N,N'-Diarylhydrazines have been prepared via the reaction of N-Boc-aryl hydrazines with boronic acids mediated by copper acetate. This mild reaction condition tolerates the presence of a variety of functional groups.
A simple, rapid, and highly sensitive LC-MS/MS method has been developed for the simultaneous and trace level quantification of underivatized boronic acids in lumacaftor active pharmaceutical ingredient. Chromatograph...A simple, rapid, and highly sensitive LC-MS/MS method has been developed for the simultaneous and trace level quantification of underivatized boronic acids in lumacaftor active pharmaceutical ingredient. Chromatographic separation of boronic acids and lumacaftor achieved using Agilent Poroshell HPH C18 150<span> </span><span>×</span><span> </span><span>4.6</span><span> </span><span>mm 2.7</span><span> </span><span>μ column with 0.1% ammonia in water as mobile phase A and 100%</span><span> </span><span>acetonitrile as mobile phase B at a flow rate of 0.25</span><span> </span><span>ml/min. Gradient elution</span><span> was</span><span> used with a total method run time of 14</span><span> </span><span>minutes. Boronic acids were successfully ionized and quantified without derivatization using electrospray ionization in negative mode using tandem quadrupole mass spectrometry in multiple reactions monitoring mode. Method validation </span><span>was </span><span>performed as per ICH guidelines with good linearity over the concentration range of 0.05 ppm to 5 ppm of Lumacaftor test concentration for both the boronic acids with a correlation coefficient of >0.99.</span><span> </span><span>Recoveries were found good at different concentration levels and within the range of 80</span><span>% </span><span>-</span><span> </span><span>120%.</span><span> </span><span>The developed method can be successfully used for the routine quantification of boronic acids at a concentration level of 20</span><span> </span><span>ng/ml (1</span><span> </span><span>ppm with respect to 20</span><span> </span><span>mg/ml lumacaftor).</span>展开更多
Herein,we discovered that the surface-confined condensation of boronic acid can happen spontaneously at room temperature,by comparing the kinetics of condensation of boronic acids with and without the negative sample ...Herein,we discovered that the surface-confined condensation of boronic acid can happen spontaneously at room temperature,by comparing the kinetics of condensation of boronic acids with and without the negative sample bias,we found that the negative sample bias indeed accelerates the self-condensation reaction of boronic acid.Combining with in-situ STM images and ultraviolet photoemission spectrum(UPS)analysis,a reversible adsorption mechanism model was proposed and reasonably explains the reversible electric-field-induced phase transformation.展开更多
Drug resistance remains to be a serious problem with type Ⅰ human immunodeficiency virus(HIV-1) nonnucleoside reverse transcriptase inhibitors(NNRTIs). A series of novel boronic acid-containing diarylpyrimidine(DAPY)...Drug resistance remains to be a serious problem with type Ⅰ human immunodeficiency virus(HIV-1) nonnucleoside reverse transcriptase inhibitors(NNRTIs). A series of novel boronic acid-containing diarylpyrimidine(DAPY) derivatives were designed via bioisosterism and scaffold-hopping strategies,taking advantage of the ability of a boronic acid group to form multiple hydrogen bonds. The target compounds were synthesized and evaluated for their anti-HIV activities and cytotoxicity in MT-4 cells.Compound 10 j yielded the most potent activity and turned out to be a single-digit nanomolar inhibitor towards the HIV-1 ⅢB [wild-type(WT) strain], L100 I and K103 N strains, with 50% effective concentration(EC_(50)) values of 7.19–9.85 nmol/L. Moreover, 10 j inhibited the double-mutant strain RES056 with an EC_(50) value of 77.9 nmol/L, which was 3.3-more potent than that of EFV(EC_(50)= 260 nmol/L) and comparable to that of ETR(EC_(50)= 32.2 nmol/L). 10j acted like classical NNRTIs with high affinity for WT HIV-1 reverse transcriptase(RT) with 50% inhibition concentration(IC_(50)) value of 0.1837 μmol/L. Furthermore,molecular dynamics simulation indicated that 10 j was proposed as a promising molecule for fighting against HIV-1 infection through inhibiting RT activity. Overall, the results demonstrated that 10 j could serve as a lead molecule for further modification to address virus-drug resistance.展开更多
An efficient and facile method for synthesis of 2-arylpyrroles through Rh(III)-catalyzed direct C--H arylation with pyrrole derivatives and aryl boronic acids has been developed. This reaction could proceed under mi...An efficient and facile method for synthesis of 2-arylpyrroles through Rh(III)-catalyzed direct C--H arylation with pyrrole derivatives and aryl boronic acids has been developed. This reaction could proceed under mild reaction conditions and afford a series of 2-arylated products in good to excellent yields. The gram-scale experiment has been conducted to demonstrate the synthetic potential of this methodology.展开更多
