Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporti...Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporting molybdenum complex on C_(3)N_(4)-K and characterized by FT-IR,XRD,SEM,XPS and ICP-OES.Heterogeneous CN–Mo-Bpy catalyst can be applied to the direct amination of nitroarenes and arylboronic acid,thus constructing various valuable diarylamines in high to excellent yields with a wide substrate scope and good functional group tolerance.It is worth noting that this heterogeneous catalyst has high chemical stability and can be recycled for at least five times without reducing its activity.展开更多
The"solid-liquid"behavior of vitrimers have not been systematically investigated.Herein,a series of"solid-liquid"vitrimers bearing varying contents of dynamic boronic ester bonds were synthesized v...The"solid-liquid"behavior of vitrimers have not been systematically investigated.Herein,a series of"solid-liquid"vitrimers bearing varying contents of dynamic boronic ester bonds were synthesized via thiol-ene click reactions.These vitrimers allow for flexibile modulation of their network structures and thus show a range of intriguing properties including high stretchability,flexible transition from elasticity to plasticity,strong strain rate dependence,and solid-liquid performance.The dynamic association rate of boronic ester bonds within these vitrimers could be apparently accelerated via increasing the content of boronic ester,which could be used to shape-program the flat vitrimer films into various complex 3D structures just with external force.Materials with such versatile dynamic behavior may open up a range of new applications.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, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic a...An efficient, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic amount of CuSO4 at 130 ℃ using water as a green solvent. The products were obtained in moderate to excellent yields;more importantly, the use of toxic ligands and solvents was avoided. A broad range of aryl boronic acids and scalable processes make this methodology valuable and versatile for the synthesis of a broad range of aryl sulfides.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
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 colorimetric method for the direct determination of hydrogen peroxide in aqueous solution is described. H2O2 stoichiometrically converts 4-nitrophenyl boronic acid or 4-nitrophenyl boronic acid pinacol ester into 4-...A colorimetric method for the direct determination of hydrogen peroxide in aqueous solution is described. H2O2 stoichiometrically converts 4-nitrophenyl boronic acid or 4-nitrophenyl boronic acid pinacol ester into 4-nitrophenol, which can be quantified by measuring the absorption at 400 nm in neutral or basic media. The reactions proceed fast under basic conditions and complete in 2 minutes to at pH 11 and 80?C. The linear range for the colorimetric method extends beyond 1.0 to 40 μM H2O2, and the limit of detection is ~1.0 μM H2O2. This method offers a convenient and practical process for rapid determination of hydrogen peroxide in aqueous media. Compared to many other techniques in H2O2 detection, this process is a direct measurement of H2O2, and is relatively unaffected by the presence of various salts, metal ions and the chelator EDTA.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
An efficient and novel methodology to access phenolic glycosides has been established by using coppermediated coupling reaction of aryl boronic acids with hemiacetals.The reaction takes place normally in the presence ...An efficient and novel methodology to access phenolic glycosides has been established by using coppermediated coupling reaction of aryl boronic acids with hemiacetals.The reaction takes place normally in the presence of Cu(OAc)_2(1.0 equiv.)and pyridine(2.0 equiv.)at 40℃.This protocol distinguishes itself by wide substrate scope,operational simplicity and giving rise to a myriad of phenolic glycosides in good to excellent yields.展开更多
Boronic acid compounds with different substituted groups were handled to synthesize various ligands encoded as B1, B2, B3, B4, BS, B6, B7 and BS. B5 and B7 were tested for the cytotoxic activity against the prostate c...Boronic acid compounds with different substituted groups were handled to synthesize various ligands encoded as B1, B2, B3, B4, BS, B6, B7 and BS. B5 and B7 were tested for the cytotoxic activity against the prostate cancer cells and it was found that the cell viability of cancer cells was decreased while most of the healthy cells could still be viable. 5 μM solutions of B5 and B7 decreased the cell viability to 33% and 44%; whereas healthy cells were 71% and 95%, respectively, after treatment. Antimicrobial properties were explored against the bacterial and fungal microorganisms with B1, B5 and BZ The inhibition zones were evaluated for all boronic structures, and the growth inhibition zones were determined in a range of 7-13 mm diameter for different microorganism species. Staphylococcus aureus was the common micro- organism that three boronic compounds with imine ligands showed the activity. Antioxidant features of B2, B3, B4, B5, B6, B7 and B8 were investigated by different processes such as Beta-carotene bleaching （BCB）, 2,2-diphenyl picryl hydrazyl （DPPH）, 2,2″-azino-bis（ 3-ethylbenzothiazoline-6-sulphonic acid） （ABTS） and CUPric reducing antioxidant capacity （CLIPRAC） methods. Significant antioxidant activity was achieved by the phenyl boronic based ligands and these compounds demonstrated as much activity as standards （α-Toc and BHT）. In addition, all structures were applied properly without any decomposition during the experiments. They were rather stable both in aqueous media and solid state.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
