With the wide applications of lithium-ion batteries(LIBs)in electronic devices and electric vehicles,it is of great importance to improve their safety and electrochemical performance.Herein,soluble polyimides(PI)conta...With the wide applications of lithium-ion batteries(LIBs)in electronic devices and electric vehicles,it is of great importance to improve their safety and electrochemical performance.Herein,soluble polyimides(PI)containing carboxyl groups(―COOH)were synthesized by a simple one-step method and PI separators with sponge-like,interpenetrating porous structures were prepared via non-solvent induced phase separation(NIPS).The obtained PI separators exhibited excellent thermal stability and fire-resistance properties,with the electrolyte uptake of 344%and good dimensional integrity in air at 200℃.The results showed that the lithium-ion transference number of the obtained PI separator could reach 0.48,which was much higher than that of the Celgard-2400 separator(0.38).The Li/LiFePO_(4) half-cell with the PI separator showed excellent cycle capability and high-rate performance with a high capacity of 121.80 mA·h·g^(-1) at 5 C,which was better than that of the cell with the Celgard-2400 separator(54.3 mA·h·g^(-1)),demonstrating the promising applications of this PI separators in LIBs.展开更多
How to rationally design effective and practical CO_(2)adsorbent is a great challenge.Herein,an ultra-microporous metal-organic framework(FJI-H19)with high concentration of free carboxyl groups and uncoordinated Lewis...How to rationally design effective and practical CO_(2)adsorbent is a great challenge.Herein,an ultra-microporous metal-organic framework(FJI-H19)with high concentration of free carboxyl groups and uncoordinated Lewis basic sites has been synthesized from a multi-dental ligand with a high proportion of polar CO_(2)-philic atoms.FJI-H19 displays a relatively high CO_(2)volumetric uptake(120 cm^3?cm^(–3))with high selectivity under practical atmosphere(298 K and 1 bar).Further researches demonstrate that such high adsorption results from an unusual synergistic effect from free carboxyl group and uncoordinated N atoms.This result will provide a potential strategy for developing more effective and pratical CO_(2)adsorbent based on MOFs.展开更多
Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chain...Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chains. In this work, crosslinked polyimide fibers(CPI fibers) were produced by intrinsic carboxyl decarboxylation for the first time. The thermal stability of the polyimide fibers containing the intrinsic carboxyl groups(PIC fibers) was studied, and the temperature of the decarboxylation-crosslinking reaction was determined to be 450 ℃. The PIC fibers were hotdrawn to initiate thermal crosslinking of the carboxyl groups and molecular chain orientation at high temperature. The CPI fibers had high tensile strengths(0.72-1.46 GPa) and compressive strengths(401-604 MPa). The oriented macromolecules and chemically crosslinked structure improved the tightness of the molecular chains and endowed the CPI fibers with excellent hydrolytic resistance. The CPI-50 fiber did not dissolve in a 0.5 wt% NaOH solution during heating at 90 ℃ for 10 h, and the tensile strength retention reached 87% when treated in 0.5 wt% NaOH solutions at 90 ℃ for 1 h, providing a guarantee for its application in alkaline corrosive environments.展开更多
Ozone treatment is a common way to functionalize commercial multi-walled carbon nanotubes （CNTs） with various oxygen functionalities like carboxyl, phenol and lactone groups, in order to enhance their textural prope...Ozone treatment is a common way to functionalize commercial multi-walled carbon nanotubes （CNTs） with various oxygen functionalities like carboxyl, phenol and lactone groups, in order to enhance their textural properties and chemical activity. In order to detail the effect of each functional group, we correlated the activity with the surface density of each group, and found that the carboxyl groups play a pivotal role in two important catalytic reactions, namely the electrochemical oxygen reduction reaction （ORR） and agar conversion to 5-hydroxymethylfurfural （HMF）. During the processes, the hydrophilic surface provides a strong affinity for reaction substrates while the improved porosity allows the efficient diffusion of reactants and products. Furthermore, the activity of functionalized CNTs for agar conversion remained almost unchanged during nine cycles of reaction. This work highlights a strategy for improving the activity of CNTs for electrochemical ORR and agar conversion reactions, as well a promising application of carboxyl-rich CNTs as a solid acid catalyst to produce high-purity HMF--an important chemical intermediate.展开更多