High sensitive immunoassay platforms have gained intense attention due to their vital roles in early-stage disease diagnosis and therapeutic information feedback. Although random covalent-binding of antibody has been ...High sensitive immunoassay platforms have gained intense attention due to their vital roles in early-stage disease diagnosis and therapeutic information feedback. Although random covalent-binding of antibody has been widely adopted in immunoassays due to its simplicity and effectiveness, it readily loses its activity and fails to exhibit high antigen-binding capacity. In this work, copolymer of zwitterionic sulfobetaine methacrylate(SBMA) and glycidyl methacrylate(GMA) brushes were immobilized onto inert polypropylene(PP) via surface-initiated atom transfer radical polymerization(ATRP) based on biomimetic dopamine pretreatment. Subsequently, boronic acid(BA) groups were covalently bonded via active GMA units, followed by the introduction of oriented immobilization of antibody. Owing to the oriented immobilization of antibody facilitated by BA groups in polymer brush, the bioactivity of antibody is well preserved, which endows the surface with significantly enhanced antigen-binding capacity. Moreover, the existence of SBMA segments in polymer brushes renders the surface high resistance to nonspecific protein adsorption, significantly alleviating the signal interference of antigen recognition. This strategy could find potential applications in developing high sensitive immunoassay platforms based on the different substrates.展开更多
A facile,one-pot synthesis of N-aryl propargylamine from aromatic boronic acid,aqueous ammonia,and propargyl bromide has been achieved under microwave-assisted conditions.The reactions can be smoothly completed within...A facile,one-pot synthesis of N-aryl propargylamine from aromatic boronic acid,aqueous ammonia,and propargyl bromide has been achieved under microwave-assisted conditions.The reactions can be smoothly completed within a total 10 min through a two-step procedure,including copper-catalyzed coupling of aromatic boronic acids with aqueous ammonia and following propargylation by propargyl bromide.展开更多
Discrimination of glycoproteins and cell types is a significant but difficult issue.Herein,we presented a novel fluorescence sensor array for the detection and identification of glycoproteins and cancer cells based on...Discrimination of glycoproteins and cell types is a significant but difficult issue.Herein,we presented a novel fluorescence sensor array for the detection and identification of glycoproteins and cancer cells based on the specific affinity between boronic acid-containing carbon dots(BA-CDs)and cis-diol residues of polysaccharides.The differential binding affinity of three BA-CDs to various glycoproteins resulted in a different fluorescence turn-on signal pattern caused by aggregation-enhanced emission(AEE),along with negligible response from other proteins.Therefore,BA-CDs encompassing sensing elements and signal indicator into one can enable a fast and accurate discrimination of glycoproteins with simple and easy operation.Seven glycoproteins could be well discriminated at a very low concentration of 10 nmol/L.The discriminating capability of glycoproteins is not sacrificed in both human urine and serum.Notably,different glycoprotein compositions of cancer cells provide more recognizable features for identification of cancer cells,comparing to the total protein.Five cell types could be identified in 15 min at a low concentration of 1000 cells/mL.This method is fast,accurate,and easy operation,and has a potential application in cancer diagnosis.展开更多
An efficient synthetic method for diarylmethylphosphonates is presented.A series of phosphonate derivatives with diverse functional groups can be accessed via a rhodium catalyzed cross-coupling reaction between a-diaz...An efficient synthetic method for diarylmethylphosphonates is presented.A series of phosphonate derivatives with diverse functional groups can be accessed via a rhodium catalyzed cross-coupling reaction between a-diazo phosphonates and aryl boronic acids.Migratory insertion of rhodium carbene intermediates is postulated to be the critical step in this transformation.展开更多
Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids und...Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids under mild reaction conditions.Even at 2 mol% catalyst loading,a wide range of substrates for both coupling partners with different steric and electronic properties were well tolerated.展开更多
