Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversi...Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion(TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer(PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3,and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated,TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive vips.展开更多
The authors regret that an error in Fig.3E in this article was found while we reviewing the published data.An inadvertent mistake occurred in the process of assembling images.The picture of the Ms215μg/mL group was w...The authors regret that an error in Fig.3E in this article was found while we reviewing the published data.An inadvertent mistake occurred in the process of assembling images.The picture of the Ms215μg/mL group was wrongly placed.展开更多
Humic acid(HA) as a natural reducing ligand was employed to accelerate the Fenton and Fenton-like processes, however, the potential role of photosensitivity was overlooked. This research showed that HA exhibits more s...Humic acid(HA) as a natural reducing ligand was employed to accelerate the Fenton and Fenton-like processes, however, the potential role of photosensitivity was overlooked. This research showed that HA exhibits more significant promotion for levofloxacin(LVF) degradation under light conditions compared to darkness. The study also proposed a mechanism involving complexation and photosensitization interactions. A strong inhibitor of ethylenediaminetetraacetic acid confirmed that the formation of organic-iron complexes was crucial. Firstly, it was proposed that complexed iron has a lower redox potential than free iron, which may be responsible for accelerating electron transfer from iron to peroxydisulfate(PDS). The density functional theory(DFT) calculations confirmed that complexed iron has a lower reaction energy barrier for PDS activation. Additionally, the excited state substances(^(*)HA and ^(*)LVF) can transfer electrons to Fe(Ⅲ) and PDS, and the generation of HA/LVF-Fe(Ⅲ)-PDS can accelerate this process. These findings could offer fresh perspectives on the combined elimination of contaminants through natural organic compounds and light exposure.展开更多
Based on a non-equilibrium kinetic extraction technique,the complexation kinetics of diethylenetriamine-pentaacetic acid(DTPA)with rare earth(RE)ions was investigated with different adding sequences of DTPA.The result...Based on a non-equilibrium kinetic extraction technique,the complexation kinetics of diethylenetriamine-pentaacetic acid(DTPA)with rare earth(RE)ions was investigated with different adding sequences of DTPA.The results indicated that the separation factors ofβTm/Er andβY/Er were higher when adding DTPA at the start of extraction than those before extraction.The extraction order for Y,Er and Tm was Tm>Y>Er.The root of discrepancy in complexation kinetics of Y,Er and Tm ions with DTPA and the enhanced kinetic separation mechanism were elucidated from the forward complex formation and reverse dissociation rates by the stopped-flow spectrophotometric technique.The apparent complexation rate constants began to decrease gradually with the increase of aqueous pH,while increased with increasing DTPA concentration.The emergence of extraction priority order as Tm>Y>Er was verified according to the calculated reaction kinetic constants of Y,Er and Tm at different pH values.展开更多
In the present study, we investigated the complexation of risperidone with hydroxypropyl-β-cyclodextrin （HP-β-CD） in aqueous solution due to the poor water solubility and low oral bioavailability of risperidone in...In the present study, we investigated the complexation of risperidone with hydroxypropyl-β-cyclodextrin （HP-β-CD） in aqueous solution due to the poor water solubility and low oral bioavailability of risperidone in humans. The effect of temperature on the complexation was examined, and thermodynamic parameters of the complexation process, such as Gibbs free energy change （AG）, enthalpy change （AH） and entropy change （AS）, were also explored. Meantime, the solid dispersion of risperidone with HP-β-CD was prepared and confirmed by Fourier IR spectroscopy and X-ray diffractometry. The experimental results suggested that the complex of the drug with HP-β-CD at a molar ratio of 1：1 could form in aqueous solution, and the complexation was an endothermic and entropy-driven process. The risperidone-HP-β-CD solid dispersion exhibited a remarkable improvement in the dissolution rate of the drug. This might be attributed to the amorphous state, the enhanced wettability as well as the complex formation of the drug with HP-β-CD in aqueous solution.展开更多
The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and t...The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and the pH of the solutions were also investigated. A timed complexatian colorimetric analysis method of Al-Fe-ferron in view of the total concentration of {AI + Fe} was then established to determine the species distribution of polymeric Al-Fe. The testing wavelength was recommended at 362 net and the testing pH value was 5. With a comparison of the ratios of n(Al)/n(Fe), the standard adsorption curves of the polymeric Al-Fe solutions were derived from the experimental results. Furthermore, the solutions' composition were carious in both the molar n(Al)/n(Fe) ratios, i.e. 0/0, 5/5, 9/1 and 0/10, and the concentrations associated with the total ( Al + Fe which ranged from 10(-5) to 10(-4) mol/L..展开更多