The effect of exogenous hydroxyl,carboxyl groups and/or Sn^(2+) on pyrolysis reactions of poly(L-lactide)(PLLA)was investigated by thermogravimetric analysis(TGA).The activation energy(fa)of pyrolysis reactions was es...The effect of exogenous hydroxyl,carboxyl groups and/or Sn^(2+) on pyrolysis reactions of poly(L-lactide)(PLLA)was investigated by thermogravimetric analysis(TGA).The activation energy(fa)of pyrolysis reactions was estimated by the Kissinger-Akahira-Sunose method.The kinetic models were also explored by the Malek method,and the random degradation behavior was determined by comparing the plots of ln{-ln[1-(1-w)05]}versus 1/7for experimental data from TGA with model reactions.The pyrolysis reaction rate of PLLA was affected slightly by exogenous hydroxyl and carboxyl groups at lower levels of Sn with 65-70 mg·kg^(-1)but increased appreciably in the presence of extraneous Sn^(2+),-COOH/Sn^(2+),or-OH/Sn^(2+).The Ea values for the pyrolysis reactions of the PLLAs that provided lactide were different under the catalysis of Sn2+in different chemical environments because Sn^(2+) can form the new Sn-carboxylate and Sn-alkoxide with exogenous carboxyl and hydroxyl groups,which were different in steric hindrance for the formation of activated complex between Sn^(2+) and PLLA.Under the catalysis of Sn^(2+),a lactide molecule can be directly eliminated selectively at a random position of PLLA molecular chains,and the molecular chain of PLLA cannot change two PLLA fragments at the elimination site of lactide.However,it was regenerated into a new PLLA molecule with the molecular weight reduced by 144 g·mol^(-1).展开更多
At 225℃. caprolactone has been polymerized in the presence of succinic acid under dry nitrogen atmosphere. Characterizations of the polymer through IR and molecular weight measurements by 1H-NMR and end group titrati...At 225℃. caprolactone has been polymerized in the presence of succinic acid under dry nitrogen atmosphere. Characterizations of the polymer through IR and molecular weight measurements by 1H-NMR and end group titration have shown that the polycaprolactone obtained is of two carboxyl end groups. The molecular weight of it increases with decreasing of the acid content in the reaction mixture under the same polymerization conditions. With a certain ratio of acid to caprolactone. the maximum of molecular weight of the polymer will be reached at the reaction time of 3h.展开更多
A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were deter...A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were determined by ^1H-NMR and IR, respectively. Their molecular weights were measured by gel permeation chromatography （ GPC ）, which showed that all the polymers had high molecule weights （ 〉 42 000）. Due to the long side chains of polymers, all the polymers had good solubility （soluble in NMP, DMAc, THF, etc. ）. The differential scanning calorimeter （DSC） detected their excellent glass transition temperatures （ Tg ） up to 195 ℃. The Tg increased with the content of carboxylic units in the polymer chains, because the interactions of H bonds increased with increasing content of carboxylic. The polymers could form transparent and flexible films, which make them a candidate for membrane materials.展开更多
Achieving high fouling resistance and permeability using membrane separation technology in water treatment processes remains a challenge.In this work,a novel mixed-matrix membrane(MMM)(poly(arylene ether ketone)[PAEK]...Achieving high fouling resistance and permeability using membrane separation technology in water treatment processes remains a challenge.In this work,a novel mixed-matrix membrane(MMM)(poly(arylene ether ketone)[PAEK]-containing carboxyl groups[PAEK-COOH]/UiO-66-NH_(2)@graphene oxide[GO])with superb fouling resistance and high permeability was prepared by the nonsolvent-induced phase separation method,by in-situ growth of UiO-66-NH_(2) on the GO layer,and by preparing hydrophilic PAEK-COOH.On the basis of the structure and performance analysis of the MMM,the maximum water flux reached 591.25 L·m^(-2)·h^(-1) for PAEK-COOH/UiO-66-NH_(2)@GO,whereas the retention rate for bovine serum albumin increased from 85.40%to 94.87%.As the loading gradually increased,the hydrophilicity of the MMMs increased,significantly enhancing their fouling resistance.The strongest anti-fouling ability observed was 94.74%,which was 2.02 times greater than that of the pure membrane.At the same time,the MMMs contained internal amide and hydrogen bonds during the preparation process,forming a cross-linked structure,which further enhanced the mechanical strength and chemical stability.In summary,the MMMs with high retention rate,strong permeability,and anti-fouling ability were successfully prepared.展开更多
Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two crit...Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two critical challenges,i.e.,zinc dendrite growth and polyiodide shuttle effect,severely impede their commercial viability.To conquer these limitations,this study develops a multifunctional separator fabricated from straw-derived carboxylated nanocellulose,with its negative charge density further reinforced by anionic polyacrylamide incorporation.This modification simultaneously improves the separator’s mechanical properties,ionic conductivity,and Zn^(2+)ion transfer number.Remarkably,despite its ultrathin 20μm profile,the engineered separator demonstrates exceptional dendrite suppression and parasitic reaction inhibition,enabling Zn//Zn symmetric cells to achieve impressive cycle life(>1800 h at 2 m A cm^(-2)/2 m Ah cm^(-2))while maintaining robust performance even at ultrahigh areal capacities(25 m Ah cm^(-2)).Additionally,the separator’s anionic characteristic effectively blocks polyiodide migration through electrostatic repulsion,yielding Zn-I_(2) batteries with outstanding rate capability(120.7 m Ah g^(-1)at 5 A g^(-1))and excellent cyclability(94.2%capacity retention after 10,000 cycles).And superior cycling stability can still be achieved under zinc-deficient condition and pouch cell configuration.This work establishes a new paradigm for designing high-performance zinc-based energy storage systems through rational separator engineering.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