The negative secondary ion mass spectrometry,in combination with the stereoselective derivatizations with substituted boronic acid RB(OH)_2,was used in the analysis of fourteen oligosac- charides.The mass spectra of t...The negative secondary ion mass spectrometry,in combination with the stereoselective derivatizations with substituted boronic acid RB(OH)_2,was used in the analysis of fourteen oligosac- charides.The mass spectra of the derivatives provide information on their linkage Positions and iso- merism of the individual monoscaccharide units.The results indicated that among the derivatives of the oligosaccharides analyzed,those with 1—4 and 1—6 linkages all presented the ion peaks at m/z 287,sometimes one more peak at m/z 449.Furthermore,a relationship was found between the linkage positions and the intensity orders of the derivative ions.Finally,the derivatives of the disaccharides with a galactose presented an intense ion peak at m/z 347,and those of oligosaccharides with 1—6 linkage to a galactose at terminal presented the ion at m/z 317.In the case of oligosaccharides with a fructose residue,characteristic ion of m/z 155 was produced.The conditions of stereoselective derivatizations and mass spectrometry were studied,in order to obtain a better reproducibility of the mass spectra.展开更多
The title compounds 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (1) and 3-(4- fluoro-3-methylphenyl)quinoline (2) were synthesized through Suzuki-Miyaura Cross coupling reaction of 3-bromoquinoloine with ary...The title compounds 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (1) and 3-(4- fluoro-3-methylphenyl)quinoline (2) were synthesized through Suzuki-Miyaura Cross coupling reaction of 3-bromoquinoloine with aryl boronic acids. The title compounds were characterized by single-crystal X-ray diffraction, 1H NMR, 13C NMR, El-MS, elemental analysis and IR. The crystals of 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (C17H9F6N, Mr = 341.25) belongs to the monoclinic system, space group P21n, a = 12.3072(13), b = 4.9378(6), c = 24.493(2) A, V= 1473.1(3) A3, Z = 4, Dc = 1.539 Mg m-3, 2 - 0.71073A, μ = 0.144 mm^-1, F(000) = 688, the final R = 0.0715 and wR = 0.1873 for 1875 obserwed reflections with I 〉 2σ(I) and the crystal of 3-(4-fluoro-3- methylphenyl)quinoline (C16H12FN, Mr= 237.27) belongs to the orthorhombic system, space group Pca21, a = 23.794(2), b = 3.9094(3), c = 25.669(2) A, V = 2387.7(4) A3, Z = 8, D, = 1.320 Mg m-3, 2 = 0.71073 A, μ = 0.088 mm-1, F(000) = 992, the final R = 0.0534 and wR = 0.1188 for 2270 observed reflections with I 〉 2σ(I).展开更多
A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich an...A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and defi- cient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halo- gen-free Cu20 as catalysts make the protocol an appealing option for aryl cyanations.展开更多
A single boronic acid-based fluorescent probe (compound CSP) for saccharides was designed and synthesized. The probe, with an a,fl-unsaturated ketone conjugated into the coumarin fluorophore, was synthesized by 4 st...A single boronic acid-based fluorescent probe (compound CSP) for saccharides was designed and synthesized. The probe, with an a,fl-unsaturated ketone conjugated into the coumarin fluorophore, was synthesized by 4 steps from the commercial material 4-diethylamino salicylaldehyde. The electron push-pull effect is enhanced with the N,N-diethyl amino as the electron donor and the carbonyl as the electron acceptor. Both the absorption (463 nm) and emission (616 nm) maxima of CSP are in the visible wavelength region with a Stokes shift of about 150 nm, which ensures CSP a potential probe for biological application. Under near physiological conditions, significant fluores- cence enhancement of CSP was observed upon the addition of some saccharides, namely, D-sorbitol, D-fructose, D-glucose, D-mannose and D-galactose. The probe showed relatively high sensitivity towards D-fructose and D-sorbitol, and their detection limits were 0.05 mmol/L and 0.1 mmol/L, respectively.展开更多
Clustered regularly interspaced short palindromic repeat(CRISPR)technologies have opened new scientific avenues widely used in biomedical research.But simple and efficient strategies to reversibly control CRISPR are l...Clustered regularly interspaced short palindromic repeat(CRISPR)technologies have opened new scientific avenues widely used in biomedical research.But simple and efficient strategies to reversibly control CRISPR are lacking.In contrast to previous methods of attaching molecules to the ribose of guide RNAs(gRNAs),we focused on molecules that can directly react with nucleobases.Here,we developed a new strategy to switch off the CRISPR system by efficiently installing 4-(bromomethyl)phenylboronic acid onto nucleobases in gRNAs.CRISPR can then be activated by hydrogen peroxide(H_(2)O_(2)).Collectively,this work demonstrates boronic acid reversibly modulating CRISPR systems through a H_(2)O_(2)-responsive manner.展开更多