A novel method for the separation and reclamation of vanadium and chromium from acidic solution was proposed. The principle for the separation is based on selective complexation. In specific, V(V) can be complexated b...A novel method for the separation and reclamation of vanadium and chromium from acidic solution was proposed. The principle for the separation is based on selective complexation. In specific, V(V) can be complexated by dithiocarbamate to form VO(R1R2NCS2)3 precipitate, leaving Cr(Ⅲ) remained in the acidic solution. Then the reclamation of V and Cr from VO(R1R2NCS2)3 precipitate and Cr(Ⅲ)-bearing solution can be reached by decomplexation and neutralization, respectively. The kinetics of the complexation reaction was studied. In addition, the precipitation ratio of vanadium reached 97% and the loss of chromium was less than 4% after process optimization. The complexing agent could be regenerated with a high ratio of 99.5%. The method was successfully applied to treating chromium-vanadium-bearing slag produced in conventional vanadium production industry. Vanadium and chromium could be extracted from the slag in the form of calcium vanadate and Cr2O3 product with a purity of over 98%.展开更多
The objectives of the study were to investigate the effects of β-cyclodextrin(βCD) and hydroxypropyl-β-cyclodextrin(HPβCD) on the solubility and dissolution rate of norfloxacin prepared using three different metho...The objectives of the study were to investigate the effects of β-cyclodextrin(βCD) and hydroxypropyl-β-cyclodextrin(HPβCD) on the solubility and dissolution rate of norfloxacin prepared using three different methods, at drug to cyclodextrin weight ratios of 1:1, 1:2, 1:4 and 1:8. All the methods increased the solubility and dissolution rate of norfloxacin via inclusion complexation with βCD and HPβCD. Norfloxacin was converted from crystalline to amorphous form through inclusion complexation. Solvent evaporation method was the most effective method in terms of norfloxacin solubilisation, while inclusion complex of HPβCD has higher solubility than βCD complex when prepared using the same procedure.展开更多
During the chemical weathering of the uranium mill tailings,released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides.A deeper understanding of the interaction between uranium ...During the chemical weathering of the uranium mill tailings,released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides.A deeper understanding of the interaction between uranium and common oxyhydroxides under environmental conditions is necessary.In this work,uranium sorption behaviors on Al-,Mn-and Fe-oxyhydroxide minerals(boehmite,manganite,goethite,and lepidocrocite)were investigated by batch experiments.Results showed that the uranium sorption on Al-oxyhydroxide behaved significantly differently from the other three minerals.The sorption edge of the Mn-and Fe-oxyhydroxides located around pH 5,while the sorption edge of boehmite shifted about 1.5 pH unit to near neutral.The sorption isotherms of uranium on manganite,goethite and lepidocrocite at pH 5.0 could be well fitted by the Langmuir model.Instead of surface complexation,sorption on boehmite happened mainly by uranium-bearing carbonates and hydroxides precipitation as illustrated by the characterization results.Both carbonate and phosphate strongly affected the uranium sorption behavior.The removal efficiency of uranium by boehmite exceeded 98%after three sorption-desorption cycles,indicating it may be a potential material for uranium removal and recovery.展开更多
A method was developed for preparing high purity Al30O8(OH)56(H2O)_(24)^(18)+(Al30) through elimination of impurities by complexation.Polyaluminum chloride II(PAC_(30))with Al_(c )content of 75%was adopted as the sour...A method was developed for preparing high purity Al30O8(OH)56(H2O)_(24)^(18)+(Al30) through elimination of impurities by complexation.Polyaluminum chloride II(PAC_(30))with Al_(c )content of 75%was adopted as the source of Al_(30).The PAC_(30)was prepared under conditions of total aluminum concentration 0.1 mol/L and OH^-/Al ratio 2.2 to obtain the highest content of Al_(30).A precipitation/metathesis method,organic solvent precipitation method and organic complexation method were examined to separate and purify Al_(30).It was found that only by the organic complexation method could high purity Al_(30)products be obtained in large yield economically.In the experiments,benzoic acid was used as the coordinating reagent to decompose the main impurity AlO_4Al_(12)(OH)_(24)(H_2O)_(12)^(7+)(Al_(13)),and the Al_(30)product could be obtained by precipitation and metathesis operations.It was noteworthy that the decomposition of impurities by benzoic acid could be completed in 2 hr.The Al_(30)product was characterized by Ferron assay,^(27)Al-NMR,SEM,XRD and TGA.The results showed that the purity of the Al_(30)product could exceed 92%.展开更多
