The photodegradation of persistent and bioaccumulative perftuorooctanoic acid （PFOA） in water by 185 nm vacuum ultraviolet （VUV） light was examined to develop an effective technology to deal with PFOA pollution. P...The photodegradation of persistent and bioaccumulative perftuorooctanoic acid （PFOA） in water by 185 nm vacuum ultraviolet （VUV） light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids （PFCAs）, that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.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
Study on a new composite of epoxy resin/elastomeric nano-particles (ENP) is re- ported in this paper, which shows that, in comparison with pure epoxy resin and epoxy toughened with CTBN, the composites of epoxy resin/...Study on a new composite of epoxy resin/elastomeric nano-particles (ENP) is re- ported in this paper, which shows that, in comparison with pure epoxy resin and epoxy toughened with CTBN, the composites of epoxy resin/carboxylic nitrile-butadiene ENP and epoxy resin/styrene butadiene vinyl-pyridine ENP possess both higher toughness and heat resistance. Both ENPs used in the study have an average size of less than 100 nm. Study on the epoxy network’s morphology and interface properties suggests that due to the chemical reaction be- tween ENP and epoxy resin and more hydrogen bonds between nitrile groups of the rubber and hydroxyl groups of the epoxy resin, stronger interaction at the larger interface may lead to the observed excellent properties of the epoxy resin toughened with ENP.展开更多
Sorption of humic acid （HA） on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants （HOCs） and carbon sequestration in soils. The objective of our study is to determine t...Sorption of humic acid （HA） on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants （HOCs） and carbon sequestration in soils. The objective of our study is to determine the fractionation behavior of HA upon sorption on mineral surfaces with varying surface properties. HA was coated sequentially on kaolinite （1：1 clay）, montmorillonite （2：1 clay）, and goethite （iron oxide） for four times. The unadsorbed HA fractions were characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy （DRIFT）, and solid state 13C nuclear magnetic resonance spectroscopy （NMR）. The mineral-HA complexes were characterized by DRIFT. Polarity index [（N＋O）/C] revealed higher polarity of the unadsorbed HA fractions after coating on kaolinite, reflecting that relatively higher polarity fractions of HA remain unadsorbed. Sorption of aiiphatic alcohol fraction along with carbohydrate was prominent on kaolinite surface. DRIFT results of the unadsorbed HA fractions indicated more sorption of aiiphatic moieties on both kaolinite and montmorillonite. DRIFT results of the unadsorbed HA fractions after sorption on kaolinite and goethite showed the sorption of the proteinaceons fractions of HA. The HA fractions obtained after coating on goethite showed significant sorption of carboxylic moieties. The results mentioned above comply reasonably well with the DRIFT spectra of the minerai-HA complexes. ^13C NMR results showed higher sorption of anomeric C on kaolinite surface. Higher sorption of paraffinic fraction waS observed on montmorillonite. NMR data inferred the sorption of carboxylic moieties on goethite surface. Overall, this study showed that aliphatic moieties of HA preferentially sorbed on kaolinite and montmorillonite, while carboxylic functional groups play a significant role in sorption of HA on goethite. The sorbed fractions of HA may modify the mineral surface properties, and thus, the interaction with organic contaminants.展开更多
The molecular transformations of carboxylic acids in heavy acidic SL crude before and after true boiling point distillation were examined by ultra-high resolution negative-ion electrospray ionization(ESI) Fourier tran...The molecular transformations of carboxylic acids in heavy acidic SL crude before and after true boiling point distillation were examined by ultra-high resolution negative-ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The acid class(heteroatom number), type(z numbers) and carbon number distributions were positively characterized. It was found out that the total acid number(TAN) of SL crude decreased after true boiling point distillation, and the abundance of O2 class in mass spectra was also found to be reduced from 67.6% to 34.5% in SL TBP mixed crude as measured by MS spectra, indicating to a potential carboxylic acid decomposition. However, it was interesting that the carboxylic acids type distribution in both oils was almost the same although their relative abundance in SL TBP mixed crude turned to be much lower, suggesting that various petroleum carboxylic acid types have the similar thermal decomposition reaction behavior. Furthermore, for each O2 type of acids in SL TBP mixed crude, the abundance of carboxylic acids with carbon number higher than 35 was reduced greatly, especially for those with carbon number higher than 60, the mass peaks of which were nearly totally removed, indicating that the large carboxylic acid molecules in heavy fractions decomposed more significantly because of longer heating time during the true boiling point distillation process. As a result, the reduction of TAN may be caused by the thermal decomposition of carboxylic acids especially those with high carbon number, suggesting that quick distillation or much lower pressure is required to avoid the thermal decomposition.展开更多
