was highly selective and showed strong anti-interference with presence of other cations.The UV-vis spectral changes in the sensing process were completely reversible by alternate addition of Zn^(2+) and F^(-),showing an efficient“on-off-on”result.展开更多
Understanding the influence of HCl on the NH_(3)-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts.The formation of chlorate species on the surface of...Understanding the influence of HCl on the NH_(3)-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts.The formation of chlorate species on the surface of the synthesized SbCeO_(x)catalyst,induced by HCl,significantly enhances low-temperature activity,as evidenced by a 30%increase in NO conversion at 155℃.Furthermore,it improves N_(2)selectivity at high temperatures,with a notable 17%increase observed at 405℃.Both experimental results and density functional theory calculations confirm that chlorate species form at Ce sites.This formation facilitates the creation of oxygen vacancies,boosting the oxygen exchange capacity.It also increases NH_(3)adsorption at the Ce sites,promotes the formation of Sb-OH,and reduces competitive OH adsorption on these sites.Notably,compared with the reaction mechanism without HCl,the presence of chlorate species enhances NH_(3)adsorption and activation,which is vital for subsequent catalytic reactions.展开更多
A hydrogen bond-assisted α-selective glycosylation reaction by using 4,6-dibenzyloxy-1,3,5-triazin-2-yl(DBT) β-glycosyl donors was developed for the efficient construction of 1,2-cis-α-glycosidic bond in natural pr...A hydrogen bond-assisted α-selective glycosylation reaction by using 4,6-dibenzyloxy-1,3,5-triazin-2-yl(DBT) β-glycosyl donors was developed for the efficient construction of 1,2-cis-α-glycosidic bond in natural products. This method was applied successfully to the direct synthesis of complex oligosaccharidederived glycolipids with simple protecting chemistry. Mechanistic studies using the NMR spectroscopy and DFT calculation provide a proof of concept for hydrogen bond-assisted glycosylation reaction towardsα-specific construction of O-glycosidic linkage.展开更多
Coal-based H2 generation has abruptly increased in recent years.The PSA-VPSA-SC process is the matured and standard framework for H2 purification and CO_(2) capture in many existing plants,including normal and vacuum ...Coal-based H2 generation has abruptly increased in recent years.The PSA-VPSA-SC process is the matured and standard framework for H2 purification and CO_(2) capture in many existing plants,including normal and vacuum pressure swing adsorption units in series(PSA-VPSA),and shallow condensation unit(SC).However,this standard process is frequently subjected to low H2 recovery ratio and high purification cost.In this work,H2-selective and C02-selective membrane units,i.e.,HM and CO_(2) M,are attempted to support the standard process and ameliorate constraints.In the beginning,HM unit is arranged after VPSA to enhance H2 recovery from the decarbonized stream,i.e.,the PSA-VPSA-SC/HM process.As a result,H2 recovery ratio can be enhanced significantly from 83%to 98%.In the following,VPSA is replaced with CO_(2) M unit to reduce investment and operation cost,i.e.,the PSA-CO_(2) M-SC/HM process.Accordingly,the specific purification cost is diminished from 33.46 to 32.02 USD·(103 m^(3) H_(2))-1,saved by 4.3%,meanwhile the construction cost is falling back and just a little higher than that for the standard process.In the end,another CO_(2) M unit is launched before PSA,i.e.,the CO_(2) M-PSA-CO_(2) M-SC/HM process,which could unbundle CO_(2) enrichment partially from H2 purification,and then save more investment and operation cost.In comparison with the standard process,this ultimate retrofitted process can be superior in all the three crucial indices,i.e.,recovery ratio,investment,and specific purification cost.On the whole,coal-based H2 generation can be ameliorated significantly through high efficient H2-selective and CO_(2)-selective membrane units.展开更多
Cellular growth,development,and differentiation are tightly controlled by a conserved biological mechanism:the cell cycle.This cycle is primarily regulated by cyclin-dependent kinase(CDK)-cyclin complexes,checkpoint k...Cellular growth,development,and differentiation are tightly controlled by a conserved biological mechanism:the cell cycle.This cycle is primarily regulated by cyclin-dependent kinase(CDK)-cyclin complexes,checkpoint kinases,and CDK inhibitors.Deregulation of the cell cycle is a hallmark of the transformation of normal cells into tumor cells.Given its importance in tumorigenesis,several cell cycle inhibitors have emerged as potential therapeutic drugs for the treatment of cancers-both as singleagent therapy and in combination with traditional cytotoxic or molecular targeting agents.In this review,we discuss the mechanisms underlying cell cycle regulation and present small-molecule anticancer drugs that are under development,including both pan-CDK inhibitors and CDK4/6-selective inhibitors.In addition,we provide an outline of some promising CDK inhibitors currently in preclinical and clinical trials that target cell cycle abnormalities in various cancers.展开更多
