Carboxylic acid-functionalized nano-sized magnetic composite polymers (COOH-NMPs) were synthesized and used for the preparation of the modified glassy carbon electrode, i.e., COOH-NMPs/GCE and DNA/COOH-NMPs/GCE. The e...Carboxylic acid-functionalized nano-sized magnetic composite polymers (COOH-NMPs) were synthesized and used for the preparation of the modified glassy carbon electrode, i.e., COOH-NMPs/GCE and DNA/COOH-NMPs/GCE. The electrochemical behaviors of melamine (MM) were investigated on COOH-NMPs/GCE by cyclic voltammetry (CV) in both cases of DNA in the solution and immobilized on the electrode surface. The electron transfer coefficient (a) and the rate constant (ks) kept unchanged in the absence and presence of DNA. Based on the electrochemical properties of the interaction of MM on the surface of the DNA/COOH-NMPs/GCE, a direct method for the determination of MM in liquid milk was established. The detection limit of this method was 2.0 ng·L﹣1, with average recoveries at 95.9% - 104.2% and RSD at 4.5% - 8.2%. The proposed method was provided to have a good accuracy, high stability and good reproducibility with a simple and environmental friendly process. 10 kinds of liquid milk samples bought from the market randomly were tested, and only 1 of them was found at relatively low level of MM residue with the amount of 0.12 ug·L﹣1.展开更多
An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acylox...An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acyloxy esters in moderate to high yields with a broad substrate scope.All starting materials are readily available,and the reactions can be conducted in the open air at room temperature.展开更多
In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using at...In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using attenuated total reflectance Fourier-transform infrared spectroscopy(ATR-FTIR),the molecular configurations of surface carboxyl groups(COOH),free carboxyl(COOH_(f))and hydrogen-bonded carboxyl(COOH_(HB),were directly correlated with the polar component of surface energy(γ^(s,p)).By decomposing theγ^(s,p)values of the PAA thin films as a sum of the contributions of COOH_(f)and COOH_(H B),the intrinsic polar component of surface energy of COOH_(H B)(γ_(H B)^(s,p*))was quantified for the first time as 8.34 mN/m,significantly lower than that of COOH_(f)(γ_(f)^(s,p*)=34 mN/m).This result highlights that hydrogen bonding markedly reduces theγ^(s,p),providing a rational explanation for the relatively large water contact angle observed on PAA thin films.Furthermore,it establishes a thermodynamic basis for estimating the fraction of surface COOH_(H B)groups(f H B)from wettability measurements.Further extension of the model to carboxyl-terminated self-assembled monolayers(COOH-SAMs)revealed that surface COOH density(ΣCOOH)critically regulates wetting behavior:whenΣCOOH ranges from 4.30 to 5.25 nm^(-2),COOH groups predominantly exist in a free state and facilitate effective hydration layers,thereby promoting superhydrophilicity.Overall,this study not only establishes a unified thermodynamic framework linking surface COOH configurations to macroscopic wettability,but also validates its universality by extending it to COOH-SAMs systems,thereby providing a unified theoretical framework for the controllable design of hydrophilicity in various COOH-functionalized surfaces.展开更多
Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding...Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding research endeavor.In this work,a new method for synthesizing redox centers spatially separated Z-scheme CdS@graphitic carbon nitride(g-C_(3)N_(4))was developed,aiming to achieve photocatalytic benzylic and aliphatic sp^(3)C-H activation as well as CO_(2)carboxylation without sacrificial agent.Notably,both benzylic and aliphatic sp^(3)C-H activation together with CO_(2)carboxylation were achieved in heterogeneous photocatalytic system,resulting in the production of carboxylic acids with increased carbon chains under mild conditions.Various methylbenzene derivatives and cycloalkanes were employed to synthesize carbon-chain increased acids via a process involving K_(3)PO_(4)-assisted photogenerated holes activation for benzyl radical generation,photoinduced CO_(2)reduction,as well as solvent-assisted chemoselective carboxylation.Various characterizations and density functional theory(DFT)results revealed that Z-scheme CdS@g-C_(3)N_(4)not just significantly enhanced separation of charges and accumulation of photoinduced electrons on g-C_(3)N_(4)but also facilitated adsorption along with activation of CO_(2).This research provided novel heterogeneous photocatalytic approach to produce carbon chains increased carboxylic acids via sp^(3)C-H activation and CO_(2)carboxylation.展开更多
