Studies on Adsorption Behavior and Mechanism of Copper(Ⅱ) onto Amino Methylene Phosphonic Acid Resin

The adsorption behavior and the mechanism of a novel chelate resin, amino methylene phosphonic acid resin(APAR) for Cu(Ⅱ) were investigated. Cu(Ⅱ) was quantitatively adsorbed by APAR in the medium of pH=4 09. The statically saturated adsorption capacity is 181 mg/(g resin). Cu(Ⅱ) adsorbed on APAR can be eluted by 1 0-3 0 mol/L HCl. The rate constant is k 298 =5 58×10 -5 s -1 . The adsorption of Cu(Ⅱ) on APAR follows the Freundlich isotherm. The Δ H of the adsorption is 3 91 kJ/mol. The apparent activation energy is E a=21 4 kJ/mol. The coordination molar ratio of APAR to Cu(Ⅱ) is 1/1. It is shown that the nitrogen and the oxygen atoms in the functional group of APAR coordinate to Cu(Ⅱ).

Sorption Behavior and Mechanism of Indium(Ⅲ) onto Amino Methylene Phosphonic Acid Resin

The sorption behavior of amino methylene phosphonic acid resin (APAR) for In (Ⅲ ) was investigated . Experimental results show that In ( Ⅲ ) adsorbed on APAR can be elated with 2mol · L -1 HCl. The apparent rate constant is k29 = 1.50 × 10-5s-1. The sorption behavior of APAR for In ( Ⅲ ) obeys the Freundlich isotherm. The themodynamic parameters of sorption, enthalpy change ()H, free energy change ()G and entropy change ()S of sorption (APAR) for In ( Ⅲ ) are 24.1 kJ·mol-1, -35. 1kJ· mol-1 and 200J· mol-1·K-1 respectively. The coordination molar ratio of the functional group of APAR to In( Ⅲ ) is 2:1. The sorption mechanism of APAR for In( Ⅲ ) was examined by IR spectrometry.

Adsorption behavior and mechanism of amino methylene phosphonic acid resin for Ag(Ⅰ)

The sorption properties of amino methylene phosphonic resin(APAR) for Ag(Ⅰ) were studied. The amino methylene phosphonic acid resin(APAR) has a good adsorption ability for Ag(Ⅰ) at pH=6.0 in the HAc-NaAc medium. The statically saturated adsorption capacity is 272 mg/g resin, Ag(Ⅰ) adsorbed on APAR can be eluted by 5% (NH2)2CS-0.5 mol/L hydrochloric acid quantitatively. The adsorption rate constants determined under various temperatures are k15℃=3.89×10?5 s?1, k25℃=5.93×10?5 s?1, k35℃=7.59×10?5 s?1, k45℃=9.45×10?5 s?1, respectively. The apparent activation energy of adsorption, Ea is 22.8 kJ/mol, the enthalpy change (?H) of sorption is 17.4 kJ/mol. The adsorption mechanism shows that the functional group of APAR coordinates with Ag(Ⅰ) to form coordination bond, the coordination molar ratio of the functional group of APAR to Ag(Ⅰ) is 1∶1.

Studies on the Adsorption of Amino Methylene Phosphonic Acid Resin for Holmium(Ⅲ)

The adsorption behavior and mechanism of a novel chelate resin, amino methylene phosphonic acid resin (APAR) for Ho(Ⅲ) were investigated. The statically saturated adsorption capacity is 258 mg·g^(-1) resin at 298 K in HAc-NaAc medium. The Ho(Ⅲ) adsorbed on APAR can be repeatedly eluted by 3.0 mol·L^(-1) HCl and the elution percentage is as high as 95.8%. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k_(298)=1.14×10^(-5) s^(-1). The adsorption behavior of APAR for Ho(Ⅲ) obeys the Freundlich isotherm. The thermodynamic adsorption parameter, enthalpy change ΔH of APAR for Ho(Ⅲ) is 11.4 kJ·mol^(-1). The apparent activation energy is E_a=15.8 kJ·mol^(-1). The molar coordination ratio of the functional group of APAR to Ho(Ⅲ) is about 2∶1. The adsorption mechanism of APAR for Ho(Ⅲ) was examined by using chemical method and IR spectrometry.