This paper describes preparation, characterization and electrochemical performance of novel planar miniaturized all-solid-state (ASS) screen-printed potentiometric sensors for the detection of Ca2+ ions in environment...This paper describes preparation, characterization and electrochemical performance of novel planar miniaturized all-solid-state (ASS) screen-printed potentiometric sensors for the detection of Ca2+ ions in environmental samples. Screen-printed graphite-based ion-selective electrodes (ISEs) and screen-printed reference electrodes based on silver-containing pastes have been applied in a space saving manner on common ceramic substrates with small dimensions. Applications to environmental samples are shown by direct potentiometry and potentiometric titrations in real water samples. Conducting polymers (CPs) have been used as solid-contact materials and as intermediate layer between the polyvinyl chloride (PVC)-containing ion-selective membrane and the graphite-containing substrate. Different diamides have been incorporated into the PVC membrane. In the range from 10-4 mol/L to 10-1 mol/L, the ISEs show linear slopes of 27 mV/decade, which is close to the Nernstian response. Moreover, the ISEs have response times of 6 months. The novel potentiometric ASS sensors enable simple and exact Ca2+ determinations in real samples.展开更多
A diester-calix[4]crown-4-ether bearing mono (azophenol) moiety shows a larger spectral change toward Ca2+ than other alkali and alkaline eafth cations.
Transition metal-catalyzed hydrostannylation of alkynes is an atom-economic way towards valuableα-vinylstannanes.However,directing-group-free examples for the construction ofα-adducts are rare and mostly undergo the...Transition metal-catalyzed hydrostannylation of alkynes is an atom-economic way towards valuableα-vinylstannanes.However,directing-group-free examples for the construction ofα-adducts are rare and mostly undergo the M-Sn species insertion process.Here,we report an efficient cobalt-catalyzed highlyα-selective hydrostannylation of terminal alkynes via M-H species,using readily available Bu3Sn H and easily accessible as well as bench-stable ligand.The robust catalytic system,bearing good functional group tolerance and operational simplicity,provides theα-vinylstannanes in moderate to excellent yields with≥97:3 rr averagely.The efficiency of the reaction is investigated with turnover number(TON)up to 10,000 and turnover frequency(TOF)up to 144,000 h^(-1),respectively.The synthetic utility of theα-vinylstannanes is proved by further derivatizations towards the 1,1-disubstituted alkenes via Kosugi-Migita-Stille cross-coupling,conjugated alkene,α-vinyliodine,α-vinylazide,and allyl alcohol.Several control experiments,deuterium-labeling experiment and density functional theory(DFT)calculations are conducted to reveal the preliminary mechanism.展开更多
A novel poly(vinyl chloride)membrane potentiometric sensor for chromium(Ⅲ)ions based on the use of 5,5′-(1,4-phenylene)bis(3-(naphthalen-1-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide)as a neutral ionophore was deve...A novel poly(vinyl chloride)membrane potentiometric sensor for chromium(Ⅲ)ions based on the use of 5,5′-(1,4-phenylene)bis(3-(naphthalen-1-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide)as a neutral ionophore was developed.The optimum composition of the best performing membrane contained ionophore,potassium tetrakis(p-chlorophenyl)borate(KTpClPB),dibutyl phthalate(DBP),and poly(vinyl chloride)(PVC)in the ratio of 5.5:1.5:55:38(mg).The sensor exhibits a working concentration range of 1.0×10^(-5)-1.0×10^(-1 )mol L^(−1) and a detection limit of 1.7×10^(-6) mol L^(−1).The sensor shows good selectivity for chromium(III)ions over a number of cations including alkali,alkaline earth,heavy and transition metals.The response time of the sensor is 8 s.In addition,the developed sensor shows good reusability and stability.The sensor operates in the wide pH range of 5.0-11.0.The sensor could be used as an indicator electrode in the quantification of Cr^(3+)ions by potentiometric titration against ethylenediaminetetraacetic acid(EDTA).Finally,this sensor was successfully used for the determination of chromium(III)in commercial water,purification water and wastewater.展开更多