To improve the low-temperature performances of Li-ion cells, three types of linear carboxylic ester-based electrolyte, such as EC/EMC/EA（1：1：2, mass ratio）, EC/EMC/EP（1：1：2, mass ratio） and EC/EMC/EB（1：1：2,...To improve the low-temperature performances of Li-ion cells, three types of linear carboxylic ester-based electrolyte, such as EC/EMC/EA（1：1：2, mass ratio）, EC/EMC/EP（1：1：2, mass ratio） and EC/EMC/EB（1：1：2, mass ratio）, were prepared to substitute for industrial electrolyte（EC/EMC/DMC）. Then, 18650-type Li Mn2O4-graphite cells（nominal capacity of 1150 mA ·h） were assembled and studied. Results show that the cells containing three types of electrolyte are able to undertake 5C discharging current with above 93% capacity retention at-20 °C. Electrochemical impedance spectra show that the discharge capacity fading of Li-ion cells at low temperature is mainly ascribed to the charge transfer resistance increasing with temperature decreasing. In comparison, the cells containing electrolyte of 1.0 mol/L LiPF6 in EC/EMC/EA（1：1：2, mass ratio） have the highest capacity retention of 90% at-40 °C and 44.41% at-60 °C, due to its lowest charge-transfer resistance.展开更多
Two new phenolic carboxylic acid esters n-butyl eucomate(1) and methyl eucomate (2) and six known compounds eucomic acid(3), 3-β-acetyl-taraxerol (4), friedelin(5),lupenone(6),methyl linoleate(7) and methy...Two new phenolic carboxylic acid esters n-butyl eucomate(1) and methyl eucomate (2) and six known compounds eucomic acid(3), 3-β-acetyl-taraxerol (4), friedelin(5),lupenone(6),methyl linoleate(7) and methyl oleate(8) were isolated from the stems of Opuntia vulgaris Mill(Cactaceae). Their structures were determined on the basis of spectral methods. Compounds 3,4,6,7,8 were isolated for the first time from this plant.展开更多
A carbon paste electrode (CPE) modified with ferrocene carboxylic acid (FcCA) and TiO2 nanoparticles was constructed by incorporating TiO2 nanoparticles and ferrocene carboxylic acid into the carbon paste matrix. The ...A carbon paste electrode (CPE) modified with ferrocene carboxylic acid (FcCA) and TiO2 nanoparticles was constructed by incorporating TiO2 nanoparticles and ferrocene carboxylic acid into the carbon paste matrix. The electrochemical behavior of captopril (CAP) at the surface of the modified electrode was investigated using electroanalytical methods. The modified electrode showed excellent electrocatalytic activity for the oxidation of CAP in aqueous solutions at physiological pH values. Cyclic voltammetric curves showed that the oxidation of CAP at the surface of the modified electrode reduced its overpotential by more than 290 mV. The modified electrode was used for detecting captopril using cyclic voltammetry and square wave voltammetry techniques. A calibration curve in the range of 0.03 to 2400 μmol/L was obtained that had a detection limit of 0.0096 μmol/L (3?) under the optimized conditions. The modified electrode was successfully used for the determination of captopril in pharmaceutical and biological samples.展开更多
Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via...Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.展开更多
An ultrasensitive electrochemical sensor based on polydopamine/carboxylic multi-walled carbon nanotubes(MWCNTs à COOH) nanocomposites modified glassy carbon electrode(GCE) was presented in this work, which has be...An ultrasensitive electrochemical sensor based on polydopamine/carboxylic multi-walled carbon nanotubes(MWCNTs à COOH) nanocomposites modified glassy carbon electrode(GCE) was presented in this work, which has been developed for highly selective and highly sensitive determination of an antimicrobial drug, metronidazole. The preparation of polydopamine/MWCNTs–COOH nanocomposites/GCE sensor is simple and possesses high reproducible, where polydopamine can be coated on the surface of MWCNTs–COOH via a simple electropolymerization process. Under optimized conditions, the proposed sensor showed ultrasensitive determination for metronidazole with a wide linear detection range from5 to 5000 mmol/dm^3 and a low detection limit of 0.25 mmol/dm^3(S/N=3). Moreover, the proposed sensor has been successfully applied for the quantitative determination of metronidazole in real drug samples. This work may provide a novel and effective analytical platform for determination of metronidazole in application of real pharmaceutical and biological samples analysis.展开更多
Complex [Sr2（pdc）2（H2O）7]·H2O （1, H2pdc = 2,3-pyrazinedicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction studies and FT-IR. Structural determination reveals that t...Complex [Sr2（pdc）2（H2O）7]·H2O （1, H2pdc = 2,3-pyrazinedicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction studies and FT-IR. Structural determination reveals that there are two crystallographically independent strontium ions in 1. The coordination geometry of Sr（1） is a nine-coordinated distorted monocapped tetragonal antiprism, while Sr（2） is a nine-coordinated distorted monocapped tetragonal prism. The ligand pdc2- takes two different connecting modes and links St（If） centers to generate a 2D layer structure. The 2D layers are linked through O-H...O and O-H...N hydrogen bonds to form a 3D framework structure. Thermal stability and luminescent properties of complex 1 are investigated. 1 belongs to the monoclinic system, space group P21/n with a = 10.7182（10）, b = 7.0377（6）, c = 29.225（3） A, β = 95.7170（10）°, Z = 4, V = 2193.5（3） A3, Mr = 651.56, Dc = 1.973 g/cm3, F（000） = 1296,μ = 4.951 mm-1, the final R = 0.0318 and wR = 0.0726 for 3938 observed reflections with I 〉 2σ（/）.展开更多
Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, elect...Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, electrochemical carboxylation, organic halides, organic triflates, alkenes, aromatic compounds, and carbonyl compounds can readily occur in the presence of an atmospheric pressure of carbon dioxide to form the corresponding carboxylic acids with high yields, when a sacrificial anode such as magnesium or aluminum is used in the electrolysis. The electrochemical carboxylation of vinyl bromides was successfully applied for the synthesis of the precursor of nonsteroidal anti-inflammatory agents such as ibuprofen and naproxen. On the other hand, supercritical carbon dioxide （scCO2） has significant potential as an environmentally benign solvent in organic synthesis and it could be used both as a solvent and as a reagent in these electrochemical carboxylations by using a small amount of cosolvent.展开更多
A metal-free cross coupling between common CH2Cl2 and carboxylic acids has been achieved with K2CO3 as the sole additive. This simple protocol is a convenient and cost-effective route to synthesize methylene diesters ...A metal-free cross coupling between common CH2Cl2 and carboxylic acids has been achieved with K2CO3 as the sole additive. This simple protocol is a convenient and cost-effective route to synthesize methylene diesters from a wide scope of carboxylic acids substrates with good functional group tolerance. Several gram-scale reactions have been performed to evaluate the effectiveness and practicality of this protocol.展开更多
To examine a） the effect of organophosphorus pesticide exposure on activity of carboxylic esterases, namely butyrylcholinesterase （BChE）, carboxylesterase （CarbE） and paraoxonase （PonE）; and b） the association...To examine a） the effect of organophosphorus pesticide exposure on activity of carboxylic esterases, namely butyrylcholinesterase （BChE）, carboxylesterase （CarbE） and paraoxonase （PonE）; and b） the association of polymorphisms of BChE and PonE with individual genetic susceptibility to organophosphorus pesticide exposure. Methods A cross-sectional study was conducted in 75 workers exposed to organophosphorus pesticides and 100 non-exposed controls. The serum activity of these enzymes was measured. Variant forms of BCHE-K, PON-192, and PON-55 were detected. A symptom score was developed as a proxy measure of clinical outcomes. Results Activities of both BChE and CarbE were lower in exposed workers （27.3±21.65 runol.hl.mL^-l and 235.6±104.03 nmol-min^-l.mL^-l） than in non-exposed workers （78.313±30.354 nmol.h^-l.mL^-1 and 362.681_＋194.997 nmol.min^-1.mL^-1）. The activity of PonE was not associated with exposure status. The AChE activity in the exposed workers with BCHE-K genotype UU （61 cases）, genotype UK （12 cases） and genotype KK （2 cases） was 105.05, 84.42 and 79.00 mmol-h^-1.mL^-1, respectively and the accumulative symptom scores were 3.74, 9.17, and 12.50 accordingly. The AChE activity in the exposed workers with PON-192 genotype BB （37）, genotype AB （27） and genotype AA （11） was 116.8, 91.2, and 72,3 mmol-h^-1.mL^-1, respectively and the symptom scores were 2.00, 6.74, and 9.73 accordingly. The AChE activity in those with PON-55 genotype LL （70） and genotype LM （5） was 102.4 and 82.8 mmol-h^-1.mL^-1 and the symptom scores were 4.53 and 9.20. The symptom score was the highest in individuals with abnormal homozygote for each of the three gene loci. Condusions Long-term exposure to organophosphorus pesticides can inhibit BChE and CarbE activity, but exerts no inhibitory effect on PonE activity. Different genotypes of BCHE-K, PON-192, and PON-55 may be related to the severity of adverse health effects of organophosphorus pesticide exposure. Implications of potentially higher susceptibility of workers with mutant homozygotes should be evaluated to reduce health risks.展开更多
A yellow, alkali-clearable azo disperse dye containing a carboxylic ester moiety was readily synthesized from the reactant p-aminobenzoic acid by successive diazotization, coupling reaction, chlorination and esterific...A yellow, alkali-clearable azo disperse dye containing a carboxylic ester moiety was readily synthesized from the reactant p-aminobenzoic acid by successive diazotization, coupling reaction, chlorination and esterification with ethanol. Then its molecular structure was characterized by FTIR,1H NMR,13 C NMR,mass spectrometry and elemental analysis. The synthesized dye and a similar control dye containing the acylamide moiety（I） were applied to dyeing poly（ethylene terephthalate） fabric and their washing and rubbing fastness properties with different post-treatment methods（reduction clearing and alkali clearing） were examined and compared. It is found that the ester-containing disperse dye shows good alkali-clear ability on poly（ethylene terephthalate） fabric and contaminates little to environment due to the absence of reductants, as well as low toxicity and easy recycling of the hydrolysates.展开更多
A highly efficient copper-catalyzed approach to form amide bonds from formamides and carboxylic acids was developed. This protocol shows broad substrate scopes and high yields in the presence of 1 mol% catalyst and 4....A highly efficient copper-catalyzed approach to form amide bonds from formamides and carboxylic acids was developed. This protocol shows broad substrate scopes and high yields in the presence of 1 mol% catalyst and 4.0 equiv, formamides.展开更多