Prostate cancer(PC)biomarker-citrate detection is clinically important to diagnose PC in early stages.Methylquinolinium iodide(Q)conjugated indole-phenylboronic acid(IB)was designed as a red-emissive QIB probe for the...Prostate cancer(PC)biomarker-citrate detection is clinically important to diagnose PC in early stages.Methylquinolinium iodide(Q)conjugated indole-phenylboronic acid(IB)was designed as a red-emissive QIB probe for the detection of citrate through Lewis acid-base reaction and intramolecular charge transfer(ICT)sensing mechanisms.Boronic acid acts as Lewis acid as well as citrate(Lewis base)recognition unit.The probe reacted with citrate,showing enhanced red emissions.Since the probe has excellent water solubility and great biocompatibility,practical application in biological systems is possible.Citrate was monitored precisely in the mitochondria organelle(in vitro)of living cells with a positive charge on QIB.Also,endogenous(in situ)citrate was detected quantitatively to discriminate non-cancerous and PC mice,observed strong and lower(negligible)emission intensity on non-cancerous and cancerous prostate tissues,respectively.Because,the concentration of citrate is higher in healthy prostate compared with PC prostate.Furthermore,the analysis of sliced prostate tissues can give PC-related information for clinical diagnosis to prevent and treat PC in the initial stages.Therefore,we believe that the present probe is a promising biochemical reagent in diagnosing PC.展开更多
A convenient and efficient protocol for the synthesis of unnatural N-glycosyl cz-amino acids was developed. Condensation of 1,3,4,6-tetra-O-actyl-/%D-glucosamine hydrochloride, alkenyl boronic acid, and glyoxylic acid...A convenient and efficient protocol for the synthesis of unnatural N-glycosyl cz-amino acids was developed. Condensation of 1,3,4,6-tetra-O-actyl-/%D-glucosamine hydrochloride, alkenyl boronic acid, and glyoxylic acid was achieved in CH2C12 to give the derivatives of 2-(N-glycosyl)aminobut-3-enoic acid which may find applications in glycobiology research and medicinal chemistry.展开更多
Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesiz...Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesized.FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other.Presence of Cu_(3)clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.展开更多
A saccharide fluorescent receptor based on 1,1'-binaphthol was developed.The boronic acids groups are di-rectly attached to the 3,3'-positions of BINOL which acted as probes to saccharides.The methyl protected...A saccharide fluorescent receptor based on 1,1'-binaphthol was developed.The boronic acids groups are di-rectly attached to the 3,3'-positions of BINOL which acted as probes to saccharides.The methyl protected receptor R1 showed better response to D-fructose compared to other saccharides in the fluorescence quenching experiment.To improve the selectivity of D-glucose,the triethylene glycol protected receptor R2 was developed.Receptor R2 has a better water-solubility than R1 that can be applied in completely aqueous environment.With receptor R2,D-glucose has a different response to other saccharides that can be useful for the distinction of D-glucose.展开更多
Considering that hydrogen peroxide(H2O2)plays significant roles in oxidative stress,the cellular signal transduction and essential biological process regulation,the detection and imaging of H2O2 in living systems unde...Considering that hydrogen peroxide(H2O2)plays significant roles in oxidative stress,the cellular signal transduction and essential biological process regulation,the detection and imaging of H2O2 in living systems undertakes critical responsibility.Herein,we have developed a novel two-photon fluorescence turn on probe,named as Pyp-B for mitochondria H2O2 detection in living systems.Selectivity studies show that probe Pyp-B exhibit highly sensitive response toward H2O2 than other reactive oxygen species(ROS)and reactive nitrogen species(RNS)as well as biologically relevant species.The fluorescence colocalization studies demonstrate that the probe can localize in the mitochondria solely.Furthermore,as a bio-compatibility molecule,the highly selective and sensitive of fluorescence probe Pyp-B have been confirmed by its cell imaging application of H2O2 in living A549 cells and zebrafishes under the physiological conditions.展开更多
文摘N,N'-Diarylhydrazines have been prepared via the reaction of N-Boc-aryl hydrazines with boronic acids mediated by copper acetate. This mild reaction condition tolerates the presence of a variety of functional groups.