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
Aqueous zinc metal batteries are regarded as the most promising energy storage system due to their advantages of high safety,low cost,and high theoretical capacity.However,the growth of dendrites and the occurrence of...Aqueous zinc metal batteries are regarded as the most promising energy storage system due to their advantages of high safety,low cost,and high theoretical capacity.However,the growth of dendrites and the occurrence of side reactions hinder the development of zinc metal batteries.Despite previous attempts to design advanced hydrogel electrolytes,achieving high mechanical performance and ionic conductivity of hydrogel electrolytes has remained challenging.In this work,a hydrogel electrolyte with an ionic crosslinked network is prepared by carboxylic bacterial cellulose fiber and imidazole-type ionic liquid,following by a covalent network of polyacrylamide.The hydrogel electrolyte possesses a superior ionic conductivity of 43.76 mS cm^(−1),leading to a Zn^(2+)migration number of 0.45,and high mechanical performance with an elastic modulus of 3.48 GPa and an elongation at breaking of 38.36%.More importantly,under the anion-coordination effect of the carboxyl group in bacterial cellulose and[BF4]−in imidazole-type ionic liquid,the solvation sheath of hydrated Zn^(2+)ions and the nucleation overpotential of Zn plating are regulated.The results of cycled testing show that the growth of zinc dendrites is effectively inhibited and the generation of irreversible by-products is reduced.With the carboxylic bacterial cellulose-based hydrogel electrolyte,the Zn||Zn symmetric batteries offer good cyclability as well as Zn||Ti batteries.展开更多
Pore structure engineering has been acknowledged as suitable approach to creating active sites and en-hancing ion transport capabilities of hard carbon anodes.However,conventional porous carbon materials exhibit high ...Pore structure engineering has been acknowledged as suitable approach to creating active sites and en-hancing ion transport capabilities of hard carbon anodes.However,conventional porous carbon materials exhibit high BET and surface defects.Additionally,the sodium storage mechanism predominantly occurs in the slope region.This contradicts practical application requirements because the capacity of the plateau region is crucial for determining the actual capacity of batteries.In our work,we prepared a novel“core-shell”carbon framework(CNA1200).Introducingclosedporesand carboxylgroupsinto coal-basedcarbon materials to enhance its sodium storage performance.The closed pore structure dominates in the“core”structure,which is attributed to the timely removal of sodium hydroxide(NaOH)to prevent further for-mation of active carbon structure.The presence of closed pores is beneficial for increasing sodium ion storage in the low-voltage plateau region.And the“shell”structure originates from coal tar pitch,it not only uniformly connects hard carbon particles together to improve cycling stability,but is also rich in carboxyl groups to enhance the reversible sodium storage performance in slope region.CNA1200 has ex-cellent electrochemical performance,it exhibits a specific capacity of 335.2 mAh g^(−1)at a current density of 20 mA g^(−1)with ICE=51.53%.In addition,CNA1200 has outstanding cycling stability with a capac-ity retention of 91.8%even when cycling over 200 times.When CNA1200 is used as anode paired with Na_(3)V_(2)(PO_(4))_(3)cathode,it demonstrates a capacity of 109.54 mAh g^(−1)at 0.1 C and capacity retention of 94.64%at 0.5 C.This work provides valuable methods for regulating the structure of sodium-ion battery(SIBs)anode and enhances the potential for commercialization.展开更多
Salination of solutions of salinity gradient releases large‐scale clean and renewable energy, which can be directly and efficiently transformed into electrical energy using ion‐selective nanofluidic channel membrane...Salination of solutions of salinity gradient releases large‐scale clean and renewable energy, which can be directly and efficiently transformed into electrical energy using ion‐selective nanofluidic channel membranes. However, conventional ion‐selective membranes are typically either cation‐ or anion‐selective. A pH‐switchable system capable of dual cation and anion transport along with salt gradient energy harvesting properties has not been demonstrated in ion‐selective membranes. Here, we constructed an amphoteric heterolayer metal–organic framework (MOF) membrane with subnanochannels modified with carboxylic and amino functional groups. The amphoteric MOF‐composite membrane, AAO/aUiO‐66‐(COOH)_(2)/UiO‐66‐NH_(2), exhibits pH‐tuneable ion conduction and achieves osmotic energy conversion of 7.4 and 5.7 W/m^(2) in acidic and alkaline conditions, respectively, using a 50‐fold salt gradient. For different anions but the same cation diffusion transport, the amphoteric membrane produces an outstanding I−/CO_(3)^(2−) selectivity of ~4160 and an osmotic energy conversion of ~133.5 W/m^(2). The amphoteric membrane concept introduces a new pathway to explore the development of ion transport and separation technologies and their application in osmotic energy‐conversion devices and flow batteries.展开更多