The mechanism of phthalic acid,a dicarboxylic acid collector,in flotation separation of fluorite and rare earth(RE)was studied in this paper.The experimental data of flotation show that phthalic acid,as the collector,...The mechanism of phthalic acid,a dicarboxylic acid collector,in flotation separation of fluorite and rare earth(RE)was studied in this paper.The experimental data of flotation show that phthalic acid,as the collector,can realize highly efficient separation of fluorite and rare earth under weakly acidic conditions.The adsorption mechanism of phthalic acid on the surface of fluorite and bastnaesite was analyzed in this paper by means of the zeta potential measurement,the Fourier transform infrared(FT-IR),the X-ray photoelectron spectroscopy(XPS)and the stability constant measurement of active metal ion and phthalic acid coo rdination complex.According to the zeta potential testing results,the surfaces of fluorite adsorb the collector phthalate ion with negative charge under weakly acidic conditions which,in turn,increases its electronegativity and results in the motion of its potential.After the reaction between phthalic acid and fluorite ores under weakly acidic conditions,the peak of the fluorite ores is found to have significant changes in the FT-IR results,indicating strong chemical adsorption on the surfaces of phthalic acid and fluorite ores.According to the XPS analysis,the peak of benzene ring of phthalic acid is as high as 2%on the surface of fluorite,while no obvious characteristic peak of benzene ring is found on the surface of bastnaesite.According to the pH potentiometric titration results,the stability constant Ktotal of calcium phthalate complex within the acid range is higher than the stability constant K’total of cerium phthalate complex,indicating that the complex generated between phthalic acid and Ca^(2+)is more stable than the complex generated between phthalic acid and Ce^(3+).The possible reason is that Ca^(2+),with the highest reticular density,plays a prevailing role in the octahedron structure of fluorite amidst the acidic media.As the active point of flotation,Ca^(2+)works with the carboxyl groups of the collector phthalic acid(-C=O-)to form polycyclic calcium phthalate complex.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
Al-base surface self-lubricating composites need thick and hard alumina membranes with large pores to add lubricants easily. This kind of porous alumina layer was fabricated in additive-containing, phosphoric acid-bas...Al-base surface self-lubricating composites need thick and hard alumina membranes with large pores to add lubricants easily. This kind of porous alumina layer was fabricated in additive-containing, phosphoric acid-based solution. The effects of additive containing organic carboxylic acid and Ce salt on the properties of the oxide film and mechanism were investigated in detail with SEM and EDAX analyses. The results show that the pore diameter is about 100 nm, the film thickness increases by 4 -5 times, and the Vickers hardness improves by about 50% through adding some amount of organic carboxylic acid and Ce salt. Such an improvement in properties is explained in terms of a lower film dissolving velocity and better film quality in compound solution.展开更多
Mitochondria and mitochondria-associated endoplasmic reticulum membrane in neurodegenerative diseases:Mitochondria generate most of the chemical energy needed to power the biochemical reactions of cells,and thus are o...Mitochondria and mitochondria-associated endoplasmic reticulum membrane in neurodegenerative diseases:Mitochondria generate most of the chemical energy needed to power the biochemical reactions of cells,and thus are often referred to as the"powerhouse"of the cell.Nevertheless,this organelle is also involved in a pleth,ora of different cellular functions such as calcium(Ca^(2+))homeostasis,apoptosis,oxidative stress,and several metabolic pathways including oxidative phosphorylation,tricarboxylic acid cycle,andβ-oxidation of fatty acids.展开更多
Carbon dioxide(CO2)is an important and appealing C1 building block in chemical synthesis due to its nontoxicity,abundance,availability and sustainability.Tremendous progress has been achieved in the chemical transform...Carbon dioxide(CO2)is an important and appealing C1 building block in chemical synthesis due to its nontoxicity,abundance,availability and sustainability.Tremendous progress has been achieved in the chemical transformation of CO2 into high valueadded organic chemicals.However,the asymmetric synthesis with CO2 to form enantioenriched molecules,especially the catalytic process,has lagged far behind.The enantioselective incorporation of CO2 into organic compounds is highly desirable,as the corresponding chiral products,such as carboxylic acids and amino acids,are common structural units in a vast array of natural products and biologically active compounds.Herein,we discuss recent progress toward the enantioselective incorporation of CO2 into organic molecules,which mainly rely on three strategies:1)kinetic resolution or desymmetrization of epoxides with CO2 to form chiral cyclic carbonates and polycarbonates;2)nucleophilic attack of O-or N-nucleophiles to CO2 in tandem with asymmetric C–O bond formation to prepare chiral cyclic carbonates and carbamates;3)direct enantioselective nucleophilic attack of organometallic reagents to CO2 with asymmetric C–C bond formation.Finally,challenges and future outlook in this area are also presented.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