A greater part of water-solnble organic substances, accounting for 6070To of the total, could be adsorbedby soils, which included strongly and weekly reducing substances, positively and negatively charged substancesan...A greater part of water-solnble organic substances, accounting for 6070To of the total, could be adsorbedby soils, which included strongly and weekly reducing substances, positively and negatively charged substancesand substances containing amido. There existed a tendency of decrease in adsorption of the negativelycharged organic substances by the soil from South China to North China, with expression as Coulombianadsorption. A simultaneous reduction of iron and manganese appeared with clear voltammetric behavioursupon oxidation of water-soluble organic substances. Complexation of organic ligands with ferrons iron andmanganous manganese was proved by differential pulse voltammetric method, with disappearance of oxidationpeaks of ferrous iron and manganous manganese at 0.00 V and 0.35 V and occurrence of Fe`+-complex andMn￣2+ -complex at 0.75 V and 1.2 V respectively, whose peak potentials shifted backward.展开更多
Based on numerous latest references, the current developments in surface complexation, surface precipitation and the corresponding models (SCMs and SPMs), were reviewed. The contents involved comparison on surface cha...Based on numerous latest references, the current developments in surface complexation, surface precipitation and the corresponding models (SCMs and SPMs), were reviewed. The contents involved comparison on surface charge composition and layer-structure of solid-solution interface for the classical 1-pK and 2-pK models. In addition, the fundamental concept and relations of the new models, i. e., multi-site complexation (MUSIC) and charge- distribution (CD) MUSIC models were described as well. To avoid misuse or abuse, it must be emphasized that the applicability and limitation for each model should be considered carefully when selecting the concerned model(s). In addition, some new powerful techniques for surface characterization and analysis applied to model establishment and modification were also briefly introduced.展开更多
Removal of Co(Ⅱ) from aqueous solutions by complexation-ultrafiltration was investigated using polyacrylic acid sodium(PAAS) as complexing agent with the help of rotating disk membrane,and the shear ability of PAA-Co...Removal of Co(Ⅱ) from aqueous solutions by complexation-ultrafiltration was investigated using polyacrylic acid sodium(PAAS) as complexing agent with the help of rotating disk membrane,and the shear ability of PAA-Co complex was studied. The effects of the mass ratio of PAAS to Co(Ⅱ)(P/M) and pH on the rejection of Co(Ⅱ) were studied,and the optimum conditions were P/M=8 and pH=7. The rejection of Co(Ⅱ) was over 97% when the rotating speed of the disk(n)was less than 710 r/min at the optimum P/M and pH. The distribution of the forms of cobalt on the membrane surface was established by the membrane partition model, and the critical shear rate,the smallest shear rate at which the PAA-Co complex begins to dissociate,was calculated to be1.4×10^4 s^-1,and the corresponding rotating speed was 710 r/min.The PAA-Co complex dissociated when the shear rate was greater than the critical one. The regeneration of PAAS and recovery of Co(Ⅱ) were achieved by shear-induced dissociation and ultrafiltration.展开更多
A series of monomethoxy poly（ethylene glycol） （mPEG） grafted copolyglutamates （PmPEGs） were synthesized through ring-opening polymerization （ROP） followed by click chemistry. Supramolecular hydrogels based on ...A series of monomethoxy poly（ethylene glycol） （mPEG） grafted copolyglutamates （PmPEGs） were synthesized through ring-opening polymerization （ROP） followed by click chemistry. Supramolecular hydrogels based on polymer inclusion complexes （ICs） between PmPEG and α-cyclodextriri （α-CD） were prepared in aqueous solution. The rheological measurements indicated their gelation properties were affected by several factors including the mPEG length, graft density and the sample concentration. These hydrogels displayed thermo-sensitive gel-sol transition under appropriate conditions due to the reversible mPEG and α-CD inclusion complexation. These hydrogels also showed pH-sensitive behavior due to the deprotonate of carboxylic acid side groups. The ICs formation of a channel-type crystalline structure induced gelation mechanism was verified by various techniques. In vitro cytotoxicity assays demonstrated that the supramolecular hydrogels are nontoxic and cytocompatible.展开更多
Accumulation of toxic ions in leachate is one factor limiting bioleaching applications. The effect of fluoride ions on the growth of bioleaching microorganisms has been extensively emphasized. In this study, HF is fou...Accumulation of toxic ions in leachate is one factor limiting bioleaching applications. The effect of fluoride ions on the growth of bioleaching microorganisms has been extensively emphasized. In this study, HF is found to be the toxic form of fluoride that affects the bacterial activity under acidic conditions. The added aluminum could compete with H^+ to complex with F-, thus significantly decrease the concentration of HF and finally reduce the toxicity of fluoride to bacteria. When F^-/Al^(3+)concentration ratio is 0.5:1.0, Fe^(2+) oxidation rate could reach 0.167 g·L^(-1)·h^(-1), close to that of the biotic control group(0.195 g·L^(-1)·h^(-1)). The competitive complexation mechanism of fluoride by AlF_n^(3-n) results in stability constants of AlF_n^(3-n) complex(7.00) that are larger than those of HF(3.18). The F^-/Al^(3+) concentration ratio in the medium could affect the speciation of AlF_n^(3-n) complex.With the decrease in F^-/Al^(3+) concentration ratio, the coordination numbers of AlF_n^(3-n) decrease. Finally, the feasibility of fluoride detoxification by aluminum ion is verified. This work has meaningful implications for fluoride-containing bacterial bioleaching systems.展开更多