SORPTION BEHAVIOR AND MECHANISM OF SAMARIUM(III) ON AMINO METHYLENE PHOSPHONIC ACID RESIN

Sm(III) was quantitatively adsorbed by amino methylene phosphonic acid resin (APAR) in the medium of pH=5.0. The statically saturated sorption capacity is 251mg/g·resin. Sm(III) adsorbed on APAR can be reductively eluted by 2.0mol/L HCl. The sorption rate constant is k298= 1.35×10-5s-1. The sorption behavior of APAR for Sm(III) obeys the Freundlich isotherm. The enthalpy change △H of sorption is 24.9kJ/mol. The apparent activation energy is Ea=11.7kJ/mol. The sorption mechanism shows that the nitrogen and oxygen atoms of the functional group of APAR coordinated with Sm(III) to form coordination bond.

Structural investigation of the zirconium-titanium based amino trimethylene phosphonate hybrid coating on aluminum alloy

A zirconium-titanium based amino trimethylene phosphonate hybrid coating on AA6061 aluminum alloys was formed by dipping in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid （ATMP） solution for improving the lacquer adhesion and corrosion resistance as a substitute of chromate coatings. The morphology and structure of the hybrid coating were studied by means of scanning electron microscopy （SEM） and atomic force microscopy （AFM）. The surface composition and structure characteristics were also investigated by means of X-ray photoelectron spectroscopy （XPS） and Fourier transformation infra-red spectroscopy （FTIR）. The results of SEM and AFM show that the hybrid coating present piece particle distribution which is much denser than that of the zirconium-titanium coating. The results of XPS and FTIR indicate that the hybrid coating is a hybrid composite structure composed of both the zirconium-titanium and amino trimethylene phosphonate coatings.

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.

Synthesis of N-methylene phosphonic chitosan(NMPCS)and its potential as gene carder

N-Methylene phosphonic chitosan （NMPCS）, an amphiphilic macromolecule with powerful chelating ability of Ca^2＋ ions, was synthesized and characterized. The physicochernical properties of NMPCS and the interactions between NMPCS and plasmid DNA were investigated by FTIR, ^13C NMR, X-ray, agarose gel electrophoresis retardation assay, atomic force microscopy （AFM） and circular dichroism （CD）. The results suggest that at charge ratio 2：1 or above, DNA could be completely entrapped and spherical complexes with mean size of 80-210 nm were formed. Taking HeLa as host cell, luciferase expression mediated by NMPCS improved about 100 times compared to the expression mediated by chitosan.

Design, synthesis and in vitro evaluation of L-amino acid esters prodrugs of acyclic nucleoside phosphonates as anti-HBV agent

A series of novel L-amino acid esters prodrugs of acyclic nucleoside phosphonates was synthesized and their anti-HBV activity was evaluated in HepG2 2.2.15 cells. Compound 1d exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil with EC50 and CC50 values of 0.207 μmol/L and 2530 μmol/L, respectively.

Iodine-catalyzed Synthesis of α-Amino Phosphonates

Iodine was found to be an efficient catalyst for the one pot synthesis of α-amino phosphonate from aldehydes, anilines and diethyl phosphite. The influences of the iodine loading, reaction solvent, the structure of aldehyde and aniline on the reaction were studied.

Preparation of a Novel Calcium Phosphate Cement Using N-methylene Phosphonic Chitosan as a Gelling Agent

A modified chitosan （ N-methylene phosphonic Chitosan, NMPC） was synthesized to improve solubility and ability to bind calcium ion. The properties of the raw material chitosan and its derivative NMPC were characterised using FTIR , ^1H- NMR . The aim of this study was to enhance the compressive CPC by reinforcing with NMPC. A formulation consisting of CPC powder , buffer solution and gelling agent was used for preparation of the CPC. CPC powder coasisted of tetracalcium phosphate（ TTCP ） and dicalcium phosphate anhydrous （ DCPA ）. NMPC which acted as the gelling ageut was dissohed into KH2PO4-Na2 HPO4 buffer solution. Each specimen in the mold was sandciched between two fritted glass sides and kept for 24 hours. Compressive strengths were determined, the setting product was identified using X-ray diffraction and scanning electron microscopy was used to investigate the hydroxyapatite particles size and porosity. The experimental results showed that the dominating influence on the compressive strengths of CPC-AMPC was the HA panicle size, its uniformity and appropriate porosity.