Objective To isolate and identify bioactive constituents from the stem barks of I//icium difengpi. Methods The chemical constituents were isolated and purified by repeated silica gel, Sephadex LH-20, recrystallization...Objective To isolate and identify bioactive constituents from the stem barks of I//icium difengpi. Methods The chemical constituents were isolated and purified by repeated silica gel, Sephadex LH-20, recrystallization, and preparative HPLC techniques. The structures of the compounds were identified on the basis of spectral data including NMR, MS, and IR. Results Two sesquiterpene lactones, majucin （I） and anisatin （2）, two steroids, l^-sitosterol （3） and daucosterol （4）, three carboxylic acids, 2-ethyldecanoic acid （5）, shikimic acid （6）, and 3,4-dihydrobenzoic acid （7）, and a flavonoid, quercetin （8）, were successively isolated from the stem barks of L difengpL Conclusion Apart from compound 3, other seven compounds are reported in this plant for the first time. The results suggested that the current studies on L difengpi is still far from being well known and therefore more studies need to be done for better understanding of this plant.展开更多
In this study, cellulose nanocrystals(CNC) with surface carboxylic groups were prepared from bleached softwood pulp by hydrolysis with concentrated citric acid at concentrations of 60 wt%~80 wt%. The solid residues fr...In this study, cellulose nanocrystals(CNC) with surface carboxylic groups were prepared from bleached softwood pulp by hydrolysis with concentrated citric acid at concentrations of 60 wt%~80 wt%. The solid residues from acid hydrolysis were collected for producing cellulose nanofibrils(CNF) via post high-pressure homogenization. Citric acid could be easily recovered after hydrolysis reactions through crystallization due to its low water solubility or through precipitation as a calcium salt followed by acidification. Several important properties of CNC and CNF, such as dimension, crystallinity, surface chemistry, thermal stability, were evaluated. Results showed that the obtained CNC and CNF surfaces contained carboxylic acid groups that facilitated functionalization and dispersion in aqueous processing. The recyclability of citric acid and the carboxylated CNC/CNF give the renewable cellulose nanomaterial huge potential for a wide range of industrial applications. Furthermore, the resultant CNC and CNF were used as reinforcing agents to make sodium carboxymethyl cellulose(CMC) films. Both CNC and CNF showed reinforcing effects in CMC composite films. The tensile strength of CMC films increased by 54.3% and 85.7% with 10 wt% inclusion of CNC and CNF, respectively. This study provides detailed information on carboxylated nanocellulose prepared by critic acid hydrolysis; a sustainable approach for the preparation of CNC/CNF is of significant importance for their various uses.展开更多
A novel decarboxylative fluorination process has been developed for the synthesis of ortho-hydroxy/amino arylfluorides from salicylic acid analogs, in which the ortho-hydroxy/amino group plays an important role in the...A novel decarboxylative fluorination process has been developed for the synthesis of ortho-hydroxy/amino arylfluorides from salicylic acid analogs, in which the ortho-hydroxy/amino group plays an important role in the transformation. In addition, various arylfluorides are obtained in good to excellent yields under mild conditions.展开更多
The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by the...The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates II containing five-membered ring were more stable than III with six-membered ring. While for intermediates III, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states IV and V involving a-COOH or b-COOH group had energy barriers of DE = 58.67 kJmol-1 and 103.94 kJmol-1, respectively. These results were in agreement with the experimental data. So the a-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not b-COOH group.展开更多