The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid（C11H9Cl N2O2, HL）（1） and [Cu（L）2（H2O）]（2） were prepared and structurally characterized by elemental analysis, IR and single-crysta...The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid（C11H9Cl N2O2, HL）（1） and [Cu（L）2（H2O）]（2） were prepared and structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1（C11H9Cl N2O2） crystallizes in the monoclinic system, space group P21/n with a = 7.249（3）, b = 20.515（10）, c = 7.249（3）,β= 96.30°, V = 1071.6（9） ？3, Z = 4, Mr = 236.65, Dc = 1.467 g/cm3, F（000） = 488, GOOF = 1.029, μ= 0.341 mm-1, the final R = 0.0736 and w R = 0.1966 for 1500 observed reflections with I 〉 2σ（I）. Compound 2（C22H18Cl2Cu N4O5） crystallizes in the monoclinic system, space group P21/c with a = 7.2931（6）, b = 24.548（2）, c = 13.2726（11）, β= 99.4040（10）°, V = 2344.2（3） ？3, Z = 4, Mr = 552.84, Dc = 1.566 g/cm3, F（000） = 1124, GOOF = 1.050, μ= 1.201 mm-1, the final R = 0.0376 and w R = 0.1000 for 3626 observed reflections with I 〉 2σ（I）. 1 and 2 are connected through hydrogen bonding interactions to generate 2D and 3D supramolecular structures, respectively. Moreover, the preliminary antibacterial activities of 1 and 2 against the gram positive bacteria（S. aureus, C. albicans and B. subtilis） and gram negative bacteria（E. coli and P. aeruginosa） have been tested by using the microdilution method, and the results indicate that 2 is more active than 1 against the tested bacteria.展开更多
The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving c...The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.展开更多
A mild,efficient and simple method for the preparation of acyl azides from carboxylic acids using chlorodiphenylphosphine in the presence of molecular iodine and sodium azide is described.
A new gadolinium porous complex,(NH4)2[Gd2(pzdc)4(H2O)2],was synthesized through hydrothermal reaction of 2,3-pyrazinedicarboxylic acid and Gd(NO3)3·6 H2O with the pH value adjusted by ammonia.It was characterize...A new gadolinium porous complex,(NH4)2[Gd2(pzdc)4(H2O)2],was synthesized through hydrothermal reaction of 2,3-pyrazinedicarboxylic acid and Gd(NO3)3·6 H2O with the pH value adjusted by ammonia.It was characterized by elemental analysis,FT-IR,TGA and further by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/c with a=14.249(7),b=15.889(8),c=12.846(7)A,β=95.724(10)°,V=2894(3)A^3,Z=4,Dc=2.385 g/cm^3,μ(Mo Ka)=4.65 mm^–1 and F(000)=1976.1976 reflections were measured and 6446 independent reflections(Rint=0.0985)were used in further refinement.The complex exhibits a 3D framework constructed from the[Gd2(pzdc)4(H2O)2]2-building blocks.It is scarce that the NH4+cations are located in the channels and balance the charge of anion framework.Furthermore,the ion exchange property of this complex has also been studied.The NH4+cations can be replaced by Na+cations,which is an uncommon phenomenon for gadolinium-containing porous complex.展开更多
The title complex [Sm2（bdc）3（phen）2]n （1, H2bdc = 1,3-benzenedicarboxylic acid, phen = 1,10-phenanthrolin）, a new samarium（III） complex based on ligand H2bdc and 1,10-phen- anthrolin, has been hydrothermally s...The title complex [Sm2（bdc）3（phen）2]n （1, H2bdc = 1,3-benzenedicarboxylic acid, phen = 1,10-phenanthrolin）, a new samarium（III） complex based on ligand H2bdc and 1,10-phen- anthrolin, has been hydrothermally synthesized and characterized by elemental analysis, FT-IR, and single-crystal X-ray diffraction. The crystal structure reveals that the Sm（1） centre adopts an eight-coordinated distorted square anti-prism coordination geometry, while the Sm（2） centre adopts a nine-coordinated distorted monocapped square prism coordination geometry. The ligand bdc2- takes two different connecting modes and links the Sm（llI） centers to give rise to a 2D network structure. Further, 2D layers of 1 are connected together to form a 3D structure through C-H-O hydrogen bonding interactions. The luminescent property and thermal stability of complex 1 are studied. 1 belongs to the triclinic system, space group P1 with a = 10.7367（5）, b = 14.3750（7）, c = 13.7505（3）A, a = 92.8840（10）, β = 104.4010（10）, ）, = 98.1400（10）°, Z= 2, V= 2143.44（18） A3, Mr = 1153.44, Dc = 1.787 g/cm3, F（000） = 1128,μ= 2.784 mm-1, the final R = 0.0279 and wR = 0.0720 for 8226 observed reflections with 1 〉 2σ（I）.展开更多
文摘Carboxylic acid-functionalized nano-sized magnetic composite polymers (COOH-NMPs) were synthesized and used for the preparation of the modified glassy carbon electrode, i.e., COOH-NMPs/GCE and DNA/COOH-NMPs/GCE. The electrochemical behaviors of melamine (MM) were investigated on COOH-NMPs/GCE by cyclic voltammetry (CV) in both cases of DNA in the solution and immobilized on the electrode surface. The electron transfer coefficient (a) and the rate constant (ks) kept unchanged in the absence and presence of DNA. Based on the electrochemical properties of the interaction of MM on the surface of the DNA/COOH-NMPs/GCE, a direct method for the determination of MM in liquid milk was established. The detection limit of this method was 2.0 ng·L﹣1, with average recoveries at 95.9% - 104.2% and RSD at 4.5% - 8.2%. The proposed method was provided to have a good accuracy, high stability and good reproducibility with a simple and environmental friendly process. 10 kinds of liquid milk samples bought from the market randomly were tested, and only 1 of them was found at relatively low level of MM residue with the amount of 0.12 ug·L﹣1.