文摘A simple, rapid, and highly sensitive LC-MS/MS method has been developed for the simultaneous and trace level quantification of underivatized boronic acids in lumacaftor active pharmaceutical ingredient. Chromatographic separation of boronic acids and lumacaftor achieved using Agilent Poroshell HPH C18 150<span> </span><span>×</span><span> </span><span>4.6</span><span> </span><span>mm 2.7</span><span> </span><span>μ column with 0.1% ammonia in water as mobile phase A and 100%</span><span> </span><span>acetonitrile as mobile phase B at a flow rate of 0.25</span><span> </span><span>ml/min. Gradient elution</span><span> was</span><span> used with a total method run time of 14</span><span> </span><span>minutes. Boronic acids were successfully ionized and quantified without derivatization using electrospray ionization in negative mode using tandem quadrupole mass spectrometry in multiple reactions monitoring mode. Method validation </span><span>was </span><span>performed as per ICH guidelines with good linearity over the concentration range of 0.05 ppm to 5 ppm of Lumacaftor test concentration for both the boronic acids with a correlation coefficient of >0.99.</span><span> </span><span>Recoveries were found good at different concentration levels and within the range of 80</span><span>% </span><span>-</span><span> </span><span>120%.</span><span> </span><span>The developed method can be successfully used for the routine quantification of boronic acids at a concentration level of 20</span><span> </span><span>ng/ml (1</span><span> </span><span>ppm with respect to 20</span><span> </span><span>mg/ml lumacaftor).</span>
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21872103,52073208).
文摘Herein,we discovered that the surface-confined condensation of boronic acid can happen spontaneously at room temperature,by comparing the kinetics of condensation of boronic acids with and without the negative sample bias,we found that the negative sample bias indeed accelerates the self-condensation reaction of boronic acid.Combining with in-situ STM images and ultraviolet photoemission spectrum(UPS)analysis,a reversible adsorption mechanism model was proposed and reasonably explains the reversible electric-field-induced phase transformation.
基金financial support from the National Natural Science Foundation of China (Nos. 81973181, 81903453)Shandong Provincial Natural Science Foundation (No. ZR2019BH011)+7 种基金Natural Science Foundation of Jiangsu Province (No. BK2019041035)China Postdoctoral Science Foundation (Nos. 2019T120596, 2018M640641)Science Foundation for Outstanding Young Scholars of Shandong Province (No. ZR2020JQ31)Science Foundation for Excellent Young Scholars of Shandong Province (No. ZR2020YQ61)National Science and Technology Major Projects for "Major New Drugs Innovation and Development" (2019ZX09301126)Shandong Provincial Key Research and Development Project (Nos. 2017CXGC1401, 2019JZZY021011)Foreign cultural and educational experts Project (No. GXL20200015001)the Taishan Scholar Program at Shandong Province and KU Leuven (No. GOA 10/014)。
文摘Drug resistance remains to be a serious problem with type Ⅰ human immunodeficiency virus(HIV-1) nonnucleoside reverse transcriptase inhibitors(NNRTIs). A series of novel boronic acid-containing diarylpyrimidine(DAPY) derivatives were designed via bioisosterism and scaffold-hopping strategies,taking advantage of the ability of a boronic acid group to form multiple hydrogen bonds. The target compounds were synthesized and evaluated for their anti-HIV activities and cytotoxicity in MT-4 cells.Compound 10 j yielded the most potent activity and turned out to be a single-digit nanomolar inhibitor towards the HIV-1 ⅢB [wild-type(WT) strain], L100 I and K103 N strains, with 50% effective concentration(EC_(50)) values of 7.19–9.85 nmol/L. Moreover, 10 j inhibited the double-mutant strain RES056 with an EC_(50) value of 77.9 nmol/L, which was 3.3-more potent than that of EFV(EC_(50)= 260 nmol/L) and comparable to that of ETR(EC_(50)= 32.2 nmol/L). 10j acted like classical NNRTIs with high affinity for WT HIV-1 reverse transcriptase(RT) with 50% inhibition concentration(IC_(50)) value of 0.1837 μmol/L. Furthermore,molecular dynamics simulation indicated that 10 j was proposed as a promising molecule for fighting against HIV-1 infection through inhibiting RT activity. Overall, the results demonstrated that 10 j could serve as a lead molecule for further modification to address virus-drug resistance.