Utilizing CO_(2)for the production of bulky and valuable chemicals presents an attractive solution to address environmental and fossil energy crises.Among the various approaches,direct carboxylation of alcohols with C...Utilizing CO_(2)for the production of bulky and valuable chemicals presents an attractive solution to address environmental and fossil energy crises.Among the various approaches,direct carboxylation of alcohols with CO_(2)stands out as an eco-friendly process capable of efficiently producing carboxylic acids in a sustainable manner.However,the high dissociation energy of the C–O bond poses a significant challenge in this process.Over the past few decades,several strategies have been developed to activate alcohols and establish efficient catalytic systems for carboxylation with CO_(2).Nevertheless,the sporadic nature of reported approaches makes it difficult to determine the most effective one.This perspective aims to provide an overview of the current state-of-the-art catalytic protocols for carboxylating alcohols with CO_(2),encompassing esterification,halogenation,and photocatalysis,while considering their respective advantages and limitations.We aim to discern the most promising avenues for future development in this field.The insights presented in this perspective will contribute to the advancement of efficient and sustainable carboxylation methods using CO_(2),leading to the production of valuable chemicals in future.展开更多
Poly(dibutyl itaconate-co-isoprene-co-methacrylic acid)(PDIM) elastomer was designed and synthesized by redox emulsion polymerization under mild conditions. PDIM has high molecular weight, relatively high yield, and l...Poly(dibutyl itaconate-co-isoprene-co-methacrylic acid)(PDIM) elastomer was designed and synthesized by redox emulsion polymerization under mild conditions. PDIM has high molecular weight, relatively high yield, and low glass transition temperature(Tg). The structure of PDIM was determined by FTIR and NMR, and the carboxyl content was obtained by titration in a non-proton solvent. Tensile strength and elongation at break increased with increasing carboxyl content. In addition, the interaction between PDIM and silica was elucidated by rubber process analyzer(RPA) and TEM, and the results showed that the silica-PDIM interaction was strong, but the silica-silica interaction was weak.展开更多
基金Project supported by the National Natural Science Foundation of China (No. 20577026) the New Century Excellent Talents in University (No. NCET-04-0090).
文摘The photodegradation of persistent and bioaccumulative perftuorooctanoic acid （PFOA） in water by 185 nm vacuum ultraviolet （VUV） light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids （PFCAs）, that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.
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 Special Funds for Major State Bas ic Research Projects(G1999064800) Funds for Nation“863”Projects(2002AA302510)
文摘Study on a new composite of epoxy resin/elastomeric nano-particles (ENP) is re- ported in this paper, which shows that, in comparison with pure epoxy resin and epoxy toughened with CTBN, the composites of epoxy resin/carboxylic nitrile-butadiene ENP and epoxy resin/styrene butadiene vinyl-pyridine ENP possess both higher toughness and heat resistance. Both ENPs used in the study have an average size of less than 100 nm. Study on the epoxy network’s morphology and interface properties suggests that due to the chemical reaction be- tween ENP and epoxy resin and more hydrogen bonds between nitrile groups of the rubber and hydroxyl groups of the epoxy resin, stronger interaction at the larger interface may lead to the observed excellent properties of the epoxy resin toughened with ENP.
基金supported by the Federal Hatch Program, USA (No.MAS 8532)the Cheung Kong Scholar Program, Ministry ofEducation of Chinathe CSREES, USDA National Research Initiative Competitive Grants Program, USA (No.2005-35107-15278).
文摘Sorption of humic acid （HA） on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants （HOCs） and carbon sequestration in soils. The objective of our study is to determine the fractionation behavior of HA upon sorption on mineral surfaces with varying surface properties. HA was coated sequentially on kaolinite （1：1 clay）, montmorillonite （2：1 clay）, and goethite （iron oxide） for four times. The unadsorbed HA fractions were characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy （DRIFT）, and solid state 13C nuclear magnetic resonance spectroscopy （NMR）. The mineral-HA complexes were characterized by DRIFT. Polarity index [（N＋O）/C] revealed higher polarity of the unadsorbed HA fractions after coating on kaolinite, reflecting that relatively higher polarity fractions of HA remain unadsorbed. Sorption of aiiphatic alcohol fraction along with carbohydrate was prominent on kaolinite surface. DRIFT results of the unadsorbed HA fractions indicated more sorption of aiiphatic moieties on both kaolinite and montmorillonite. DRIFT results of the unadsorbed HA fractions after sorption on kaolinite and goethite showed the sorption of the proteinaceons fractions of HA. The HA fractions obtained after coating on goethite showed significant sorption of carboxylic moieties. The results mentioned above comply reasonably well with the DRIFT spectra of the minerai-HA complexes. ^13C NMR results showed higher sorption of anomeric C on kaolinite surface. Higher sorption of paraffinic fraction waS observed on montmorillonite. NMR data inferred the sorption of carboxylic moieties on goethite surface. Overall, this study showed that aliphatic moieties of HA preferentially sorbed on kaolinite and montmorillonite, while carboxylic functional groups play a significant role in sorption of HA on goethite. The sorbed fractions of HA may modify the mineral surface properties, and thus, the interaction with organic contaminants.