文摘An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acyloxy esters in moderate to high yields with a broad substrate scope.All starting materials are readily available,and the reactions can be conducted in the open air at room temperature.
文摘In this study,polyacrylic acid(PAA)films were employed as a model system,and a series of PAA films with tunable water wettability was systematically prepared by varying molecular weight and curing temperature.Using attenuated total reflectance Fourier-transform infrared spectroscopy(ATR-FTIR),the molecular configurations of surface carboxyl groups(COOH),free carboxyl(COOH_(f))and hydrogen-bonded carboxyl(COOH_(HB),were directly correlated with the polar component of surface energy(γ^(s,p)).By decomposing theγ^(s,p)values of the PAA thin films as a sum of the contributions of COOH_(f)and COOH_(H B),the intrinsic polar component of surface energy of COOH_(H B)(γ_(H B)^(s,p*))was quantified for the first time as 8.34 mN/m,significantly lower than that of COOH_(f)(γ_(f)^(s,p*)=34 mN/m).This result highlights that hydrogen bonding markedly reduces theγ^(s,p),providing a rational explanation for the relatively large water contact angle observed on PAA thin films.Furthermore,it establishes a thermodynamic basis for estimating the fraction of surface COOH_(H B)groups(f H B)from wettability measurements.Further extension of the model to carboxyl-terminated self-assembled monolayers(COOH-SAMs)revealed that surface COOH density(ΣCOOH)critically regulates wetting behavior:whenΣCOOH ranges from 4.30 to 5.25 nm^(-2),COOH groups predominantly exist in a free state and facilitate effective hydration layers,thereby promoting superhydrophilicity.Overall,this study not only establishes a unified thermodynamic framework linking surface COOH configurations to macroscopic wettability,but also validates its universality by extending it to COOH-SAMs systems,thereby providing a unified theoretical framework for the controllable design of hydrophilicity in various COOH-functionalized surfaces.
基金financially supported by Natural Science Foundation Project of CQ(No.CSTB2023NSCQ-LZX0067)Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJZD-K202200804)+1 种基金Venture&Innovation Support Program for Chongqing Overseas Returnees(No.cx2020113)National Natural Science Foundation of China(No.21201184).
文摘Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding research endeavor.In this work,a new method for synthesizing redox centers spatially separated Z-scheme CdS@graphitic carbon nitride(g-C_(3)N_(4))was developed,aiming to achieve photocatalytic benzylic and aliphatic sp^(3)C-H activation as well as CO_(2)carboxylation without sacrificial agent.Notably,both benzylic and aliphatic sp^(3)C-H activation together with CO_(2)carboxylation were achieved in heterogeneous photocatalytic system,resulting in the production of carboxylic acids with increased carbon chains under mild conditions.Various methylbenzene derivatives and cycloalkanes were employed to synthesize carbon-chain increased acids via a process involving K_(3)PO_(4)-assisted photogenerated holes activation for benzyl radical generation,photoinduced CO_(2)reduction,as well as solvent-assisted chemoselective carboxylation.Various characterizations and density functional theory(DFT)results revealed that Z-scheme CdS@g-C_(3)N_(4)not just significantly enhanced separation of charges and accumulation of photoinduced electrons on g-C_(3)N_(4)but also facilitated adsorption along with activation of CO_(2).This research provided novel heterogeneous photocatalytic approach to produce carbon chains increased carboxylic acids via sp^(3)C-H activation and CO_(2)carboxylation.