Commercially available coal-based activated carbon was treated by nitric acid with different concentrations and the resultant samples were used as catalysts for the direct hydroxylation of benzene to phenol in acetoni...Commercially available coal-based activated carbon was treated by nitric acid with different concentrations and the resultant samples were used as catalysts for the direct hydroxylation of benzene to phenol in acetonitrile. Boehm titration, X-ray photoelectron spectroscopy, scanning electron microscope coupled with an energy dispersive X-ray microanalyzer, and Brunauer-Emmett-Teller method were used to characterize the samples. The number of carboxyl groups on the surface was found to be the main factor affecting the catalytic activity. An optimum catalytic performance with a yield of 15.7% and a selectivity of 87.2% to phenol was obtained.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
An alkaline earth metal-organic framework [Ba（Hsip）（H2O）4]n （1, NaH2sip = 5-sulfoisophthalic acid sodium） has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba（II） ...An alkaline earth metal-organic framework [Ba（Hsip）（H2O）4]n （1, NaH2sip = 5-sulfoisophthalic acid sodium） has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba（II） atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a （6, 3） topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333（2）, b = 16.7044（3）, c = 10.4817（2）, Z = 4, V = 1283.99（5）3, Mr = 453.58, Dc = 2.346 g/cm3, F（000） = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ（I）.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
Cellulose nanofibrils(CNFs)are promising sustainable materials that can be applied to nanocomposites,as well as medical and life-sciences devices.However,methods for the preparation of these important materials are en...Cellulose nanofibrils(CNFs)are promising sustainable materials that can be applied to nanocomposites,as well as medical and life-sciences devices.However,methods for the preparation of these important materials are energy intensive because heating and mechanical disintegration are required to produce cellulose fibers below 100 nm in size.In this study,CNFs were prepared through the multi-site regioselective oxidation of cellulose with 2,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO)and periodate at room temperature(20–25°C),without any mechanical-disintegration treatment.Transmission electron microscopy(TEM)revealed that the CNFs had the average widths of 14.1,55.4,and 81.9 nm for three different treatments.Fourier-transform infrared spectroscopy revealed that carboxyl groups were created on the surfaces of the microfibrils,while X-ray diffraction studies showed that the cellulose I structure was maintained after oxidation,and that the cellulose nanofibril crystallinity index exceeded 70%.These results demonstrate that CNFs can be prepared by multi-site regioselective oxidation at room temperature in the absence of mechanical disintegration.In addition,a model was developed to calculate the total content of carboxylate and aldehyde groups of CNFs prepared by the TEMPO mediate oxidation,the periodate oxidation,and the multi-site regioselective oxidation methods based on the particle width determined by TEM.The calculated values of the model were in good agreement with the total content(experimental value)of carboxylate and aldehyde groups of CNFs prepared by the TEMPO-mediated oxidation and the multi-site regioselective oxidation methods.However,the model was not valid for CNFs prepared by the periodate oxidation method.展开更多
Limonoid bitterness is a serious problem in the citrus industry worldwide. Limonoid glucosyltransferase is an enzyme that catalyzes the conversion of bitter limonoid into non-bitter limonoid glucoside while retaining ...Limonoid bitterness is a serious problem in the citrus industry worldwide. Limonoid glucosyltransferase is an enzyme that catalyzes the conversion of bitter limonoid into non-bitter limonoid glucoside while retaining the health benefit of limonoids in the juice. The immobilization of this enzyme in a column can solve the juice bitterness problem. More information about the catalytic residues of the enzyme is needed in this immobilization process. Glutamate/aspartate,histidine,lysine,tryptophan,serine,and cysteine residues were chemi-cally modified to investigate their roles in the catalytic function of limonoid glucosyltransferase. Inactivation of the enzyme following modi-fication of carboxyl and imidazole moieties was a consequence of a loss in substrate binding and catalysis in the glucosyltransfer reaction. The modification of a single histidine residue completely destroyed the ability of limonoid glucosyltransferase to transfer the D-glucopyranosyl unit. Tryptophan seemed to have some role in maintaining the active conformation of the catalytic site. Lysine also seemed to have some direct or indirect role in this catalysis but the modification of serine and cysteine did not have any effect on catalysis. Therefore,we conclude that the carboxyl and imidazole groups containing amino acids are responsible for the catalytic action of the enzyme.展开更多
基金the National Natural Science Foundation of China(Nos.U21A2087,51903038 and 21975040).