基金We are grateful to the National Natural Science Foundation of China (No. 21302064) and Scientific Research Project of Hubei Provincial Department of Education (No. 2015231) for support of this research.
文摘An efficient and facile method for synthesis of 2-arylpyrroles through Rh(III)-catalyzed direct C--H arylation with pyrrole derivatives and aryl boronic acids has been developed. This reaction could proceed under mild reaction conditions and afford a series of 2-arylated products in good to excellent yields. The gram-scale experiment has been conducted to demonstrate the synthetic potential of this methodology.
基金financially supported by the Research Program Funds of Jilin University(Nos.419080500665 and 451170301076)
文摘High sensitive immunoassay platforms have gained intense attention due to their vital roles in early-stage disease diagnosis and therapeutic information feedback. Although random covalent-binding of antibody has been widely adopted in immunoassays due to its simplicity and effectiveness, it readily loses its activity and fails to exhibit high antigen-binding capacity. In this work, copolymer of zwitterionic sulfobetaine methacrylate(SBMA) and glycidyl methacrylate(GMA) brushes were immobilized onto inert polypropylene(PP) via surface-initiated atom transfer radical polymerization(ATRP) based on biomimetic dopamine pretreatment. Subsequently, boronic acid(BA) groups were covalently bonded via active GMA units, followed by the introduction of oriented immobilization of antibody. Owing to the oriented immobilization of antibody facilitated by BA groups in polymer brush, the bioactivity of antibody is well preserved, which endows the surface with significantly enhanced antigen-binding capacity. Moreover, the existence of SBMA segments in polymer brushes renders the surface high resistance to nonspecific protein adsorption, significantly alleviating the signal interference of antigen recognition. This strategy could find potential applications in developing high sensitive immunoassay platforms based on the different substrates.
基金the National Natural Science Foundation of China (No. 21262020)the Science and Technology Planning Project of Yunnan Province (No. KKSY201207140)+1 种基金the Natural Science Foundation of Yunnan Education Department (No. 09Y0081)the Analysis and Measurement Foundation of Kunming University of Science and Technology (No. 20130560) for their financial supports
文摘A facile,one-pot synthesis of N-aryl propargylamine from aromatic boronic acid,aqueous ammonia,and propargyl bromide has been achieved under microwave-assisted conditions.The reactions can be smoothly completed within a total 10 min through a two-step procedure,including copper-catalyzed coupling of aromatic boronic acids with aqueous ammonia and following propargylation by propargyl bromide.
基金financially supported by the National Natural Science Foundation of China(Nos.21922402,21874017 and21727811)Liaoning Provincial Program for Promoting Talents(Nos.XLYC1807005 and XLYC1802016)the Key Laboratory of Data Analytics and Optimization for Smart Industry(Northeastern University,Ministry of Education,China,111 Project,No.B16009)。
文摘Discrimination of glycoproteins and cell types is a significant but difficult issue.Herein,we presented a novel fluorescence sensor array for the detection and identification of glycoproteins and cancer cells based on the specific affinity between boronic acid-containing carbon dots(BA-CDs)and cis-diol residues of polysaccharides.The differential binding affinity of three BA-CDs to various glycoproteins resulted in a different fluorescence turn-on signal pattern caused by aggregation-enhanced emission(AEE),along with negligible response from other proteins.Therefore,BA-CDs encompassing sensing elements and signal indicator into one can enable a fast and accurate discrimination of glycoproteins with simple and easy operation.Seven glycoproteins could be well discriminated at a very low concentration of 10 nmol/L.The discriminating capability of glycoproteins is not sacrificed in both human urine and serum.Notably,different glycoprotein compositions of cancer cells provide more recognizable features for identification of cancer cells,comparing to the total protein.Five cell types could be identified in 15 min at a low concentration of 1000 cells/mL.This method is fast,accurate,and easy operation,and has a potential application in cancer diagnosis.
文摘An efficient synthetic method for diarylmethylphosphonates is presented.A series of phosphonate derivatives with diverse functional groups can be accessed via a rhodium catalyzed cross-coupling reaction between a-diazo phosphonates and aryl boronic acids.Migratory insertion of rhodium carbene intermediates is postulated to be the critical step in this transformation.