Catechol pollutants(CATPs)serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes.Little information is available on the effects of complexation of metal ions on CATPs d...Catechol pollutants(CATPs)serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes.Little information is available on the effects of complexation of metal ions on CATPs degradation.This work presents a systematical study of·OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes(AOPs).Results show that the pH-dependent complexation of metal ions(Zn^(2+),Cu^(2+),Ti^(4+)and Fe^(3+))promotes the deprotonation of catechol under neutral and even acidic conditions.The radical adduct formation(RAF)reactions are both thermodynamically and kinetically favorable for all dissociation and complexa-tion species,and-OH/-O-group-containing C positions are more vulnerable to·OH attack.The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation.At pH 7,the apparent rate constant(k_(app))values for different systems follow the order of catechol+Ti^(4+)≈catechol+Zn^(2+)>catechol+Cu^(2+)>catechol+Fe^(3+)>catechol.The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs.The toxicity assessment indicates that the·OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.展开更多
The layer by layer complexation technique of polymer and metal ion was successfully utilized to fabricate the ultrathin multilayer film of poly(3 thiophene acetic acid (PTAA) and Tb 3+ ion by dipping the subst...The layer by layer complexation technique of polymer and metal ion was successfully utilized to fabricate the ultrathin multilayer film of poly(3 thiophene acetic acid (PTAA) and Tb 3+ ion by dipping the substrates alternatively in polymer and Tb 3+ ion aqueous solutions. UV-vis measurement revealed that the absorbance has linearity with the bilayer number from layer to layer and the X ray photoelectron spectrum (XPS) confirmed the existence of Tb 3+ ion. The pH of both the polymer and TbCl 3 solutions influence the thickness dramatically while the concentration of the solutions is not so sensitive. The luminescent spectrum of the complex film shows the characteristic emission of Tb 3+ ion as well as the ligand indicating the formation of the complex.展开更多
An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C_2H_4 on MX(M=Ag, Cu; X=F, Cl). The calculated results show the following order of adsorptio...An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C_2H_4 on MX(M=Ag, Cu; X=F, Cl). The calculated results show the following order of adsorption strength: F ->Cl - for anions; Cu +>Ag + for cations. The results can be explained by the detailed analysis of atomic charge, orbital energy and orbital population by using the natural bond orbital(NBO) theory: (1) anions with stronger electronegativity can attract more electrons from the s orbital of M, while at the same time it does not obviously weaken the d orbital occupation of M, thus the nearly vacant s orbital and the sufficiently filled d orbitals of M help with forming σ-donation and d-π * backdonation with the π orbital and the π * orbital of olefin, respectively; (2) a smaller energy gap of symmetry-adapted orbitals between olefin and a cation can favor the electron transfer, that is why Cu + forms stronger adsorption with olefin than Ag + does.展开更多
The complexation capacity for heavy metals (Cu, Cd, Pb) were determined by anodic stripping voltammetry in South China Sea, Hulun Lake and Wuliang Suhai. The conditional stability constants and complexation capacity i...The complexation capacity for heavy metals (Cu, Cd, Pb) were determined by anodic stripping voltammetry in South China Sea, Hulun Lake and Wuliang Suhai. The conditional stability constants and complexation capacity index were calculated. The data showed that the complexation capacity of the Hulun Lake was greater than that of seawater and Wuliang Suhai. The sequence of complexation capacity is C (CuL)> C (CdL)> C (PbL), the values are in concord with results of analysis on dissolved organic carbon. The conditional stability constants were in an opposite sequence: K (CuL)< K (CdL)< K (PbL). When log K are similar, the greater the complexation capacity, the greater the complexation capacity index.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 22171194, 21971169, 92056116 and 21871194)the Fundamental Research Funds for the Central Universities (No. 20826041D4117)the Science & Technology Department of Sichuan Province (Nos. 2022YFH0095 and 2021ZYD0052)。
文摘Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion(TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer(PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3,and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated,TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive vips.