文摘With the wide applications of lithium-ion batteries(LIBs)in electronic devices and electric vehicles,it is of great importance to improve their safety and electrochemical performance.Herein,soluble polyimides(PI)containing carboxyl groups(―COOH)were synthesized by a simple one-step method and PI separators with sponge-like,interpenetrating porous structures were prepared via non-solvent induced phase separation(NIPS).The obtained PI separators exhibited excellent thermal stability and fire-resistance properties,with the electrolyte uptake of 344%and good dimensional integrity in air at 200℃.The results showed that the lithium-ion transference number of the obtained PI separator could reach 0.48,which was much higher than that of the Celgard-2400 separator(0.38).The Li/LiFePO_(4) half-cell with the PI separator showed excellent cycle capability and high-rate performance with a high capacity of 121.80 mA·h·g^(-1) at 5 C,which was better than that of the cell with the Celgard-2400 separator(54.3 mA·h·g^(-1)),demonstrating the promising applications of this PI separators in LIBs.
基金supported by the National Natural Science Foundation of China(21390392,21471148)the Youth Innovation Promotion Association CAS
文摘How to rationally design effective and practical CO_(2)adsorbent is a great challenge.Herein,an ultra-microporous metal-organic framework(FJI-H19)with high concentration of free carboxyl groups and uncoordinated Lewis basic sites has been synthesized from a multi-dental ligand with a high proportion of polar CO_(2)-philic atoms.FJI-H19 displays a relatively high CO_(2)volumetric uptake(120 cm^3?cm^(–3))with high selectivity under practical atmosphere(298 K and 1 bar).Further researches demonstrate that such high adsorption results from an unusual synergistic effect from free carboxyl group and uncoordinated N atoms.This result will provide a potential strategy for developing more effective and pratical CO_(2)adsorbent based on MOFs.
基金financially supported by the Scientific Research Innovation Plan of Shanghai Education Commission (No. 2019-01-07-00-03-E00001)the National Natural Science Foundation of China (Nos. U21A2087 and 21975040)the Natural Science Foundation of Shanghai (No. 21ZR1400200)。
文摘Easy hydrolysis in alkaline environments limits the use of polyimide fibers in environmental protection. The hydrolysis resistance levels of polyimide fibers can be improved by crosslinking of the macromolecular chains. In this work, crosslinked polyimide fibers(CPI fibers) were produced by intrinsic carboxyl decarboxylation for the first time. The thermal stability of the polyimide fibers containing the intrinsic carboxyl groups(PIC fibers) was studied, and the temperature of the decarboxylation-crosslinking reaction was determined to be 450 ℃. The PIC fibers were hotdrawn to initiate thermal crosslinking of the carboxyl groups and molecular chain orientation at high temperature. The CPI fibers had high tensile strengths(0.72-1.46 GPa) and compressive strengths(401-604 MPa). The oriented macromolecules and chemically crosslinked structure improved the tightness of the molecular chains and endowed the CPI fibers with excellent hydrolytic resistance. The CPI-50 fiber did not dissolve in a 0.5 wt% NaOH solution during heating at 90 ℃ for 10 h, and the tensile strength retention reached 87% when treated in 0.5 wt% NaOH solutions at 90 ℃ for 1 h, providing a guarantee for its application in alkaline corrosive environments.
文摘Ozone treatment is a common way to functionalize commercial multi-walled carbon nanotubes （CNTs） with various oxygen functionalities like carboxyl, phenol and lactone groups, in order to enhance their textural properties and chemical activity. In order to detail the effect of each functional group, we correlated the activity with the surface density of each group, and found that the carboxyl groups play a pivotal role in two important catalytic reactions, namely the electrochemical oxygen reduction reaction （ORR） and agar conversion to 5-hydroxymethylfurfural （HMF）. During the processes, the hydrophilic surface provides a strong affinity for reaction substrates while the improved porosity allows the efficient diffusion of reactants and products. Furthermore, the activity of functionalized CNTs for agar conversion remained almost unchanged during nine cycles of reaction. This work highlights a strategy for improving the activity of CNTs for electrochemical ORR and agar conversion reactions, as well a promising application of carboxyl-rich CNTs as a solid acid catalyst to produce high-purity HMF--an important chemical intermediate.
基金the National Key Research and Development Program of China(No.2016YFB0302500)the National Natural Science Foundation of China(Nos.51873209,51873210,51773194 and 51973219)Jilin Scientific and Technological Development Program,China(No.20200403022SF).
文摘The effect of exogenous hydroxyl,carboxyl groups and/or Sn^(2+) on pyrolysis reactions of poly(L-lactide)(PLLA)was investigated by thermogravimetric analysis(TGA).The activation energy(fa)of pyrolysis reactions was estimated by the Kissinger-Akahira-Sunose method.The kinetic models were also explored by the Malek method,and the random degradation behavior was determined by comparing the plots of ln{-ln[1-(1-w)05]}versus 1/7for experimental data from TGA with model reactions.The pyrolysis reaction rate of PLLA was affected slightly by exogenous hydroxyl and carboxyl groups at lower levels of Sn with 65-70 mg·kg^(-1)but increased appreciably in the presence of extraneous Sn^(2+),-COOH/Sn^(2+),or-OH/Sn^(2+).The Ea values for the pyrolysis reactions of the PLLAs that provided lactide were different under the catalysis of Sn2+in different chemical environments because Sn^(2+) can form the new Sn-carboxylate and Sn-alkoxide with exogenous carboxyl and hydroxyl groups,which were different in steric hindrance for the formation of activated complex between Sn^(2+) and PLLA.Under the catalysis of Sn^(2+),a lactide molecule can be directly eliminated selectively at a random position of PLLA molecular chains,and the molecular chain of PLLA cannot change two PLLA fragments at the elimination site of lactide.However,it was regenerated into a new PLLA molecule with the molecular weight reduced by 144 g·mol^(-1).