This work describes stereoselective preparation ofβ-C-aryl/vinyl glucosides via mild Ni-catalyzed reductive arylation and vinylation of C1-glucosyl halides with aryl and vinyl halides.A broad range of aryl halides an...This work describes stereoselective preparation ofβ-C-aryl/vinyl glucosides via mild Ni-catalyzed reductive arylation and vinylation of C1-glucosyl halides with aryl and vinyl halides.A broad range of aryl halides and vinyl halides were employed to yield C-aryl/vinyl glucosides in 42%–93%yields.Good to excellentβ-selectivities were obtained for C-glucosides by using tridentate ligand.展开更多
A simple methodology has been developed for the synthesis of highlyβ-selective O-glycosylation scaffolds of wider substrate scope under mild conditions using a self-assembled hexameric capsule.The reaction conditions...A simple methodology has been developed for the synthesis of highlyβ-selective O-glycosylation scaffolds of wider substrate scope under mild conditions using a self-assembled hexameric capsule.The reaction conditions are compatible with a wide range of functional groups.Extensive control experiments and theoretical studies established that the reaction takes place inside the capsule cavity.The substrates are activated via a proton wire as seen in some enzymes,and the reactions follow an SN2 pathway through a loose transition state.The advantages of this methodology are selectivity,high yields and scalability;the catalyst is readily recovered and reused.The methodology was adapted to the synthesis of mesomorphic glycosides and anti-tumour agents in short synthetic routes.展开更多
Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NOx with NH3. A series of characterization including X-ray d...Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NOx with NH3. A series of characterization including X-ray diffraction （XRD）, high-resolution transmission electron microscope （HR-TEM）, Bmnaue-Emmett-Teller （BET） surface area analysis, H2 temperature- programmed reduction （H2-TPR）, and X-ray photoelectron spectroscopy （XPS） were used to evaluate the influence of the physicochemical properties on NH3-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO2-CeO2 binary oxide for the low temperature NH3-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO2 and H2O. Cr-Zr-Ce mixed oxide exhibited〉80% NO,. conversion at a wide temperature window of 100 ℃ 300℃. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence ofCr6 ＋. The present mixed oxide can be a candidate for the low temperature abatement of NOx.展开更多
In this paper,we report the fabrication of cobalt-doped de-NO_(x)catalyst by pyrolyzing an analogous metal-organic framework-74(MOF-74)containing Fe&Mn.The resulted catalyst exhibits distinctive microstructures of...In this paper,we report the fabrication of cobalt-doped de-NO_(x)catalyst by pyrolyzing an analogous metal-organic framework-74(MOF-74)containing Fe&Mn.The resulted catalyst exhibits distinctive microstructures of manganese,cobalt,and iron immobilized on N-doped carbon nanotubes(CNTs).It is found through experiments that the trimetallic catalyst Fe_(2)Mn_(1)Co_(0.5)/CNTs-50 has the best NH_(3)-selective catalytic reduction(SCR)performance.The Fe_(2)Mn_(1)Co_(0.5)/CNTs-50 exhibited excellent water and sulfur resistance and good stability under the harsh gas environment of 250℃ and/or 170℃,NO=NH_(3)=1,000 ppm,8 vol.%O_(2),20 vol.%H2O,1,000 ppm SO_(2),and gas hourly space velocity(GHSV)=75,000 h^(-1).The de-NO_(x)conversion was maintained about 55%and 25%after 192 h.The water and sulfur resistance performance were much higher than commercial vanadium series catalyst.The highly water and sulfur resistance performance may be attributed to the unique core-shell microstructure and the synergistic effect of manganese,cobalt,and iron which helps reduce the formation for byproducts(NH_(4)HSO_(4)).This study may promote to explore the development of a high stability catalyst for low-temperature selective catalytic reduction of NO_(x)with NH_(3).展开更多
基金supported by the National Natural Science Foundation of China (21272268 and 21472237)~~
文摘An efficient new method has been developed to synthesize N2‐alkyl 1,2,3‐triazole products by tol‐uenesulfonic acid （TsOH） catalyzed addition of N1‐Ts substituted 1,2,3‐triazoles to olefins. The reac‐tions of monosubstituted and unsubstituted triazole substrates with various olefins, including vinyl esters, are explored.