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
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
A DFT-based theoretical investigation is reported here to clarify the mechanism of action of a recently synthesized Ir(Ⅲ)complex,Ir-B(OH)_(2),characterized by the presence of an aryl boronic acid moiety on one bident...A DFT-based theoretical investigation is reported here to clarify the mechanism of action of a recently synthesized Ir(Ⅲ)complex,Ir-B(OH)_(2),characterized by the presence of an aryl boronic acid moiety on one bidentate ligand that can detect H_(2)O_(2) in cancer cells.The H_(2)O_(2)-mediated oxidation of boronic acids under physiological conditions affords the active complex for PDT application,Ir-OH,and a quinone methide(QM)as a by-product,which in turn can scavenge glutathione(GSH)compromising one of the most powerful cellular defence against the ROS produced by PDT treatments.The most plausible reaction mechanism for the oxidation of the aryl boronic acid by H_(2)O_(2) is described.The formation of the products,namely the PS Ir-OH and the QM,is achieved overcoming an energy barrier of 33 kcal mol^(−1) and with a considerable energy gain.The description of the subsequent GSH scavenging mechanism by the released QM evidences that the reaction occurs with a low energy expense.Moreover,the computation of the photophysical properties,needed for evaluating the occurrence of type Ⅰ and type Ⅱ processes,of the prodrug Ir-B(OH)_(2) and the active PS Ir-OH suggests that they are both able to generate the singlet molecular oxygen,^(1)O_(2),while other ROS cannot be achieved.Moreover,the MOs involved in the excited states population,both singlet and triplet,unravel the key role of the metal centre in the ISC process.展开更多
Dynamic room-temperature phosphorescence(RTP)materials with color-tunable afterglow characteristics hold great promise for advanced anti-counterfeiting and multidimensional encryption applications.In this work,we succ...Dynamic room-temperature phosphorescence(RTP)materials with color-tunable afterglow characteristics hold great promise for advanced anti-counterfeiting and multidimensional encryption applications.In this work,we successfully synthesized a novel two-dimensional phenylammonium cadmium chloride perovskite(B-PACC)with enhanced RTP efficiency via boronic acid group-assisted crystallization.Furthermore,a precise doping strategy was employed to introduce Mn^(2+),which assembled into Mn^(2+)pairs forming a Mn^(2+)-based inorganic layer.This layer,together with B-PACC,constructed a heterojunction structure with different interlayer spacings,enabling dynamic afterglow emission color modulation from red to blue.Moreover,tuning the Mn^(2+)concentration enables precise modulation of the energy transfer rates from the singlet and triplet states of the organic moieties to the Mn^(2+)layer,thereby allowing fine control over the dynamic RTP behavior.Benefiting from the minimal background interference and large chromaticity contrast associated with the red-to-blue phosphorescence transition,the system exhibited high visual detectability.Based on this dynamic afterglow behavior,we successfully developed time-resolved anti-counterfeiting patterns and constructed dynamic room-temperature phosphorescence-based four-dimensional(4D)codes,providing new insights into the design of dynamic RTP materials and highly secure encryption strategies.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
Interests in intracellular peptide delivery have continued to grow,significantly fueled by the importance of peptides and their mimetics in modern cell biology and pharmaceutical industry.However,efficient intracellul...Interests in intracellular peptide delivery have continued to grow,significantly fueled by the importance of peptides and their mimetics in modern cell biology and pharmaceutical industry.However,efficient intracellular delivery of membrane-impermeable peptides of different polarities remains a challenging task.In this study,we develop a general and robust strategy for intracellular peptide delivery by using a boronic acid-rich dendrimer.The designed material is capable of transporting peptides with different polarities and charge properties into the cytosol of various cell lines without inducing additional cytotoxicity.The transduction efficacy and proteolytic stability of cargo peptides delivered by the boronic acid-rich dendrimer are much superior to peptides conjugated with cell penetrant peptides such as octaarginine.In addition,the bioactivities of pro-apoptotic peptides are maintained after intracellular delivery.This study provides a versatile and robust platform for the intracellular delivery of membrane-impermeable peptides.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
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
基金support for this work by Hebei Education Department(No.JZX2024004)Central Guidance on Local Science and Technology Development Fund of Hebei Province(No.236Z1404G)+3 种基金the National Natural Science Foundation of China(Nos.22301060 and 21272053)China Postdoctoral Science Foundation(No.2023M730914)the Natural Science Foundation of Hebei Province(Biopharmaceutical Joint Fund No.B2022206008)Project of Science and Technology Department of Hebei Province(No.22567622H)。
文摘Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporting molybdenum complex on C_(3)N_(4)-K and characterized by FT-IR,XRD,SEM,XPS and ICP-OES.Heterogeneous CN–Mo-Bpy catalyst can be applied to the direct amination of nitroarenes and arylboronic acid,thus constructing various valuable diarylamines in high to excellent yields with a wide substrate scope and good functional group tolerance.It is worth noting that this heterogeneous catalyst has high chemical stability and can be recycled for at least five times without reducing its activity.