基金financially supported by the National Key Basic Research Development Program "973" Project (2006CB202501)
文摘The molecular transformations of carboxylic acids in heavy acidic SL crude before and after true boiling point distillation were examined by ultra-high resolution negative-ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The acid class(heteroatom number), type(z numbers) and carbon number distributions were positively characterized. It was found out that the total acid number(TAN) of SL crude decreased after true boiling point distillation, and the abundance of O2 class in mass spectra was also found to be reduced from 67.6% to 34.5% in SL TBP mixed crude as measured by MS spectra, indicating to a potential carboxylic acid decomposition. However, it was interesting that the carboxylic acids type distribution in both oils was almost the same although their relative abundance in SL TBP mixed crude turned to be much lower, suggesting that various petroleum carboxylic acid types have the similar thermal decomposition reaction behavior. Furthermore, for each O2 type of acids in SL TBP mixed crude, the abundance of carboxylic acids with carbon number higher than 35 was reduced greatly, especially for those with carbon number higher than 60, the mass peaks of which were nearly totally removed, indicating that the large carboxylic acid molecules in heavy fractions decomposed more significantly because of longer heating time during the true boiling point distillation process. As a result, the reduction of TAN may be caused by the thermal decomposition of carboxylic acids especially those with high carbon number, suggesting that quick distillation or much lower pressure is required to avoid the thermal decomposition.
基金Project supported by the National Natural Science Foundation of China(51634005,51564042)Inner Mongolia Autonomous Region Natural Science Foundation(2014ZD04.2016ZD05)。
文摘The mechanism of phthalic acid,a dicarboxylic acid collector,in flotation separation of fluorite and rare earth(RE)was studied in this paper.The experimental data of flotation show that phthalic acid,as the collector,can realize highly efficient separation of fluorite and rare earth under weakly acidic conditions.The adsorption mechanism of phthalic acid on the surface of fluorite and bastnaesite was analyzed in this paper by means of the zeta potential measurement,the Fourier transform infrared(FT-IR),the X-ray photoelectron spectroscopy(XPS)and the stability constant measurement of active metal ion and phthalic acid coo rdination complex.According to the zeta potential testing results,the surfaces of fluorite adsorb the collector phthalate ion with negative charge under weakly acidic conditions which,in turn,increases its electronegativity and results in the motion of its potential.After the reaction between phthalic acid and fluorite ores under weakly acidic conditions,the peak of the fluorite ores is found to have significant changes in the FT-IR results,indicating strong chemical adsorption on the surfaces of phthalic acid and fluorite ores.According to the XPS analysis,the peak of benzene ring of phthalic acid is as high as 2%on the surface of fluorite,while no obvious characteristic peak of benzene ring is found on the surface of bastnaesite.According to the pH potentiometric titration results,the stability constant Ktotal of calcium phthalate complex within the acid range is higher than the stability constant K’total of cerium phthalate complex,indicating that the complex generated between phthalic acid and Ca^(2+)is more stable than the complex generated between phthalic acid and Ce^(3+).The possible reason is that Ca^(2+),with the highest reticular density,plays a prevailing role in the octahedron structure of fluorite amidst the acidic media.As the active point of flotation,Ca^(2+)works with the carboxyl groups of the collector phthalic acid(-C=O-)to form polycyclic calcium phthalate complex.
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.
文摘Al-base surface self-lubricating composites need thick and hard alumina membranes with large pores to add lubricants easily. This kind of porous alumina layer was fabricated in additive-containing, phosphoric acid-based solution. The effects of additive containing organic carboxylic acid and Ce salt on the properties of the oxide film and mechanism were investigated in detail with SEM and EDAX analyses. The results show that the pore diameter is about 100 nm, the film thickness increases by 4 -5 times, and the Vickers hardness improves by about 50% through adding some amount of organic carboxylic acid and Ce salt. Such an improvement in properties is explained in terms of a lower film dissolving velocity and better film quality in compound solution.