基金financially supported by National Natural Science Foundation of China(No.52264043).
文摘To explore the denitration mechanism of iron-vanadium/activated carbon(Fe-V/AC)catalysts in ammonia-selective catalytic reduction(NH_(3)-SCR),the physicochemical properties of Fe-V/AC catalysts were characterized.The denitration activities of the Fe-V/AC catalysts in the range of 150-300℃ were evaluated.The increase in denitration temperature leads to the highest and fastest recovery rate of NO conversion in the 10Fe-15V/AC catalyst.However,more metal oxides were attached to the catalyst surface as the V loading increased,and the accumulation occurred.The surface-active components are FeO,Fe_(2)O_(3),Fe_(3)O_(4),VO_(2),and V_(2)O_(5).In addition,the increase in the V loading induced a series of modification effects.A large amount of Fe^(3+)was reduced to Fe^(2+),and a large amount of V^(4+)was oxidized to V^(5+).The surface oxygen species(O_(α))were transformed into lattice oxygen(O_(β)).The presence of a large amount of V species deteriorated the pore-structure parameters and destroyed the oxygen-containing functional groups.Increasing the V loading can effectively increase the Lewis acid sites,thereby promoting NH_(3) adsorption and NO reduction and increasing the stretching vibration of weakly adsorbed ammonia species on the catalyst.The NH_(3) adsorption process produces a notable increase in the concentration of monodentate nitrite(NH_(4)^(+)).The NH_(3)-SCR denitration mechanism of the Fe-V/AC catalyst includes reaction gas adsorption,catalytic denitration of metal active components,and gas desorption.
基金the National Natural Science Foundation of China(Nos.21472211,21502212,21772211)Youth Innovation Promotion Association CAS(Nos.2014229 and2018293)+1 种基金Institutes for Drug Discovery and Development,Chinese Academy of Sciences(No.CASIMM 0120163006)Science and Technology Commission of Shanghai Municipality(No.17JC1405000)for financial support
文摘A copper-catalyzedα-selective C–H trifluoromethylation of acrylamides with TMSCF3 is described.A wide range of arenes and heteroarenes at theβ-position of acrylamides are compatible with the reaction,affording the corresponding(E)-trifluoromethylated products in moderate to good yields.The reaction proceeded fast and can be completed within 30 min.
基金financially supported by the National Natural Science Foundation of China (Nos. 21634007 and 51773193)the Department of Science and Technology of Jilin Province(No. 20180101171JC)。
文摘Polymerization of 2-(4-halophenyl)-1,3-butadiene(2-XPB) and their copolymerization with isoprene using a yttrium catalyst have been examined. The β-diketiminato yttrium bis(alkyl) complex(1) activated by [Ph_3 C][B(C_(6) F_(5))_(4)] and Ali Bu3 shows high cis-1,4-selectivity(>98%) for the polymerization of 2-XPB(2-XPB = 2-FPB, 2-Cl PB and 2-Br PB) to afford halogenated plastic poly(dienes) with glass transition temperatures of30–55 ℃. Moreover, the copolymerization of 2-XPB with isoprene(IP) has also been achieved by this catalyst, and the insertion ratios of 2-XPB can be facilely tuned in a full range of 0%–100% simply by changing the 2-XPB-to-IP ratio. Quantitative hydrogenation of cis-1,4-poly(2-XPB) results in perfect alternating ethylene-halostyrene copolymers, and an alternating copolymer of 4-vinylbenzoic acid with ethylene is obtained by a consecutive reaction of ethylene-4-bromostyrene copolymer with ^(n)Bu Li, CO_(2) and HCl.