文摘The authors regret that an error in Fig.3E in this article was found while we reviewing the published data.An inadvertent mistake occurred in the process of assembling images.The picture of the Ms215μg/mL group was wrongly placed.
基金supported by the Natural Science Foundation of China (No. 42107073)Central Guidance for Local Science and Technology Development Fund Projects (No. 2024ZYD0030)+1 种基金Natural Science Foundation of Sichuan Province (No. 2024NSFSC0130)the Sichuan Science and Technology Program (No. 2024NSFTD0014)。
文摘Humic acid(HA) as a natural reducing ligand was employed to accelerate the Fenton and Fenton-like processes, however, the potential role of photosensitivity was overlooked. This research showed that HA exhibits more significant promotion for levofloxacin(LVF) degradation under light conditions compared to darkness. The study also proposed a mechanism involving complexation and photosensitization interactions. A strong inhibitor of ethylenediaminetetraacetic acid confirmed that the formation of organic-iron complexes was crucial. Firstly, it was proposed that complexed iron has a lower redox potential than free iron, which may be responsible for accelerating electron transfer from iron to peroxydisulfate(PDS). The density functional theory(DFT) calculations confirmed that complexed iron has a lower reaction energy barrier for PDS activation. Additionally, the excited state substances(^(*)HA and ^(*)LVF) can transfer electrons to Fe(Ⅲ) and PDS, and the generation of HA/LVF-Fe(Ⅲ)-PDS can accelerate this process. These findings could offer fresh perspectives on the combined elimination of contaminants through natural organic compounds and light exposure.
基金funded by Key Laboratory of Ionic Rare Earth Resources and Environment,Ministry of Natural Resources,China(No.2022IRERE206)financially supported by the National Natural Science Foundation of China(Nos.51904027,52074031)。
文摘Based on a non-equilibrium kinetic extraction technique,the complexation kinetics of diethylenetriamine-pentaacetic acid(DTPA)with rare earth(RE)ions was investigated with different adding sequences of DTPA.The results indicated that the separation factors ofβTm/Er andβY/Er were higher when adding DTPA at the start of extraction than those before extraction.The extraction order for Y,Er and Tm was Tm>Y>Er.The root of discrepancy in complexation kinetics of Y,Er and Tm ions with DTPA and the enhanced kinetic separation mechanism were elucidated from the forward complex formation and reverse dissociation rates by the stopped-flow spectrophotometric technique.The apparent complexation rate constants began to decrease gradually with the increase of aqueous pH,while increased with increasing DTPA concentration.The emergence of extraction priority order as Tm>Y>Er was verified according to the calculated reaction kinetic constants of Y,Er and Tm at different pH values.
基金Science and Technology Million Project of Inner Mongolia Medical University(Grant No.YKD2014KJBW012)
文摘In the present study, we investigated the complexation of risperidone with hydroxypropyl-β-cyclodextrin （HP-β-CD） in aqueous solution due to the poor water solubility and low oral bioavailability of risperidone in humans. The effect of temperature on the complexation was examined, and thermodynamic parameters of the complexation process, such as Gibbs free energy change （AG）, enthalpy change （AH） and entropy change （AS）, were also explored. Meantime, the solid dispersion of risperidone with HP-β-CD was prepared and confirmed by Fourier IR spectroscopy and X-ray diffractometry. The experimental results suggested that the complex of the drug with HP-β-CD at a molar ratio of 1：1 could form in aqueous solution, and the complexation was an endothermic and entropy-driven process. The risperidone-HP-β-CD solid dispersion exhibited a remarkable improvement in the dissolution rate of the drug. This might be attributed to the amorphous state, the enhanced wettability as well as the complex formation of the drug with HP-β-CD in aqueous solution.