基金the National Natural Science Foundation of China (Nos. 21572036, 21172045 and 91127041)the Changjiang Scholars and Innovative Research Team in University (No. IRT-15R12)+2 种基金the Shanghai International Cooperation Program (No. 14230710600)the Doctoral Fund of Ministry of Education of China (No. 20130071110032)Department of Chemistry Fudan University
文摘Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids under mild reaction conditions.Even at 2 mol% catalyst loading,a wide range of substrates for both coupling partners with different steric and electronic properties were well tolerated.
基金Project supported by the National Natural Science Foundation of China
文摘The negative secondary ion mass spectrometry,in combination with the stereoselective derivatizations with substituted boronic acid RB(OH)_2,was used in the analysis of fourteen oligosac- charides.The mass spectra of the derivatives provide information on their linkage Positions and iso- merism of the individual monoscaccharide units.The results indicated that among the derivatives of the oligosaccharides analyzed,those with 1—4 and 1—6 linkages all presented the ion peaks at m/z 287,sometimes one more peak at m/z 449.Furthermore,a relationship was found between the linkage positions and the intensity orders of the derivative ions.Finally,the derivatives of the disaccharides with a galactose presented an intense ion peak at m/z 347,and those of oligosaccharides with 1—6 linkage to a galactose at terminal presented the ion at m/z 317.In the case of oligosaccharides with a fructose residue,characteristic ion of m/z 155 was produced.The conditions of stereoselective derivatizations and mass spectrometry were studied,in order to obtain a better reproducibility of the mass spectra.
文摘The title compounds 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (1) and 3-(4- fluoro-3-methylphenyl)quinoline (2) were synthesized through Suzuki-Miyaura Cross coupling reaction of 3-bromoquinoloine with aryl boronic acids. The title compounds were characterized by single-crystal X-ray diffraction, 1H NMR, 13C NMR, El-MS, elemental analysis and IR. The crystals of 3-(3,5-bis(trifluoromethyl)phenyl)quinoline (C17H9F6N, Mr = 341.25) belongs to the monoclinic system, space group P21n, a = 12.3072(13), b = 4.9378(6), c = 24.493(2) A, V= 1473.1(3) A3, Z = 4, Dc = 1.539 Mg m-3, 2 - 0.71073A, μ = 0.144 mm^-1, F(000) = 688, the final R = 0.0715 and wR = 0.1873 for 1875 obserwed reflections with I 〉 2σ(I) and the crystal of 3-(4-fluoro-3- methylphenyl)quinoline (C16H12FN, Mr= 237.27) belongs to the orthorhombic system, space group Pca21, a = 23.794(2), b = 3.9094(3), c = 25.669(2) A, V = 2387.7(4) A3, Z = 8, D, = 1.320 Mg m-3, 2 = 0.71073 A, μ = 0.088 mm-1, F(000) = 992, the final R = 0.0534 and wR = 0.1188 for 2270 observed reflections with I 〉 2σ(I).
文摘A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and defi- cient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halo- gen-free Cu20 as catalysts make the protocol an appealing option for aryl cyanations.
文摘A single boronic acid-based fluorescent probe (compound CSP) for saccharides was designed and synthesized. The probe, with an a,fl-unsaturated ketone conjugated into the coumarin fluorophore, was synthesized by 4 steps from the commercial material 4-diethylamino salicylaldehyde. The electron push-pull effect is enhanced with the N,N-diethyl amino as the electron donor and the carbonyl as the electron acceptor. Both the absorption (463 nm) and emission (616 nm) maxima of CSP are in the visible wavelength region with a Stokes shift of about 150 nm, which ensures CSP a potential probe for biological application. Under near physiological conditions, significant fluores- cence enhancement of CSP was observed upon the addition of some saccharides, namely, D-sorbitol, D-fructose, D-glucose, D-mannose and D-galactose. The probe showed relatively high sensitivity towards D-fructose and D-sorbitol, and their detection limits were 0.05 mmol/L and 0.1 mmol/L, respectively.
基金the National Natural Science Foundation of China(grant nos.22177089,91853119,21721005,91753201,21877086,and 22177088)the Hubei Natural Science Foundation for Distinguished Young Scholars(grant no.2019CFA064)the Fundamental Research Funds for the Central Universities(grant no.2042019-kf0189).