基金Supported by the National Natural Science Foundation of China （20836006）, the National Basic Research Program （2009CB623405）, the Science ＆ Technology Pillar Program of Tianjin （10ZCKFSH01700）, the Programme of Introducing Talents of Discipline to Universities （B06006）, and the Cheung Kong Scholar Program for Innovative Teams of the Ministry of Education （IRT0641）.
文摘Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost targets for CO2 capture. This study attempts to develop membranes with multiple permselective mechanisms in order to enhance CO2 separation performance of fixed carder membrane. In this study, a novel membrane with multiplepermselective mechanisms of solubility selectivity and reaction selectivity was developed by incorporating CO2-selective adsorptive silica nanoparticles in situ into the tertiary amine containing polyamide membrane formed by interfacial polymerization （IP）. Various techniques were employed to characterize the polyamide and polyam-ide-silica composite membranes. The TGA result shows that nanocomposite membranes exhlbit superior-thermal stability than pure polyamide membranes. In addition, gas permeation experiments show that both nanocomposite membranes have larger CO2 permeance than pure polyamide membranes. The enhanced CO2/N2 separation performance for nanocomposite membranes is mainly due to the thin film thickness, and multiple permselective mechanisms of solubility selectivity and reaction selectivity.
文摘Based on poly(vinyl chloride) membranes, a novel miniaturized screen-printed all-solid-state copper(II)-selective electrode has been developed for applications in environmental monitoring. Performance and applicability of the ion-selective electrode (ISE) have been proved by potentiometric investigations. Conducting polymers were used as intermediate layers and as solid contacts between the ion-selective membrane and the graphite transducer. The ion-complexing reagent 2-mercapto-benzoxazole was incorporated into poly(vinyl chloride) membranes. In the concentration range 10<sup>-6</sup> - 10<sup>-2</sup> mol/L, the ISE exhibited a linear Nernstian potential response to copper(II) with an average slope value of 28 mV/decade. The detection limit was 3 × 10<sup>-7</sup> mol/L. The electrode exhibits a short response time (<10 s) and can be used in the range of pH = 3 - 7. Selectivity coefficents against certain interfering ions are investigated. The life time of the electrode under laboratory conditions was approximately 12-month. The electrode was applied in the investigation of different aqueous environmental samples and the electrode characteristics were described. The copper(II) ASS electrode has also successfully been used in potentiometric, complexometric titrations with ethylenediaminetetraacetic acid.
基金supported by National Natural Science Foundation of China(Nos.21971223 and 21772178).
文摘Tetra(amino)azacalix[4]arene skeleton was functionalized at the bridging NH sites using various aromatic aldehydes via formation of imidazobenzimidazole fused heterocycles.X-ray single crystal analysis revealed distorted 1,3-alternate conformations for the resulting macrocycles.Anthracenyl and pyrenyl modified imidazobenzimidazole fused aza-calix[4]arenes existed as dimers in the solid state,associated mainly through-stacking interactions between the planar polycyclic fluorophores.The tetrapyrenyl modified product was further used as a Zn^(2+)-selective sensor,which showed naked-eye detected color change and enhanced excimer emission.The stoichiometry between the sensor and Zn2+was determined to be 1:1 and the association constant was 1.1×10^(5)L/mol.The sensing process was highly selective and showed strong anti-interference with presence of other cations.The UV-vis spectral changes in the sensing process were completely reversible by alternate addition of Zn^(2+) and F^(-),showing an efficient“on-off-on”result.