基金supported by LifeArc Philanthropic Fund(P2019-0004)LifeArc Pathfinder Award+7 种基金along with Wellcome Trust Seed Award(109626/Z/15/Z)FA PESP-UoB Strategic Collaboration FundBirmingham Fellowship(to SS)grants from Laboratoire d'Excellence Revive(Investissement d'AvenirANR-10-LABX-73)the Region lle-de-France via doctoral school Innovation Therapeutique,du Fondamentalàl'Appliqué(ED569)from Universite Paris-Saclay(to LA)Medical Research Council(MRC)Developmental Pathway Funding Scheme(DPFS)grant(MR/P007732/1)(to TB)supported by the Association Fran?aise contre les Myopathies(AFM-Téléthon)。
文摘Mitochondria and mitochondria-associated endoplasmic reticulum membrane in neurodegenerative diseases:Mitochondria generate most of the chemical energy needed to power the biochemical reactions of cells,and thus are often referred to as the"powerhouse"of the cell.Nevertheless,this organelle is also involved in a pleth,ora of different cellular functions such as calcium(Ca^(2+))homeostasis,apoptosis,oxidative stress,and several metabolic pathways including oxidative phosphorylation,tricarboxylic acid cycle,andβ-oxidation of fatty acids.
基金supported by the National Natural Science Foundation of China(21801176,91956111)the Sichuan Science and Technology Program(2019YJ0379,20CXTD0112)the Fundamental Research Funds for the Central Universities。
文摘Carbon dioxide(CO2)is an important and appealing C1 building block in chemical synthesis due to its nontoxicity,abundance,availability and sustainability.Tremendous progress has been achieved in the chemical transformation of CO2 into high valueadded organic chemicals.However,the asymmetric synthesis with CO2 to form enantioenriched molecules,especially the catalytic process,has lagged far behind.The enantioselective incorporation of CO2 into organic compounds is highly desirable,as the corresponding chiral products,such as carboxylic acids and amino acids,are common structural units in a vast array of natural products and biologically active compounds.Herein,we discuss recent progress toward the enantioselective incorporation of CO2 into organic molecules,which mainly rely on three strategies:1)kinetic resolution or desymmetrization of epoxides with CO2 to form chiral cyclic carbonates and polycarbonates;2)nucleophilic attack of O-or N-nucleophiles to CO2 in tandem with asymmetric C–O bond formation to prepare chiral cyclic carbonates and carbamates;3)direct enantioselective nucleophilic attack of organometallic reagents to CO2 with asymmetric C–C bond formation.Finally,challenges and future outlook in this area are also presented.
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.
文摘Objective To isolate and identify bioactive constituents from the stem barks of I//icium difengpi. Methods The chemical constituents were isolated and purified by repeated silica gel, Sephadex LH-20, recrystallization, and preparative HPLC techniques. The structures of the compounds were identified on the basis of spectral data including NMR, MS, and IR. Results Two sesquiterpene lactones, majucin （I） and anisatin （2）, two steroids, l^-sitosterol （3） and daucosterol （4）, three carboxylic acids, 2-ethyldecanoic acid （5）, shikimic acid （6）, and 3,4-dihydrobenzoic acid （7）, and a flavonoid, quercetin （8）, were successively isolated from the stem barks of L difengpL Conclusion Apart from compound 3, other seven compounds are reported in this plant for the first time. The results suggested that the current studies on L difengpi is still far from being well known and therefore more studies need to be done for better understanding of this plant.