基金Project(2007BAE12B01)supported by the National Key Technology Research and Development Program of ChinaProject(20803095)supported by the National Natural Science Foundation of China
文摘To improve the low-temperature performances of Li-ion cells, three types of linear carboxylic ester-based electrolyte, such as EC/EMC/EA（1：1：2, mass ratio）, EC/EMC/EP（1：1：2, mass ratio） and EC/EMC/EB（1：1：2, mass ratio）, were prepared to substitute for industrial electrolyte（EC/EMC/DMC）. Then, 18650-type Li Mn2O4-graphite cells（nominal capacity of 1150 mA ·h） were assembled and studied. Results show that the cells containing three types of electrolyte are able to undertake 5C discharging current with above 93% capacity retention at-20 °C. Electrochemical impedance spectra show that the discharge capacity fading of Li-ion cells at low temperature is mainly ascribed to the charge transfer resistance increasing with temperature decreasing. In comparison, the cells containing electrolyte of 1.0 mol/L LiPF6 in EC/EMC/EA（1：1：2, mass ratio） have the highest capacity retention of 90% at-40 °C and 44.41% at-60 °C, due to its lowest charge-transfer resistance.
文摘Two new phenolic carboxylic acid esters n-butyl eucomate(1) and methyl eucomate (2) and six known compounds eucomic acid(3), 3-β-acetyl-taraxerol (4), friedelin(5),lupenone(6),methyl linoleate(7) and methyl oleate(8) were isolated from the stems of Opuntia vulgaris Mill(Cactaceae). Their structures were determined on the basis of spectral methods. Compounds 3,4,6,7,8 were isolated for the first time from this plant.
文摘A carbon paste electrode (CPE) modified with ferrocene carboxylic acid (FcCA) and TiO2 nanoparticles was constructed by incorporating TiO2 nanoparticles and ferrocene carboxylic acid into the carbon paste matrix. The electrochemical behavior of captopril (CAP) at the surface of the modified electrode was investigated using electroanalytical methods. The modified electrode showed excellent electrocatalytic activity for the oxidation of CAP in aqueous solutions at physiological pH values. Cyclic voltammetric curves showed that the oxidation of CAP at the surface of the modified electrode reduced its overpotential by more than 290 mV. The modified electrode was used for detecting captopril using cyclic voltammetry and square wave voltammetry techniques. A calibration curve in the range of 0.03 to 2400 μmol/L was obtained that had a detection limit of 0.0096 μmol/L (3?) under the optimized conditions. The modified electrode was successfully used for the determination of captopril in pharmaceutical and biological samples.
基金supported by the National Nature Science Foundation of China (J1210060, 21143002)
文摘Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.21475046,21427809)
文摘An ultrasensitive electrochemical sensor based on polydopamine/carboxylic multi-walled carbon nanotubes(MWCNTs à COOH) nanocomposites modified glassy carbon electrode(GCE) was presented in this work, which has been developed for highly selective and highly sensitive determination of an antimicrobial drug, metronidazole. The preparation of polydopamine/MWCNTs–COOH nanocomposites/GCE sensor is simple and possesses high reproducible, where polydopamine can be coated on the surface of MWCNTs–COOH via a simple electropolymerization process. Under optimized conditions, the proposed sensor showed ultrasensitive determination for metronidazole with a wide linear detection range from5 to 5000 mmol/dm^3 and a low detection limit of 0.25 mmol/dm^3(S/N=3). Moreover, the proposed sensor has been successfully applied for the quantitative determination of metronidazole in real drug samples. This work may provide a novel and effective analytical platform for determination of metronidazole in application of real pharmaceutical and biological samples analysis.
基金supported by the University Science Foundation of Anhui Province(No.KJ2011Z271)Anhui Province Natural Science Foundation(No.1208085MB31)the Applied Chemistry Key Constructing Subject of Anhui Province(No.200802187C)
文摘Complex [Sr2（pdc）2（H2O）7]·H2O （1, H2pdc = 2,3-pyrazinedicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction studies and FT-IR. Structural determination reveals that there are two crystallographically independent strontium ions in 1. The coordination geometry of Sr（1） is a nine-coordinated distorted monocapped tetragonal antiprism, while Sr（2） is a nine-coordinated distorted monocapped tetragonal prism. The ligand pdc2- takes two different connecting modes and links St（If） centers to generate a 2D layer structure. The 2D layers are linked through O-H...O and O-H...N hydrogen bonds to form a 3D framework structure. Thermal stability and luminescent properties of complex 1 are investigated. 1 belongs to the monoclinic system, space group P21/n with a = 10.7182（10）, b = 7.0377（6）, c = 29.225（3） A, β = 95.7170（10）°, Z = 4, V = 2193.5（3） A3, Mr = 651.56, Dc = 1.973 g/cm3, F（000） = 1296,μ = 4.951 mm-1, the final R = 0.0318 and wR = 0.0726 for 3938 observed reflections with I 〉 2σ（/）.