文摘Understanding the influence of HCl on the NH_(3)-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts.The formation of chlorate species on the surface of the synthesized SbCeO_(x)catalyst,induced by HCl,significantly enhances low-temperature activity,as evidenced by a 30%increase in NO conversion at 155℃.Furthermore,it improves N_(2)selectivity at high temperatures,with a notable 17%increase observed at 405℃.Both experimental results and density functional theory calculations confirm that chlorate species form at Ce sites.This formation facilitates the creation of oxygen vacancies,boosting the oxygen exchange capacity.It also increases NH_(3)adsorption at the Ce sites,promotes the formation of Sb-OH,and reduces competitive OH adsorption on these sites.Notably,compared with the reaction mechanism without HCl,the presence of chlorate species enhances NH_(3)adsorption and activation,which is vital for subsequent catalytic reactions.
基金financially supported by the State Key Laboratory of Natural and Biomimetic Drugs (No. K202216)the National Natural Science Foundation of China (Nos. 21907004 and 81821004)+2 种基金the National Key R&D Program of China (No.2018YFA0507602)the Beijing Outstanding Young Scientist Program(No. BJJWZYJH01201910001001)a Grant-in-Aid for Scientific Research from the Ministry of Education,Culture,Sports,Science and Technology,Japan。
文摘A hydrogen bond-assisted α-selective glycosylation reaction by using 4,6-dibenzyloxy-1,3,5-triazin-2-yl(DBT) β-glycosyl donors was developed for the efficient construction of 1,2-cis-α-glycosidic bond in natural products. This method was applied successfully to the direct synthesis of complex oligosaccharidederived glycolipids with simple protecting chemistry. Mechanistic studies using the NMR spectroscopy and DFT calculation provide a proof of concept for hydrogen bond-assisted glycosylation reaction towardsα-specific construction of O-glycosidic linkage.
基金financial supports from the National Natural Science Foundation of China(Grant No.21978033,U1663223&21978035)China Postdoctoral Science Foundation(2019M650055)+3 种基金Liaoning Province Funds(XLYC1907063)the Changjiang Scholars Program(T2012049)the Fundamental Research Funds for the Central Universities(DUT19TD33)the Opening Project of Guangxi Key Laboratory of Petrochemical Resource Processing&Process Intensification Technology(2018K009)。
文摘Coal-based H2 generation has abruptly increased in recent years.The PSA-VPSA-SC process is the matured and standard framework for H2 purification and CO_(2) capture in many existing plants,including normal and vacuum pressure swing adsorption units in series(PSA-VPSA),and shallow condensation unit(SC).However,this standard process is frequently subjected to low H2 recovery ratio and high purification cost.In this work,H2-selective and C02-selective membrane units,i.e.,HM and CO_(2) M,are attempted to support the standard process and ameliorate constraints.In the beginning,HM unit is arranged after VPSA to enhance H2 recovery from the decarbonized stream,i.e.,the PSA-VPSA-SC/HM process.As a result,H2 recovery ratio can be enhanced significantly from 83%to 98%.In the following,VPSA is replaced with CO_(2) M unit to reduce investment and operation cost,i.e.,the PSA-CO_(2) M-SC/HM process.Accordingly,the specific purification cost is diminished from 33.46 to 32.02 USD·(103 m^(3) H_(2))-1,saved by 4.3%,meanwhile the construction cost is falling back and just a little higher than that for the standard process.In the end,another CO_(2) M unit is launched before PSA,i.e.,the CO_(2) M-PSA-CO_(2) M-SC/HM process,which could unbundle CO_(2) enrichment partially from H2 purification,and then save more investment and operation cost.In comparison with the standard process,this ultimate retrofitted process can be superior in all the three crucial indices,i.e.,recovery ratio,investment,and specific purification cost.On the whole,coal-based H2 generation can be ameliorated significantly through high efficient H2-selective and CO_(2)-selective membrane units.