Swelling Properties of New Hydrogels Based on the Dimethyl Amino Ethyl Acrylate Methyl Chloride Quaternary Salt with Acrylic Acid and 2-Methylene Butane-1,4-Dioic Acid Monomers in Aqueous Solutions

Hydrogels of dimethylaminoethyl acrylate methyl chloride quaternary salt (Q9) have been synthesized with different monomer ratio by copolymerization of this poorly studied monomer either with acrylic acid or with 2-methylene bu-tane-1,4-dioic acid. Hydrogel swelling was measured as a function of the composition of the hydrogel and of the crosslinking agent ratio. High values of swelling have been obtained at very high crosslinking values (【14 wt %) and the equilibrium swelling was reached at very low time (less than 15 minutes). The swelling isotherms consisted of a steep initial portion and then levelled off as asymptotically to the equilibrium swelling limit. The experimental data suggest clearly that the swelling process obeys second-order kinetics. According to this, the kinetics rate constant and the equilibrium water content were determined at different comonomer composition and crosslinker concentration. The calculated kinetic constants ranged from 0.48 to 3.76 ×10-2 min-1 for poly (acrylic acid-co-Q9) hydrogels and from 0.68 to 4.0 ×10-2 min-1 for poly (2-methylene butane-1,4-dioic acid-co-Q9) hydrogels depending on the hydrogels composition. The diffusion process was evaluated for each hydrogel showing a non-Fickian type diffusion. In all cases was observed a considerable increase in diffusion coefficient as Q9 content increases.

Novel Phosphonoacetic Acid Derivatives.Synthesis of N-(Ethoxycarbonylmethylphosphonyl)-α-Amino Esters and-α-Amino Phosphonic Acid Esters and Their Bioactivities

A series of novel phosphonoacetic acid derivatives, N-(ethoxycarbonylmethy-ethoxyphosphonyl)-α-amino acid esters and α-amino phosphonates, were synthesized via the reaction of the corresponding phosphonyl chloride with amino acid ester hydrochlorides or amino phosphonates in the presence of a base. The preliminary bioassay shows that some compounds show significant anti-viral activity against tobacco mosaic virus (TMV)

Synthesis of New Germanium Compounds Containing α-Amino AcidEster or α-Phosphonate Groups

A series of new type of germasesquioxides. germatranes, and β-trichlorogermylpropionic acid derivatives containing a-tmino group or a-aminophosphonyl group were synthesized by a convenient condensation reaction of β-trichlorogermyl propionyl chloride with a-amino acid esters or a-phosphonates in the presense of organic base. The mectures of products were detethened by 1HNMR 31PNMR MS, elemental analysis' and X-ray diffraction.

DTPMP在萤石和方解石浮选分离中的应用及机理

萤石(CaF_(2))是一种关键战略性矿产资源,在自然界中常与同为含钙矿物的方解石(CaCO_(3))共生。泡沫浮选是分离这两种含钙矿物最主要的方法,但萤石和方解石表面的钙活性位点相似,导致其选择性分离一直是世界性难题。萤石浮选中常用水玻璃抑制方解石,实现萤石正浮选富集。然而,水玻璃选择性低且用量大,导致部分萤石被抑制无法回收,且因其分散性好会造成尾矿难以沉降、尾水难以处理等问题。本文提出了抑制萤石浮选方解石的反浮选思路,并开发了一种绿色萤石抑制剂—二乙烯三胺五甲叉膦酸(DTPMP)。单矿物、二元混合矿及实际矿浮选试验表明,在中性pH下,以油酸钠(NaOL)作捕收剂、低用量的DTPMP作抑制剂,可实现萤石的反浮选分离。药剂吸附量检测和傅里叶变换红外光谱(FTIR)表明,DTPMP在萤石表面的吸附量更多、吸附强度更大。密度泛函理论(DFT)计算结果表明,DTPMP更容易在萤石表面吸附,且DTPMP膦酸基团中的H原子与萤石表面的F原子生成的氢键作用较强。因此,DTPMP作为一种绿色高效的抑制剂,在萤石浮选领域具有较好的工业应用前景。