文摘Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, electrochemical carboxylation, organic halides, organic triflates, alkenes, aromatic compounds, and carbonyl compounds can readily occur in the presence of an atmospheric pressure of carbon dioxide to form the corresponding carboxylic acids with high yields, when a sacrificial anode such as magnesium or aluminum is used in the electrolysis. The electrochemical carboxylation of vinyl bromides was successfully applied for the synthesis of the precursor of nonsteroidal anti-inflammatory agents such as ibuprofen and naproxen. On the other hand, supercritical carbon dioxide （scCO2） has significant potential as an environmentally benign solvent in organic synthesis and it could be used both as a solvent and as a reagent in these electrochemical carboxylations by using a small amount of cosolvent.
基金Financial support from the National Natural Science Foundation of China(NSFC, Nos. 21761021 and 21571094)Natural Science Foundation of Jiangxi Province(No. 20171BAB203002)Sci & Tech Project of Education Department of Jiangxi Province(No. 60007)
文摘A metal-free cross coupling between common CH2Cl2 and carboxylic acids has been achieved with K2CO3 as the sole additive. This simple protocol is a convenient and cost-effective route to synthesize methylene diesters from a wide scope of carboxylic acids substrates with good functional group tolerance. Several gram-scale reactions have been performed to evaluate the effectiveness and practicality of this protocol.
基金This work was supported by the grant from National 973 Project (2002CB512902) and the grant from Shanghai Shuguang Program.
文摘To examine a） the effect of organophosphorus pesticide exposure on activity of carboxylic esterases, namely butyrylcholinesterase （BChE）, carboxylesterase （CarbE） and paraoxonase （PonE）; and b） the association of polymorphisms of BChE and PonE with individual genetic susceptibility to organophosphorus pesticide exposure. Methods A cross-sectional study was conducted in 75 workers exposed to organophosphorus pesticides and 100 non-exposed controls. The serum activity of these enzymes was measured. Variant forms of BCHE-K, PON-192, and PON-55 were detected. A symptom score was developed as a proxy measure of clinical outcomes. Results Activities of both BChE and CarbE were lower in exposed workers （27.3±21.65 runol.hl.mL^-l and 235.6±104.03 nmol-min^-l.mL^-l） than in non-exposed workers （78.313±30.354 nmol.h^-l.mL^-1 and 362.681_＋194.997 nmol.min^-1.mL^-1）. The activity of PonE was not associated with exposure status. The AChE activity in the exposed workers with BCHE-K genotype UU （61 cases）, genotype UK （12 cases） and genotype KK （2 cases） was 105.05, 84.42 and 79.00 mmol-h^-1.mL^-1, respectively and the accumulative symptom scores were 3.74, 9.17, and 12.50 accordingly. The AChE activity in the exposed workers with PON-192 genotype BB （37）, genotype AB （27） and genotype AA （11） was 116.8, 91.2, and 72,3 mmol-h^-1.mL^-1, respectively and the symptom scores were 2.00, 6.74, and 9.73 accordingly. The AChE activity in those with PON-55 genotype LL （70） and genotype LM （5） was 102.4 and 82.8 mmol-h^-1.mL^-1 and the symptom scores were 4.53 and 9.20. The symptom score was the highest in individuals with abnormal homozygote for each of the three gene loci. Condusions Long-term exposure to organophosphorus pesticides can inhibit BChE and CarbE activity, but exerts no inhibitory effect on PonE activity. Different genotypes of BCHE-K, PON-192, and PON-55 may be related to the severity of adverse health effects of organophosphorus pesticide exposure. Implications of potentially higher susceptibility of workers with mutant homozygotes should be evaluated to reduce health risks.
基金supported by the National Natural Science Foundation of China(Nos.51173168,21106135)Zhejiang Provincial Key Innovation Team(No.2010R50038)+1 种基金Zhejiang Provincial Top Key Academic Discipline of Chemical Engineering and Technology of Zhejiang Sci-Tech University‘‘521’’ Talent Project of Zhejiang Sci-Tech University
文摘A yellow, alkali-clearable azo disperse dye containing a carboxylic ester moiety was readily synthesized from the reactant p-aminobenzoic acid by successive diazotization, coupling reaction, chlorination and esterification with ethanol. Then its molecular structure was characterized by FTIR,1H NMR,13 C NMR,mass spectrometry and elemental analysis. The synthesized dye and a similar control dye containing the acylamide moiety（I） were applied to dyeing poly（ethylene terephthalate） fabric and their washing and rubbing fastness properties with different post-treatment methods（reduction clearing and alkali clearing） were examined and compared. It is found that the ester-containing disperse dye shows good alkali-clear ability on poly（ethylene terephthalate） fabric and contaminates little to environment due to the absence of reductants, as well as low toxicity and easy recycling of the hydrolysates.
基金supported by the National Natural Science Foundation of China(No.21372176)Tongji University 985 Phase Ⅲ funds+1 种基金Pujiang Project of Shanghai Science and Technology Commission(No.11 J1409800)the Program for Professor of Special Appointment(Eastern Scholar) at Shanghai Institutions of Higher Learning
文摘A highly efficient copper-catalyzed approach to form amide bonds from formamides and carboxylic acids was developed. This protocol shows broad substrate scopes and high yields in the presence of 1 mol% catalyst and 4.0 equiv, formamides.