文摘Cellular growth,development,and differentiation are tightly controlled by a conserved biological mechanism:the cell cycle.This cycle is primarily regulated by cyclin-dependent kinase(CDK)-cyclin complexes,checkpoint kinases,and CDK inhibitors.Deregulation of the cell cycle is a hallmark of the transformation of normal cells into tumor cells.Given its importance in tumorigenesis,several cell cycle inhibitors have emerged as potential therapeutic drugs for the treatment of cancers-both as singleagent therapy and in combination with traditional cytotoxic or molecular targeting agents.In this review,we discuss the mechanisms underlying cell cycle regulation and present small-molecule anticancer drugs that are under development,including both pan-CDK inhibitors and CDK4/6-selective inhibitors.In addition,we provide an outline of some promising CDK inhibitors currently in preclinical and clinical trials that target cell cycle abnormalities in various cancers.
文摘This paper describes preparation, characterization and electrochemical performance of novel planar miniaturized all-solid-state (ASS) screen-printed potentiometric sensors for the detection of Ca2+ ions in environmental samples. Screen-printed graphite-based ion-selective electrodes (ISEs) and screen-printed reference electrodes based on silver-containing pastes have been applied in a space saving manner on common ceramic substrates with small dimensions. Applications to environmental samples are shown by direct potentiometry and potentiometric titrations in real water samples. Conducting polymers (CPs) have been used as solid-contact materials and as intermediate layer between the polyvinyl chloride (PVC)-containing ion-selective membrane and the graphite-containing substrate. Different diamides have been incorporated into the PVC membrane. In the range from 10-4 mol/L to 10-1 mol/L, the ISEs show linear slopes of 27 mV/decade, which is close to the Nernstian response. Moreover, the ISEs have response times of 6 months. The novel potentiometric ASS sensors enable simple and exact Ca2+ determinations in real samples.
文摘A diester-calix[4]crown-4-ether bearing mono (azophenol) moiety shows a larger spectral change toward Ca2+ than other alkali and alkaline eafth cations.
基金supported by the National Key R&D Program of China(2021YFF0701600,2021YFA1500200)the National Natural Science Foundation of China(22271249)+2 种基金the Zhejiang Provincial Natural Science Foundation of China(LR19B020001)the Fundamental Research Funds for the Central Universities(226-2022-00224,226-202400003)the Center of Chemistry for Frontier Technologies,Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province(PSFM 2021-05)。
文摘Transition metal-catalyzed hydrostannylation of alkynes is an atom-economic way towards valuableα-vinylstannanes.However,directing-group-free examples for the construction ofα-adducts are rare and mostly undergo the M-Sn species insertion process.Here,we report an efficient cobalt-catalyzed highlyα-selective hydrostannylation of terminal alkynes via M-H species,using readily available Bu3Sn H and easily accessible as well as bench-stable ligand.The robust catalytic system,bearing good functional group tolerance and operational simplicity,provides theα-vinylstannanes in moderate to excellent yields with≥97:3 rr averagely.The efficiency of the reaction is investigated with turnover number(TON)up to 10,000 and turnover frequency(TOF)up to 144,000 h^(-1),respectively.The synthetic utility of theα-vinylstannanes is proved by further derivatizations towards the 1,1-disubstituted alkenes via Kosugi-Migita-Stille cross-coupling,conjugated alkene,α-vinyliodine,α-vinylazide,and allyl alcohol.Several control experiments,deuterium-labeling experiment and density functional theory(DFT)calculations are conducted to reveal the preliminary mechanism.
文摘A novel poly(vinyl chloride)membrane potentiometric sensor for chromium(Ⅲ)ions based on the use of 5,5′-(1,4-phenylene)bis(3-(naphthalen-1-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide)as a neutral ionophore was developed.The optimum composition of the best performing membrane contained ionophore,potassium tetrakis(p-chlorophenyl)borate(KTpClPB),dibutyl phthalate(DBP),and poly(vinyl chloride)(PVC)in the ratio of 5.5:1.5:55:38(mg).The sensor exhibits a working concentration range of 1.0×10^(-5)-1.0×10^(-1 )mol L^(−1) and a detection limit of 1.7×10^(-6) mol L^(−1).The sensor shows good selectivity for chromium(III)ions over a number of cations including alkali,alkaline earth,heavy and transition metals.The response time of the sensor is 8 s.In addition,the developed sensor shows good reusability and stability.The sensor operates in the wide pH range of 5.0-11.0.The sensor could be used as an indicator electrode in the quantification of Cr^(3+)ions by potentiometric titration against ethylenediaminetetraacetic acid(EDTA).Finally,this sensor was successfully used for the determination of chromium(III)in commercial water,purification water and wastewater.