文摘Clustered regularly interspaced short palindromic repeat(CRISPR)technologies have opened new scientific avenues widely used in biomedical research.But simple and efficient strategies to reversibly control CRISPR are lacking.In contrast to previous methods of attaching molecules to the ribose of guide RNAs(gRNAs),we focused on molecules that can directly react with nucleobases.Here,we developed a new strategy to switch off the CRISPR system by efficiently installing 4-(bromomethyl)phenylboronic acid onto nucleobases in gRNAs.CRISPR can then be activated by hydrogen peroxide(H_(2)O_(2)).Collectively,this work demonstrates boronic acid reversibly modulating CRISPR systems through a H_(2)O_(2)-responsive manner.
基金financially supported by the National Natural Science Foundation of China(No.22150410327)the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT&Future Planning(No.2020R1A2C1102741).
文摘Prostate cancer(PC)biomarker-citrate detection is clinically important to diagnose PC in early stages.Methylquinolinium iodide(Q)conjugated indole-phenylboronic acid(IB)was designed as a red-emissive QIB probe for the detection of citrate through Lewis acid-base reaction and intramolecular charge transfer(ICT)sensing mechanisms.Boronic acid acts as Lewis acid as well as citrate(Lewis base)recognition unit.The probe reacted with citrate,showing enhanced red emissions.Since the probe has excellent water solubility and great biocompatibility,practical application in biological systems is possible.Citrate was monitored precisely in the mitochondria organelle(in vitro)of living cells with a positive charge on QIB.Also,endogenous(in situ)citrate was detected quantitatively to discriminate non-cancerous and PC mice,observed strong and lower(negligible)emission intensity on non-cancerous and cancerous prostate tissues,respectively.Because,the concentration of citrate is higher in healthy prostate compared with PC prostate.Furthermore,the analysis of sliced prostate tissues can give PC-related information for clinical diagnosis to prevent and treat PC in the initial stages.Therefore,we believe that the present probe is a promising biochemical reagent in diagnosing PC.
基金the Natural Science Foundation of Jiangsu Province(No.BK20130404)the Scientific and Technological Research Project of Lianyungang(No.CG1303)the project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘A convenient and efficient protocol for the synthesis of unnatural N-glycosyl cz-amino acids was developed. Condensation of 1,3,4,6-tetra-O-actyl-/%D-glucosamine hydrochloride, alkenyl boronic acid, and glyoxylic acid was achieved in CH2C12 to give the derivatives of 2-(N-glycosyl)aminobut-3-enoic acid which may find applications in glycobiology research and medicinal chemistry.
基金the National Natural Science Foundation of China(No.22005306)for financial support。
文摘Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesized.FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other.Presence of Cu_(3)clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.
基金supported by the National Program on Key Basic Research Project of China (973 Program,Nos.2012CB720603 and 2013CB328900)the National Science Foundation of China (Nos.21232005,21321061,J1310008 and J1103315)the Specialized Research Fund for the Doctoral Program of Higher Education in China (No.20120181130006).
文摘A saccharide fluorescent receptor based on 1,1'-binaphthol was developed.The boronic acids groups are di-rectly attached to the 3,3'-positions of BINOL which acted as probes to saccharides.The methyl protected receptor R1 showed better response to D-fructose compared to other saccharides in the fluorescence quenching experiment.To improve the selectivity of D-glucose,the triethylene glycol protected receptor R2 was developed.Receptor R2 has a better water-solubility than R1 that can be applied in completely aqueous environment.With receptor R2,D-glucose has a different response to other saccharides that can be useful for the distinction of D-glucose.
基金the financial support from the National Natural Science Foundation of China(No.81860630)the China Postdoctoral Science Foundation(No.2019M662968)GuangdongBasic and Applied Basic Research Foundation(Nos.2019A1515110356,2019A1515110877)。
文摘Considering that hydrogen peroxide(H2O2)plays significant roles in oxidative stress,the cellular signal transduction and essential biological process regulation,the detection and imaging of H2O2 in living systems undertakes critical responsibility.Herein,we have developed a novel two-photon fluorescence turn on probe,named as Pyp-B for mitochondria H2O2 detection in living systems.Selectivity studies show that probe Pyp-B exhibit highly sensitive response toward H2O2 than other reactive oxygen species(ROS)and reactive nitrogen species(RNS)as well as biologically relevant species.The fluorescence colocalization studies demonstrate that the probe can localize in the mitochondria solely.Furthermore,as a bio-compatibility molecule,the highly selective and sensitive of fluorescence probe Pyp-B have been confirmed by its cell imaging application of H2O2 in living A549 cells and zebrafishes under the physiological conditions.