基金financial support for this work is from the National Science&Technology Pillar Program during the Twelfth Five-year Plan Period(No.2015BAD14B06)the National Natural Science Foundation of China(No.31470609,No.25106240 and No.21433001)+1 种基金the Primary Research and Development Plan of Shandong Province(No.2016GGX104003 and No.2016CYJS07A02)the Young Taishan Scholars Program of Shandong Province(No.tsqn20161052)
文摘In this study, cellulose nanocrystals(CNC) with surface carboxylic groups were prepared from bleached softwood pulp by hydrolysis with concentrated citric acid at concentrations of 60 wt%~80 wt%. The solid residues from acid hydrolysis were collected for producing cellulose nanofibrils(CNF) via post high-pressure homogenization. Citric acid could be easily recovered after hydrolysis reactions through crystallization due to its low water solubility or through precipitation as a calcium salt followed by acidification. Several important properties of CNC and CNF, such as dimension, crystallinity, surface chemistry, thermal stability, were evaluated. Results showed that the obtained CNC and CNF surfaces contained carboxylic acid groups that facilitated functionalization and dispersion in aqueous processing. The recyclability of citric acid and the carboxylated CNC/CNF give the renewable cellulose nanomaterial huge potential for a wide range of industrial applications. Furthermore, the resultant CNC and CNF were used as reinforcing agents to make sodium carboxymethyl cellulose(CMC) films. Both CNC and CNF showed reinforcing effects in CMC composite films. The tensile strength of CMC films increased by 54.3% and 85.7% with 10 wt% inclusion of CNC and CNF, respectively. This study provides detailed information on carboxylated nanocellulose prepared by critic acid hydrolysis; a sustainable approach for the preparation of CNC/CNF is of significant importance for their various uses.
基金We are grateful for the financial support from the National Natural Science Foundation of China （24172219, 21532009, 21761142010 and 21790330）, the National Basic Research Program of China （973-2015CB856600）, the strategic Priority Research Program （XDB20000000）, the Key Research Program of Froniter Science （QYZDJSSW-SLH055）, CAS, and the Science Technology Commission of the Shanghai Municipality （17XD140500 and 17JC1401200）. This research was partially supported by CAS Interdisciplinary Innovation Team.
文摘A novel decarboxylative fluorination process has been developed for the synthesis of ortho-hydroxy/amino arylfluorides from salicylic acid analogs, in which the ortho-hydroxy/amino group plays an important role in the transformation. In addition, various arylfluorides are obtained in good to excellent yields under mild conditions.
基金the National Natural Science Foundation of China (No. 29802006) the Teaching and Research Award Program for Outstanding Young Teachers in Higher Education Institutions of MOE P.R.C. and Tsinghua University.
文摘The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates II containing five-membered ring were more stable than III with six-membered ring. While for intermediates III, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states IV and V involving a-COOH or b-COOH group had energy barriers of DE = 58.67 kJmol-1 and 103.94 kJmol-1, respectively. These results were in agreement with the experimental data. So the a-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not b-COOH group.
基金Financial support from the National Natural Science Foundation of China(No.22271060)the Department of Chemistry at Fudan UniversityNanjing Forestry University。
文摘Utilizing CO_(2)for the production of bulky and valuable chemicals presents an attractive solution to address environmental and fossil energy crises.Among the various approaches,direct carboxylation of alcohols with CO_(2)stands out as an eco-friendly process capable of efficiently producing carboxylic acids in a sustainable manner.However,the high dissociation energy of the C–O bond poses a significant challenge in this process.Over the past few decades,several strategies have been developed to activate alcohols and establish efficient catalytic systems for carboxylation with CO_(2).Nevertheless,the sporadic nature of reported approaches makes it difficult to determine the most effective one.This perspective aims to provide an overview of the current state-of-the-art catalytic protocols for carboxylating alcohols with CO_(2),encompassing esterification,halogenation,and photocatalysis,while considering their respective advantages and limitations.We aim to discern the most promising avenues for future development in this field.The insights presented in this perspective will contribute to the advancement of efficient and sustainable carboxylation methods using CO_(2),leading to the production of valuable chemicals in future.
基金supported by the National Natural Science Foundation of China(50933001,51221102)the National Science Fund for Distinguished Young Scholars(50725310)+3 种基金the National Basic Research Program of China(2011 CB606003)the Beijing Nova Program(Z131102000413015)the Beijing Municipal Training Program Foundation for the Talents(2013D003034 00041)the Goodyear Tire & Rubber Company
文摘Poly(dibutyl itaconate-co-isoprene-co-methacrylic acid)(PDIM) elastomer was designed and synthesized by redox emulsion polymerization under mild conditions. PDIM has high molecular weight, relatively high yield, and low glass transition temperature(Tg). The structure of PDIM was determined by FTIR and NMR, and the carboxyl content was obtained by titration in a non-proton solvent. Tensile strength and elongation at break increased with increasing carboxyl content. In addition, the interaction between PDIM and silica was elucidated by rubber process analyzer(RPA) and TEM, and the results showed that the silica-PDIM interaction was strong, but the silica-silica interaction was weak.