基金TheNationalNaturalScienceFoundationofChina (No .2 96 770 0 4)
文摘The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and the pH of the solutions were also investigated. A timed complexatian colorimetric analysis method of Al-Fe-ferron in view of the total concentration of {AI + Fe} was then established to determine the species distribution of polymeric Al-Fe. The testing wavelength was recommended at 362 net and the testing pH value was 5. With a comparison of the ratios of n(Al)/n(Fe), the standard adsorption curves of the polymeric Al-Fe solutions were derived from the experimental results. Furthermore, the solutions' composition were carious in both the molar n(Al)/n(Fe) ratios, i.e. 0/0, 5/5, 9/1 and 0/10, and the concentrations associated with the total ( Al + Fe which ranged from 10(-5) to 10(-4) mol/L..
基金Project(51674230) supported by the National Natural Science Foundation of ChinaProject(2018YFC1900505) supported by the National Key R&D Program of China
文摘A novel method for the separation and reclamation of vanadium and chromium from acidic solution was proposed. The principle for the separation is based on selective complexation. In specific, V(V) can be complexated by dithiocarbamate to form VO(R1R2NCS2)3 precipitate, leaving Cr(Ⅲ) remained in the acidic solution. Then the reclamation of V and Cr from VO(R1R2NCS2)3 precipitate and Cr(Ⅲ)-bearing solution can be reached by decomplexation and neutralization, respectively. The kinetics of the complexation reaction was studied. In addition, the precipitation ratio of vanadium reached 97% and the loss of chromium was less than 4% after process optimization. The complexing agent could be regenerated with a high ratio of 99.5%. The method was successfully applied to treating chromium-vanadium-bearing slag produced in conventional vanadium production industry. Vanadium and chromium could be extracted from the slag in the form of calcium vanadate and Cr2O3 product with a purity of over 98%.
文摘The objectives of the study were to investigate the effects of β-cyclodextrin(βCD) and hydroxypropyl-β-cyclodextrin(HPβCD) on the solubility and dissolution rate of norfloxacin prepared using three different methods, at drug to cyclodextrin weight ratios of 1:1, 1:2, 1:4 and 1:8. All the methods increased the solubility and dissolution rate of norfloxacin via inclusion complexation with βCD and HPβCD. Norfloxacin was converted from crystalline to amorphous form through inclusion complexation. Solvent evaporation method was the most effective method in terms of norfloxacin solubilisation, while inclusion complex of HPβCD has higher solubility than βCD complex when prepared using the same procedure.
基金National Natural Science Foundation of China(NSFC,No.11475008)。
文摘During the chemical weathering of the uranium mill tailings,released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides.A deeper understanding of the interaction between uranium and common oxyhydroxides under environmental conditions is necessary.In this work,uranium sorption behaviors on Al-,Mn-and Fe-oxyhydroxide minerals(boehmite,manganite,goethite,and lepidocrocite)were investigated by batch experiments.Results showed that the uranium sorption on Al-oxyhydroxide behaved significantly differently from the other three minerals.The sorption edge of the Mn-and Fe-oxyhydroxides located around pH 5,while the sorption edge of boehmite shifted about 1.5 pH unit to near neutral.The sorption isotherms of uranium on manganite,goethite and lepidocrocite at pH 5.0 could be well fitted by the Langmuir model.Instead of surface complexation,sorption on boehmite happened mainly by uranium-bearing carbonates and hydroxides precipitation as illustrated by the characterization results.Both carbonate and phosphate strongly affected the uranium sorption behavior.The removal efficiency of uranium by boehmite exceeded 98%after three sorption-desorption cycles,indicating it may be a potential material for uranium removal and recovery.