文摘At 225℃. caprolactone has been polymerized in the presence of succinic acid under dry nitrogen atmosphere. Characterizations of the polymer through IR and molecular weight measurements by 1H-NMR and end group titration have shown that the polycaprolactone obtained is of two carboxyl end groups. The molecular weight of it increases with decreasing of the acid content in the reaction mixture under the same polymerization conditions. With a certain ratio of acid to caprolactone. the maximum of molecular weight of the polymer will be reached at the reaction time of 3h.
基金Supported by Open Project of State Key Laboratory of Supramolecular Structure and Materials(SKLSSM201114)the National Natural Science Foundation of China(51103010)
文摘A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were determined by ^1H-NMR and IR, respectively. Their molecular weights were measured by gel permeation chromatography （ GPC ）, which showed that all the polymers had high molecule weights （ 〉 42 000）. Due to the long side chains of polymers, all the polymers had good solubility （soluble in NMP, DMAc, THF, etc. ）. The differential scanning calorimeter （DSC） detected their excellent glass transition temperatures （ Tg ） up to 195 ℃. The Tg increased with the content of carboxylic units in the polymer chains, because the interactions of H bonds increased with increasing content of carboxylic. The polymers could form transparent and flexible films, which make them a candidate for membrane materials.
基金support of this work by National Natural Science Foundation of China(22075031,51673030,51603017 and 51803011)Jilin Provincial Science&Technology Department(20220201105GX)Chang Bai Mountain Scholars Program of Jilin Province.
文摘Achieving high fouling resistance and permeability using membrane separation technology in water treatment processes remains a challenge.In this work,a novel mixed-matrix membrane(MMM)(poly(arylene ether ketone)[PAEK]-containing carboxyl groups[PAEK-COOH]/UiO-66-NH_(2)@graphene oxide[GO])with superb fouling resistance and high permeability was prepared by the nonsolvent-induced phase separation method,by in-situ growth of UiO-66-NH_(2) on the GO layer,and by preparing hydrophilic PAEK-COOH.On the basis of the structure and performance analysis of the MMM,the maximum water flux reached 591.25 L·m^(-2)·h^(-1) for PAEK-COOH/UiO-66-NH_(2)@GO,whereas the retention rate for bovine serum albumin increased from 85.40%to 94.87%.As the loading gradually increased,the hydrophilicity of the MMMs increased,significantly enhancing their fouling resistance.The strongest anti-fouling ability observed was 94.74%,which was 2.02 times greater than that of the pure membrane.At the same time,the MMMs contained internal amide and hydrogen bonds during the preparation process,forming a cross-linked structure,which further enhanced the mechanical strength and chemical stability.In summary,the MMMs with high retention rate,strong permeability,and anti-fouling ability were successfully prepared.
基金the financial support from the Natural Science Foundation of Jiangsu Province(BK20231292)the Jiangsu Agricultural Science and Technology Innovation Fund(CX(24)3091)+6 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX25_1429)the National Key R&D Program of China(2024YFE0109200)the Fundamental Research Funds for the Central Universities(No.2024300440)Guangdong Basic and Applied Basic Research Foundation(2025A1515011098)the National Natural Science Foundation of China(12464032)the Natural Science Foundation of Jiangxi Province(20232BAB201032)Ji'an Science and Technology Plan Project(2024H-100301)。
文摘Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two critical challenges,i.e.,zinc dendrite growth and polyiodide shuttle effect,severely impede their commercial viability.To conquer these limitations,this study develops a multifunctional separator fabricated from straw-derived carboxylated nanocellulose,with its negative charge density further reinforced by anionic polyacrylamide incorporation.This modification simultaneously improves the separator’s mechanical properties,ionic conductivity,and Zn^(2+)ion transfer number.Remarkably,despite its ultrathin 20μm profile,the engineered separator demonstrates exceptional dendrite suppression and parasitic reaction inhibition,enabling Zn//Zn symmetric cells to achieve impressive cycle life(>1800 h at 2 m A cm^(-2)/2 m Ah cm^(-2))while maintaining robust performance even at ultrahigh areal capacities(25 m Ah cm^(-2)).Additionally,the separator’s anionic characteristic effectively blocks polyiodide migration through electrostatic repulsion,yielding Zn-I_(2) batteries with outstanding rate capability(120.7 m Ah g^(-1)at 5 A g^(-1))and excellent cyclability(94.2%capacity retention after 10,000 cycles).And superior cycling stability can still be achieved under zinc-deficient condition and pouch cell configuration.This work establishes a new paradigm for designing high-performance zinc-based energy storage systems through rational separator engineering.