氨基三亚甲基膦酸的电化学高级氧化降解

为探索电化学高级氧化法对ATMP的降解效能,利用板框式电化学高级氧化装置,考察了溶液流速、温度、pH值、电流密度及Na_(2)SO_(4)浓度等关键参数对ATMP降解效果的影响;利用电子顺磁共振测试、自由基猝灭实验和ATMP降解动力学探讨了ATMP的降解机制.结果表明,溶液流速为450mL/min,温度为30℃,pH值为9,电流密度为300A/m^(2),电解质Na_(2)SO_(4)浓度为0.10mol/L时,ATMP的降解率最高,80min内可达99.7%,电化学高级氧化技术(EAOPs)能够有效降解ATMP;操作条件中电流密度、溶液流速和温度均影响ATMP降解率,但温度改变需要的能耗较高,而溶液流速对降解率影响较小,仅电流密度改变具有能耗小且对ATMP降解率影响显著的优点,因此本体系适合以电流密度作为反应的核心控制参数;研究采用的EAOPs体系产生的⋅OH(羟基自由基)和SO_(4)^(-)⋅(硫酸根自由基)均参与降解ATMP,反应速率常数分别为k_(•OH,ATMP)=(7.50±0.05)×10^(8)L/(mol·s)和k_(SO_(4)^(-)•,ATMPP)=(5.63±1.20)×10^(7)L/(mol·s),⋅OH在降解ATMP的过程中起主要作用.

新型有机抑制剂对萤石和方解石浮选分离的影响及作用机理

萤石与方解石具有类似的表面性质,即相同的活性钙质点,导致2种矿物在浮选过程中的分离十分困难。首次提出采用环保型水溶性膦酸盐乙二胺四亚甲基膦酸钠(EDTMPS)作抑制剂强化萤石与方解石的浮选分离,并开展了相关的浮选试验。研究结果表明,在矿浆pH值为7~9的条件下,EDTMPS可有效抑制方解石的上浮,而对萤石的浮选行为影响较小,人工混合矿浮选试验验证了采用EDTMPS作为抑制剂可实现方解石与萤石的分离。对EDTMPS抑制剂实现方解石与萤石分离的机理进行了研究分析,发现EDTMPS分子结构中的膦酸根离子与方解石表面的钙离子发生化学吸附,阻碍了油酸根离子的进一步吸附,相比较而言,EDTMPS在萤石表面的吸附极小,对其可浮性的影响很小。EDTMPS抑制剂可选择性抑制方解石,在方解石与萤石的浮选分离中具有广泛的应用前景。

LA-ICP-MS测定单颗粒氨基膦酸螯合树脂中的铀分布

以利用氨基膦酸螯合树脂从湿法磷酸(WPA)中回收铀为研究背景,对单颗粒氨基膦酸螯合树脂中铀分布进行研究,得到以下结论:确定激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)最佳的激光频率为6 Hz、束斑直径为44μm、能量密度为6 J/cm^(2)。选择吸附饱和的树脂和洗脱完全的树脂分别作为吸附和淋洗过程的外标,对其进行均匀性测试,吸附饱和树脂中铀含量的相对标准偏差为3.87%(n=9),洗脱完全树脂中铀含量的相对标准偏差为3.52%(n=9),均一性良好。利用LA-ICP-MS对氨基膦酸螯合树脂中的铀进行原位微区分析,结果表明:铀在树脂上的吸附过程是由外向内逐渐完成,淋洗过程是由外向内逐渐完成,树脂内外铀浓度逐渐均匀统一,最终达到吸附饱和和淋洗完全。

胆固醇修饰的氨基酸类有机凝胶因子去除水中亚甲基蓝的研究

设计合成了胆固醇修饰的氨基酸类有机凝胶因子CH-1和CH-2,并对其去除水中的亚甲基蓝进行了系统地研究.结果表明,CH-2粉末能够去除水中的亚甲基蓝,CH-1与低毒的苯甲醇形成的凝胶也可以快速去除水中的亚甲基蓝.

氨基三亚甲基膦酸对氟磷灰石和白云石选择性抑制机理研究

钙镁质磷矿反浮选过程中,氟磷灰石的选择性抑制是实现高效浮选分离的前提。通过单矿物浮选试验、FTIR分析、XPS测试、Zeta电位测试和气泡-颗粒黏附动力学(BPWA)测试等手段,研究了氨基三亚甲基膦酸(ATMP)对氟磷灰石和白云石浮选行为的影响及其选择性抑制机理,结果表明:ATMP会抑制氟磷灰石上浮,但对白云石的抑制作用有限;ATMP在氟磷灰石表面的吸附作用大于白云石,更倾向于选择吸附在氟磷灰石表面;ATMP主要与氟磷灰石表面的Ca原子作用,表现为化学吸附,占据Ca位点后降低了油酸钠(NaOL)的吸附作用,导致氟磷灰石被抑制,可浮性降低。