基金supported by the National Natural Science Foundation of China(21871173,21572140,21372151)
文摘This work describes stereoselective preparation ofβ-C-aryl/vinyl glucosides via mild Ni-catalyzed reductive arylation and vinylation of C1-glucosyl halides with aryl and vinyl halides.A broad range of aryl halides and vinyl halides were employed to yield C-aryl/vinyl glucosides in 42%–93%yields.Good to excellentβ-selectivities were obtained for C-glucosides by using tridentate ligand.
基金This work was supported by the National Natural Science Foundation of China(Nos.22071144 and 21801164)by Shanghai Scientific and Technological Committee(No.22010500300).
文摘A simple methodology has been developed for the synthesis of highlyβ-selective O-glycosylation scaffolds of wider substrate scope under mild conditions using a self-assembled hexameric capsule.The reaction conditions are compatible with a wide range of functional groups.Extensive control experiments and theoretical studies established that the reaction takes place inside the capsule cavity.The substrates are activated via a proton wire as seen in some enzymes,and the reactions follow an SN2 pathway through a loose transition state.The advantages of this methodology are selectivity,high yields and scalability;the catalyst is readily recovered and reused.The methodology was adapted to the synthesis of mesomorphic glycosides and anti-tumour agents in short synthetic routes.
文摘Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NOx with NH3. A series of characterization including X-ray diffraction （XRD）, high-resolution transmission electron microscope （HR-TEM）, Bmnaue-Emmett-Teller （BET） surface area analysis, H2 temperature- programmed reduction （H2-TPR）, and X-ray photoelectron spectroscopy （XPS） were used to evaluate the influence of the physicochemical properties on NH3-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO2-CeO2 binary oxide for the low temperature NH3-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO2 and H2O. Cr-Zr-Ce mixed oxide exhibited〉80% NO,. conversion at a wide temperature window of 100 ℃ 300℃. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence ofCr6 ＋. The present mixed oxide can be a candidate for the low temperature abatement of NOx.
基金The authors acknowledge financial support from the National Natural Science Foundation of China(No.21573286)the Key scientific and technological innovation projects in Shandong Province(No.2019JZZY010343).
文摘In this paper,we report the fabrication of cobalt-doped de-NO_(x)catalyst by pyrolyzing an analogous metal-organic framework-74(MOF-74)containing Fe&Mn.The resulted catalyst exhibits distinctive microstructures of manganese,cobalt,and iron immobilized on N-doped carbon nanotubes(CNTs).It is found through experiments that the trimetallic catalyst Fe_(2)Mn_(1)Co_(0.5)/CNTs-50 has the best NH_(3)-selective catalytic reduction(SCR)performance.The Fe_(2)Mn_(1)Co_(0.5)/CNTs-50 exhibited excellent water and sulfur resistance and good stability under the harsh gas environment of 250℃ and/or 170℃,NO=NH_(3)=1,000 ppm,8 vol.%O_(2),20 vol.%H2O,1,000 ppm SO_(2),and gas hourly space velocity(GHSV)=75,000 h^(-1).The de-NO_(x)conversion was maintained about 55%and 25%after 192 h.The water and sulfur resistance performance were much higher than commercial vanadium series catalyst.The highly water and sulfur resistance performance may be attributed to the unique core-shell microstructure and the synergistic effect of manganese,cobalt,and iron which helps reduce the formation for byproducts(NH_(4)HSO_(4)).This study may promote to explore the development of a high stability catalyst for low-temperature selective catalytic reduction of NO_(x)with NH_(3).