基金supported by the National Natural Science Foundation of China (Nos. 21507149, 51338010)the National Water Pollution Control and Treatment Science and Technology Major Project (No. 2015ZX07406005-002)
文摘A method was developed for preparing high purity Al30O8(OH)56(H2O)_(24)^(18)+(Al30) through elimination of impurities by complexation.Polyaluminum chloride II(PAC_(30))with Al_(c )content of 75%was adopted as the source of Al_(30).The PAC_(30)was prepared under conditions of total aluminum concentration 0.1 mol/L and OH^-/Al ratio 2.2 to obtain the highest content of Al_(30).A precipitation/metathesis method,organic solvent precipitation method and organic complexation method were examined to separate and purify Al_(30).It was found that only by the organic complexation method could high purity Al_(30)products be obtained in large yield economically.In the experiments,benzoic acid was used as the coordinating reagent to decompose the main impurity AlO_4Al_(12)(OH)_(24)(H_2O)_(12)^(7+)(Al_(13)),and the Al_(30)product could be obtained by precipitation and metathesis operations.It was noteworthy that the decomposition of impurities by benzoic acid could be completed in 2 hr.The Al_(30)product was characterized by Ferron assay,^(27)Al-NMR,SEM,XRD and TGA.The results showed that the purity of the Al_(30)product could exceed 92%.
文摘A greater part of water-solnble organic substances, accounting for 6070To of the total, could be adsorbedby soils, which included strongly and weekly reducing substances, positively and negatively charged substancesand substances containing amido. There existed a tendency of decrease in adsorption of the negativelycharged organic substances by the soil from South China to North China, with expression as Coulombianadsorption. A simultaneous reduction of iron and manganese appeared with clear voltammetric behavioursupon oxidation of water-soluble organic substances. Complexation of organic ligands with ferrons iron andmanganous manganese was proved by differential pulse voltammetric method, with disappearance of oxidationpeaks of ferrous iron and manganous manganese at 0.00 V and 0.35 V and occurrence of Fe`+-complex andMn￣2+ -complex at 0.75 V and 1.2 V respectively, whose peak potentials shifted backward.
文摘Based on numerous latest references, the current developments in surface complexation, surface precipitation and the corresponding models (SCMs and SPMs), were reviewed. The contents involved comparison on surface charge composition and layer-structure of solid-solution interface for the classical 1-pK and 2-pK models. In addition, the fundamental concept and relations of the new models, i. e., multi-site complexation (MUSIC) and charge- distribution (CD) MUSIC models were described as well. To avoid misuse or abuse, it must be emphasized that the applicability and limitation for each model should be considered carefully when selecting the concerned model(s). In addition, some new powerful techniques for surface characterization and analysis applied to model establishment and modification were also briefly introduced.
基金Project(24176265)supported by the National Natural Science Foundation of China
文摘Removal of Co(Ⅱ) from aqueous solutions by complexation-ultrafiltration was investigated using polyacrylic acid sodium(PAAS) as complexing agent with the help of rotating disk membrane,and the shear ability of PAA-Co complex was studied. The effects of the mass ratio of PAAS to Co(Ⅱ)(P/M) and pH on the rejection of Co(Ⅱ) were studied,and the optimum conditions were P/M=8 and pH=7. The rejection of Co(Ⅱ) was over 97% when the rotating speed of the disk(n)was less than 710 r/min at the optimum P/M and pH. The distribution of the forms of cobalt on the membrane surface was established by the membrane partition model, and the critical shear rate,the smallest shear rate at which the PAA-Co complex begins to dissociate,was calculated to be1.4×10^4 s^-1,and the corresponding rotating speed was 710 r/min.The PAA-Co complex dissociated when the shear rate was greater than the critical one. The regeneration of PAAS and recovery of Co(Ⅱ) were achieved by shear-induced dissociation and ultrafiltration.
基金financially supported by the National Natural Science Fund for Distinguished Young Scholars(No.51225306)the National Natural Science Foundation of China(No.21434008)
文摘A series of monomethoxy poly（ethylene glycol） （mPEG） grafted copolyglutamates （PmPEGs） were synthesized through ring-opening polymerization （ROP） followed by click chemistry. Supramolecular hydrogels based on polymer inclusion complexes （ICs） between PmPEG and α-cyclodextriri （α-CD） were prepared in aqueous solution. The rheological measurements indicated their gelation properties were affected by several factors including the mPEG length, graft density and the sample concentration. These hydrogels displayed thermo-sensitive gel-sol transition under appropriate conditions due to the reversible mPEG and α-CD inclusion complexation. These hydrogels also showed pH-sensitive behavior due to the deprotonate of carboxylic acid side groups. The ICs formation of a channel-type crystalline structure induced gelation mechanism was verified by various techniques. In vitro cytotoxicity assays demonstrated that the supramolecular hydrogels are nontoxic and cytocompatible.