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（/）.
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）.
基金National Natural Science Foundation of China(51903113,51763014,and 52073133)China Postdoctoral Science Foundation(2022T150282,2019M663858)Program for Hongliu Excellent and Distinguished Young Scholars at Lanzhou University of Technology.
文摘Aqueous zinc metal batteries are regarded as the most promising energy storage system due to their advantages of high safety,low cost,and high theoretical capacity.However,the growth of dendrites and the occurrence of side reactions hinder the development of zinc metal batteries.Despite previous attempts to design advanced hydrogel electrolytes,achieving high mechanical performance and ionic conductivity of hydrogel electrolytes has remained challenging.In this work,a hydrogel electrolyte with an ionic crosslinked network is prepared by carboxylic bacterial cellulose fiber and imidazole-type ionic liquid,following by a covalent network of polyacrylamide.The hydrogel electrolyte possesses a superior ionic conductivity of 43.76 mS cm^(−1),leading to a Zn^(2+)migration number of 0.45,and high mechanical performance with an elastic modulus of 3.48 GPa and an elongation at breaking of 38.36%.More importantly,under the anion-coordination effect of the carboxyl group in bacterial cellulose and[BF4]−in imidazole-type ionic liquid,the solvation sheath of hydrated Zn^(2+)ions and the nucleation overpotential of Zn plating are regulated.The results of cycled testing show that the growth of zinc dendrites is effectively inhibited and the generation of irreversible by-products is reduced.With the carboxylic bacterial cellulose-based hydrogel electrolyte,the Zn||Zn symmetric batteries offer good cyclability as well as Zn||Ti batteries.
基金the National Natural Science Foundation of China(No.21978164,22078189 and 22105120)the Outstanding Youth Science Fund of Shaanxi Province(No.2021JC-046)and the Special Support Program for high level talents of Shaanxi Province+3 种基金the Innovation Support Program of Shaanxi Province(2021JZY-001)the Key Research and Development Program of Shaanxi Province(No.2020GY-243)the Special Research Fund of Education Department of Shaanxi(No.20JK0535)the National High-end Foreign Expert Project(No.GDW20186100428).
文摘Pore structure engineering has been acknowledged as suitable approach to creating active sites and en-hancing ion transport capabilities of hard carbon anodes.However,conventional porous carbon materials exhibit high BET and surface defects.Additionally,the sodium storage mechanism predominantly occurs in the slope region.This contradicts practical application requirements because the capacity of the plateau region is crucial for determining the actual capacity of batteries.In our work,we prepared a novel“core-shell”carbon framework(CNA1200).Introducingclosedporesand carboxylgroupsinto coal-basedcarbon materials to enhance its sodium storage performance.The closed pore structure dominates in the“core”structure,which is attributed to the timely removal of sodium hydroxide(NaOH)to prevent further for-mation of active carbon structure.The presence of closed pores is beneficial for increasing sodium ion storage in the low-voltage plateau region.And the“shell”structure originates from coal tar pitch,it not only uniformly connects hard carbon particles together to improve cycling stability,but is also rich in carboxyl groups to enhance the reversible sodium storage performance in slope region.CNA1200 has ex-cellent electrochemical performance,it exhibits a specific capacity of 335.2 mAh g^(−1)at a current density of 20 mA g^(−1)with ICE=51.53%.In addition,CNA1200 has outstanding cycling stability with a capac-ity retention of 91.8%even when cycling over 200 times.When CNA1200 is used as anode paired with Na_(3)V_(2)(PO_(4))_(3)cathode,it demonstrates a capacity of 109.54 mAh g^(−1)at 0.1 C and capacity retention of 94.64%at 0.5 C.This work provides valuable methods for regulating the structure of sodium-ion battery(SIBs)anode and enhances the potential for commercialization.
基金the support provided by the Surface Analysis Laboratory, Solid State and Elemental Analysis Unit, Mark Wainwright Analytical Centre of the University of New South Walesthe support of the Iranian Research Organization for Science and Technology (IROST), contract no. 034592
文摘Salination of solutions of salinity gradient releases large‐scale clean and renewable energy, which can be directly and efficiently transformed into electrical energy using ion‐selective nanofluidic channel membranes. However, conventional ion‐selective membranes are typically either cation‐ or anion‐selective. A pH‐switchable system capable of dual cation and anion transport along with salt gradient energy harvesting properties has not been demonstrated in ion‐selective membranes. Here, we constructed an amphoteric heterolayer metal–organic framework (MOF) membrane with subnanochannels modified with carboxylic and amino functional groups. The amphoteric MOF‐composite membrane, AAO/aUiO‐66‐(COOH)_(2)/UiO‐66‐NH_(2), exhibits pH‐tuneable ion conduction and achieves osmotic energy conversion of 7.4 and 5.7 W/m^(2) in acidic and alkaline conditions, respectively, using a 50‐fold salt gradient. For different anions but the same cation diffusion transport, the amphoteric membrane produces an outstanding I−/CO_(3)^(2−) selectivity of ~4160 and an osmotic energy conversion of ~133.5 W/m^(2). The amphoteric membrane concept introduces a new pathway to explore the development of ion transport and separation technologies and their application in osmotic energy‐conversion devices and flow batteries.