基金supported by the National Natural Science Foundation of China(No.51973023)Sichuan Science and Technology Program(No.2021JDRC0014).
文摘The"solid-liquid"behavior of vitrimers have not been systematically investigated.Herein,a series of"solid-liquid"vitrimers bearing varying contents of dynamic boronic ester bonds were synthesized via thiol-ene click reactions.These vitrimers allow for flexibile modulation of their network structures and thus show a range of intriguing properties including high stretchability,flexible transition from elasticity to plasticity,strong strain rate dependence,and solid-liquid performance.The dynamic association rate of boronic ester bonds within these vitrimers could be apparently accelerated via increasing the content of boronic ester,which could be used to shape-program the flat vitrimer films into various complex 3D structures just with external force.Materials with such versatile dynamic behavior may open up a range of new applications.
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Funded by the National Natural Science Foundation of China(No.21571144)
文摘An efficient, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic amount of CuSO4 at 130 ℃ using water as a green solvent. The products were obtained in moderate to excellent yields;more importantly, the use of toxic ligands and solvents was avoided. A broad range of aryl boronic acids and scalable processes make this methodology valuable and versatile for the synthesis of a broad range of aryl sulfides.
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.
文摘A colorimetric method for the direct determination of hydrogen peroxide in aqueous solution is described. H2O2 stoichiometrically converts 4-nitrophenyl boronic acid or 4-nitrophenyl boronic acid pinacol ester into 4-nitrophenol, which can be quantified by measuring the absorption at 400 nm in neutral or basic media. The reactions proceed fast under basic conditions and complete in 2 minutes to at pH 11 and 80?C. The linear range for the colorimetric method extends beyond 1.0 to 40 μM H2O2, and the limit of detection is ~1.0 μM H2O2. This method offers a convenient and practical process for rapid determination of hydrogen peroxide in aqueous media. Compared to many other techniques in H2O2 detection, this process is a direct measurement of H2O2, and is relatively unaffected by the presence of various salts, metal ions and the chelator EDTA.
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 Key R&D Program of China (No. 2018YFA0507602)the National Natural Science Foundation of China (Nos. 21572012, 21772006)the State Key Laboratory of Drug Research (No. SIMM1803KF-02)
文摘An efficient and novel methodology to access phenolic glycosides has been established by using coppermediated coupling reaction of aryl boronic acids with hemiacetals.The reaction takes place normally in the presence of Cu(OAc)_2(1.0 equiv.)and pyridine(2.0 equiv.)at 40℃.This protocol distinguishes itself by wide substrate scope,operational simplicity and giving rise to a myriad of phenolic glycosides in good to excellent yields.
基金Dicle University Science and Technology Research Center(DUBTAM)Dicle University Scientific and Technological Research Council(DUBAP)with Grant Number:14–EZF–14 are gratefully acknowledged for their analysis and financial supports
文摘Boronic acid compounds with different substituted groups were handled to synthesize various ligands encoded as B1, B2, B3, B4, BS, B6, B7 and BS. B5 and B7 were tested for the cytotoxic activity against the prostate cancer cells and it was found that the cell viability of cancer cells was decreased while most of the healthy cells could still be viable. 5 μM solutions of B5 and B7 decreased the cell viability to 33% and 44%; whereas healthy cells were 71% and 95%, respectively, after treatment. Antimicrobial properties were explored against the bacterial and fungal microorganisms with B1, B5 and BZ The inhibition zones were evaluated for all boronic structures, and the growth inhibition zones were determined in a range of 7-13 mm diameter for different microorganism species. Staphylococcus aureus was the common micro- organism that three boronic compounds with imine ligands showed the activity. Antioxidant features of B2, B3, B4, B5, B6, B7 and B8 were investigated by different processes such as Beta-carotene bleaching （BCB）, 2,2-diphenyl picryl hydrazyl （DPPH）, 2,2″-azino-bis（ 3-ethylbenzothiazoline-6-sulphonic acid） （ABTS） and CUPric reducing antioxidant capacity （CLIPRAC） methods. Significant antioxidant activity was achieved by the phenyl boronic based ligands and these compounds demonstrated as much activity as standards （α-Toc and BHT）. In addition, all structures were applied properly without any decomposition during the experiments. They were rather stable both in aqueous media and solid state.