基金financially supported by the National Natural Science Foundation of China (Nos. 51404031 and U1608254)
文摘Accumulation of toxic ions in leachate is one factor limiting bioleaching applications. The effect of fluoride ions on the growth of bioleaching microorganisms has been extensively emphasized. In this study, HF is found to be the toxic form of fluoride that affects the bacterial activity under acidic conditions. The added aluminum could compete with H^+ to complex with F-, thus significantly decrease the concentration of HF and finally reduce the toxicity of fluoride to bacteria. When F^-/Al^(3+)concentration ratio is 0.5:1.0, Fe^(2+) oxidation rate could reach 0.167 g·L^(-1)·h^(-1), close to that of the biotic control group(0.195 g·L^(-1)·h^(-1)). The competitive complexation mechanism of fluoride by AlF_n^(3-n) results in stability constants of AlF_n^(3-n) complex(7.00) that are larger than those of HF(3.18). The F^-/Al^(3+) concentration ratio in the medium could affect the speciation of AlF_n^(3-n) complex.With the decrease in F^-/Al^(3+) concentration ratio, the coordination numbers of AlF_n^(3-n) decrease. Finally, the feasibility of fluoride detoxification by aluminum ion is verified. This work has meaningful implications for fluoride-containing bacterial bioleaching systems.
基金This work was supported by the National Natural Science Foundation of China(Nos.21777087,21876099 and 21477065)the Fundamental Research Fund of Shandong University(No.2018JC015).
文摘Catechol pollutants(CATPs)serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes.Little information is available on the effects of complexation of metal ions on CATPs degradation.This work presents a systematical study of·OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes(AOPs).Results show that the pH-dependent complexation of metal ions(Zn^(2+),Cu^(2+),Ti^(4+)and Fe^(3+))promotes the deprotonation of catechol under neutral and even acidic conditions.The radical adduct formation(RAF)reactions are both thermodynamically and kinetically favorable for all dissociation and complexa-tion species,and-OH/-O-group-containing C positions are more vulnerable to·OH attack.The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation.At pH 7,the apparent rate constant(k_(app))values for different systems follow the order of catechol+Ti^(4+)≈catechol+Zn^(2+)>catechol+Cu^(2+)>catechol+Fe^(3+)>catechol.The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs.The toxicity assessment indicates that the·OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.
文摘The layer by layer complexation technique of polymer and metal ion was successfully utilized to fabricate the ultrathin multilayer film of poly(3 thiophene acetic acid (PTAA) and Tb 3+ ion by dipping the substrates alternatively in polymer and Tb 3+ ion aqueous solutions. UV-vis measurement revealed that the absorbance has linearity with the bilayer number from layer to layer and the X ray photoelectron spectrum (XPS) confirmed the existence of Tb 3+ ion. The pH of both the polymer and TbCl 3 solutions influence the thickness dramatically while the concentration of the solutions is not so sensitive. The luminescent spectrum of the complex film shows the characteristic emission of Tb 3+ ion as well as the ligand indicating the formation of the complex.
文摘An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C_2H_4 on MX(M=Ag, Cu; X=F, Cl). The calculated results show the following order of adsorption strength: F ->Cl - for anions; Cu +>Ag + for cations. The results can be explained by the detailed analysis of atomic charge, orbital energy and orbital population by using the natural bond orbital(NBO) theory: (1) anions with stronger electronegativity can attract more electrons from the s orbital of M, while at the same time it does not obviously weaken the d orbital occupation of M, thus the nearly vacant s orbital and the sufficiently filled d orbitals of M help with forming σ-donation and d-π * backdonation with the π orbital and the π * orbital of olefin, respectively; (2) a smaller energy gap of symmetry-adapted orbitals between olefin and a cation can favor the electron transfer, that is why Cu + forms stronger adsorption with olefin than Ag + does.
文摘The complexation capacity for heavy metals (Cu, Cd, Pb) were determined by anodic stripping voltammetry in South China Sea, Hulun Lake and Wuliang Suhai. The conditional stability constants and complexation capacity index were calculated. The data showed that the complexation capacity of the Hulun Lake was greater than that of seawater and Wuliang Suhai. The sequence of complexation capacity is C (CuL)> C (CdL)> C (PbL), the values are in concord with results of analysis on dissolved organic carbon. The conditional stability constants were in an opposite sequence: K (CuL)< K (CdL)< K (PbL). When log K are similar, the greater the complexation capacity, the greater the complexation capacity index.