基金Supported by the National Natural Science Foundation of China(No.20662007)the Bureau of Education of Jiangxi Province(No.GJJ09064)Jiangxi Science and Technology Support Program(20112BBF60009)
文摘The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid（C11H9Cl N2O2, HL）（1） and [Cu（L）2（H2O）]（2） were prepared and structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1（C11H9Cl N2O2） crystallizes in the monoclinic system, space group P21/n with a = 7.249（3）, b = 20.515（10）, c = 7.249（3）,β= 96.30°, V = 1071.6（9） ？3, Z = 4, Mr = 236.65, Dc = 1.467 g/cm3, F（000） = 488, GOOF = 1.029, μ= 0.341 mm-1, the final R = 0.0736 and w R = 0.1966 for 1500 observed reflections with I 〉 2σ（I）. Compound 2（C22H18Cl2Cu N4O5） crystallizes in the monoclinic system, space group P21/c with a = 7.2931（6）, b = 24.548（2）, c = 13.2726（11）, β= 99.4040（10）°, V = 2344.2（3） ？3, Z = 4, Mr = 552.84, Dc = 1.566 g/cm3, F（000） = 1124, GOOF = 1.050, μ= 1.201 mm-1, the final R = 0.0376 and w R = 0.1000 for 3626 observed reflections with I 〉 2σ（I）. 1 and 2 are connected through hydrogen bonding interactions to generate 2D and 3D supramolecular structures, respectively. Moreover, the preliminary antibacterial activities of 1 and 2 against the gram positive bacteria（S. aureus, C. albicans and B. subtilis） and gram negative bacteria（E. coli and P. aeruginosa） have been tested by using the microdilution method, and the results indicate that 2 is more active than 1 against the tested bacteria.
基金financial support from the King Abdullah University of Science and Technology(KAUST).
文摘The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.
基金the Persian Gulf University Research Council for generous partial financial support of this study
文摘A mild,efficient and simple method for the preparation of acyl azides from carboxylic acids using chlorodiphenylphosphine in the presence of molecular iodine and sodium azide is described.
基金supported by the National Natural Science Foundation of China(No.51563019)the Natural Science Foundation of Inner Mongolia(No.2013MS0212,2018BS02009)
文摘A new gadolinium porous complex,(NH4)2[Gd2(pzdc)4(H2O)2],was synthesized through hydrothermal reaction of 2,3-pyrazinedicarboxylic acid and Gd(NO3)3·6 H2O with the pH value adjusted by ammonia.It was characterized by elemental analysis,FT-IR,TGA and further by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/c with a=14.249(7),b=15.889(8),c=12.846(7)A,β=95.724(10)°,V=2894(3)A^3,Z=4,Dc=2.385 g/cm^3,μ(Mo Ka)=4.65 mm^–1 and F(000)=1976.1976 reflections were measured and 6446 independent reflections(Rint=0.0985)were used in further refinement.The complex exhibits a 3D framework constructed from the[Gd2(pzdc)4(H2O)2]2-building blocks.It is scarce that the NH4+cations are located in the channels and balance the charge of anion framework.Furthermore,the ion exchange property of this complex has also been studied.The NH4+cations can be replaced by Na+cations,which is an uncommon phenomenon for gadolinium-containing porous complex.
基金supported by the Natural Science Foundation of Anhui Province(1208085MB31)NNSFC(21271106)+1 种基金the Applied Chemistry Key Constructing Subject of Anhui Province(200802187C)Student Research Project of Chuzhou University(2012XS18,2012XS19)
文摘The title complex [Sm2（bdc）3（phen）2]n （1, H2bdc = 1,3-benzenedicarboxylic acid, phen = 1,10-phenanthrolin）, a new samarium（III） complex based on ligand H2bdc and 1,10-phen- anthrolin, has been hydrothermally synthesized and characterized by elemental analysis, FT-IR, and single-crystal X-ray diffraction. The crystal structure reveals that the Sm（1） centre adopts an eight-coordinated distorted square anti-prism coordination geometry, while the Sm（2） centre adopts a nine-coordinated distorted monocapped square prism coordination geometry. The ligand bdc2- takes two different connecting modes and links the Sm（llI） centers to give rise to a 2D network structure. Further, 2D layers of 1 are connected together to form a 3D structure through C-H-O hydrogen bonding interactions. The luminescent property and thermal stability of complex 1 are studied. 1 belongs to the triclinic system, space group P1 with a = 10.7367（5）, b = 14.3750（7）, c = 13.7505（3）A, a = 92.8840（10）, β = 104.4010（10）, ）, = 98.1400（10）°, Z= 2, V= 2143.44（18） A3, Mr = 1153.44, Dc = 1.787 g/cm3, F（000） = 1128,μ= 2.784 mm-1, the final R = 0.0279 and wR = 0.0720 for 8226 observed reflections with 1 〉 2σ（I）.