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supported by the University of Calabria.The authors gratefully acknowledge the computing time granted by the CINECA(project IsCa3_MoAMCPCT).
文摘A DFT-based theoretical investigation is reported here to clarify the mechanism of action of a recently synthesized Ir(Ⅲ)complex,Ir-B(OH)_(2),characterized by the presence of an aryl boronic acid moiety on one bidentate ligand that can detect H_(2)O_(2) in cancer cells.The H_(2)O_(2)-mediated oxidation of boronic acids under physiological conditions affords the active complex for PDT application,Ir-OH,and a quinone methide(QM)as a by-product,which in turn can scavenge glutathione(GSH)compromising one of the most powerful cellular defence against the ROS produced by PDT treatments.The most plausible reaction mechanism for the oxidation of the aryl boronic acid by H_(2)O_(2) is described.The formation of the products,namely the PS Ir-OH and the QM,is achieved overcoming an energy barrier of 33 kcal mol^(−1) and with a considerable energy gain.The description of the subsequent GSH scavenging mechanism by the released QM evidences that the reaction occurs with a low energy expense.Moreover,the computation of the photophysical properties,needed for evaluating the occurrence of type Ⅰ and type Ⅱ processes,of the prodrug Ir-B(OH)_(2) and the active PS Ir-OH suggests that they are both able to generate the singlet molecular oxygen,^(1)O_(2),while other ROS cannot be achieved.Moreover,the MOs involved in the excited states population,both singlet and triplet,unravel the key role of the metal centre in the ISC process.
基金supported by Foundation of Graphene Powder&Composite Research Centre of Fujian Province(No.2017H_(2)001)Pilot Project of Fujian Province(No.2021H0017).
文摘Dynamic room-temperature phosphorescence(RTP)materials with color-tunable afterglow characteristics hold great promise for advanced anti-counterfeiting and multidimensional encryption applications.In this work,we successfully synthesized a novel two-dimensional phenylammonium cadmium chloride perovskite(B-PACC)with enhanced RTP efficiency via boronic acid group-assisted crystallization.Furthermore,a precise doping strategy was employed to introduce Mn^(2+),which assembled into Mn^(2+)pairs forming a Mn^(2+)-based inorganic layer.This layer,together with B-PACC,constructed a heterojunction structure with different interlayer spacings,enabling dynamic afterglow emission color modulation from red to blue.Moreover,tuning the Mn^(2+)concentration enables precise modulation of the energy transfer rates from the singlet and triplet states of the organic moieties to the Mn^(2+)layer,thereby allowing fine control over the dynamic RTP behavior.Benefiting from the minimal background interference and large chromaticity contrast associated with the red-to-blue phosphorescence transition,the system exhibited high visual detectability.Based on this dynamic afterglow behavior,we successfully developed time-resolved anti-counterfeiting patterns and constructed dynamic room-temperature phosphorescence-based four-dimensional(4D)codes,providing new insights into the design of dynamic RTP materials and highly secure encryption strategies.
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.
基金supported by the National Natural Science Foundation of China (21725402)the Science and Technology Commission of Shanghai Municipality (17XD1401600)+1 种基金Guangdong Innovative and Entrepreneurial Research Team Program (2016ZT06C322)supports from the Flow Cytometry Core Facility and the Confocal Microscopy Facility at ECNU
文摘Interests in intracellular peptide delivery have continued to grow,significantly fueled by the importance of peptides and their mimetics in modern cell biology and pharmaceutical industry.However,efficient intracellular delivery of membrane-impermeable peptides of different polarities remains a challenging task.In this study,we develop a general and robust strategy for intracellular peptide delivery by using a boronic acid-rich dendrimer.The designed material is capable of transporting peptides with different polarities and charge properties into the cytosol of various cell lines without inducing additional cytotoxicity.The transduction efficacy and proteolytic stability of cargo peptides delivered by the boronic acid-rich dendrimer are much superior to peptides conjugated with cell penetrant peptides such as octaarginine.In addition,the bioactivities of pro-apoptotic peptides are maintained after intracellular delivery.This study provides a versatile and robust platform for the intracellular delivery of membrane-impermeable peptides.
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.