基金This work was supported by the National Natural Science Foundation of China （No.20502017, No.20872102, and No.21021001）, the Program for Changjiang Scholars and Innovative Research Team in University （No.IRT0846）, and the characterization of the catalyst from Analytic and Testing Center of Sichuan University are greatly appreciated.
文摘Commercially available coal-based activated carbon was treated by nitric acid with different concentrations and the resultant samples were used as catalysts for the direct hydroxylation of benzene to phenol in acetonitrile. Boehm titration, X-ray photoelectron spectroscopy, scanning electron microscope coupled with an energy dispersive X-ray microanalyzer, and Brunauer-Emmett-Teller method were used to characterize the samples. The number of carboxyl groups on the surface was found to be the main factor affecting the catalytic activity. An optimum catalytic performance with a yield of 15.7% and a selectivity of 87.2% to phenol was obtained.
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supported by the University Science Foundation of Anhui Province (No. KJ2011Z271)the Applied Chemistry Key Constructing Subject of Anhui Province (No. 200802187C)
文摘An alkaline earth metal-organic framework [Ba（Hsip）（H2O）4]n （1, NaH2sip = 5-sulfoisophthalic acid sodium） has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba（II） atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a （6, 3） topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333（2）, b = 16.7044（3）, c = 10.4817（2）, Z = 4, V = 1283.99（5）3, Mr = 453.58, Dc = 2.346 g/cm3, F（000） = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ（I）.
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This research was funded by The Talents Project for Harbin Science and Technology Innovation,grant number 2016RAXXJ006China Postdoctoral Science Foundation,grant number 2017M611341.
文摘Cellulose nanofibrils(CNFs)are promising sustainable materials that can be applied to nanocomposites,as well as medical and life-sciences devices.However,methods for the preparation of these important materials are energy intensive because heating and mechanical disintegration are required to produce cellulose fibers below 100 nm in size.In this study,CNFs were prepared through the multi-site regioselective oxidation of cellulose with 2,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO)and periodate at room temperature(20–25°C),without any mechanical-disintegration treatment.Transmission electron microscopy(TEM)revealed that the CNFs had the average widths of 14.1,55.4,and 81.9 nm for three different treatments.Fourier-transform infrared spectroscopy revealed that carboxyl groups were created on the surfaces of the microfibrils,while X-ray diffraction studies showed that the cellulose I structure was maintained after oxidation,and that the cellulose nanofibril crystallinity index exceeded 70%.These results demonstrate that CNFs can be prepared by multi-site regioselective oxidation at room temperature in the absence of mechanical disintegration.In addition,a model was developed to calculate the total content of carboxylate and aldehyde groups of CNFs prepared by the TEMPO mediate oxidation,the periodate oxidation,and the multi-site regioselective oxidation methods based on the particle width determined by TEM.The calculated values of the model were in good agreement with the total content(experimental value)of carboxylate and aldehyde groups of CNFs prepared by the TEMPO-mediated oxidation and the multi-site regioselective oxidation methods.However,the model was not valid for CNFs prepared by the periodate oxidation method.
基金Supported by Ministry of Education,Culture,Sports,Science and Technology of Japan
文摘Limonoid bitterness is a serious problem in the citrus industry worldwide. Limonoid glucosyltransferase is an enzyme that catalyzes the conversion of bitter limonoid into non-bitter limonoid glucoside while retaining the health benefit of limonoids in the juice. The immobilization of this enzyme in a column can solve the juice bitterness problem. More information about the catalytic residues of the enzyme is needed in this immobilization process. Glutamate/aspartate,histidine,lysine,tryptophan,serine,and cysteine residues were chemi-cally modified to investigate their roles in the catalytic function of limonoid glucosyltransferase. Inactivation of the enzyme following modi-fication of carboxyl and imidazole moieties was a consequence of a loss in substrate binding and catalysis in the glucosyltransfer reaction. The modification of a single histidine residue completely destroyed the ability of limonoid glucosyltransferase to transfer the D-glucopyranosyl unit. Tryptophan seemed to have some role in maintaining the active conformation of the catalytic site. Lysine also seemed to have some direct or indirect role in this catalysis but the modification of serine and cysteine did not have any effect on catalysis. Therefore,we conclude that the carboxyl and imidazole groups containing amino acids are responsible for the catalytic action of the enzyme.
