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.

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 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.

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.

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.

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)

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.

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。

Mesoporous silica SBA-15 functionalized with phosphonate and amino groups for uranium uptake

Mesoporous silicas have a very attractive ability of sorption and enrichment of metal ions due to their huge surface area and facile functionalization by organic ligands. In this work, phosphonate-amino hifunctionalized mesoporous silica SBA-15 （PA-SBA-15） as U（VI） sorbent was fabricated through post-grafting method. The obtained mesoporous silica was character- ized by SEM, XRD, NMR and nitrogen sorption/desorption experiments, which revealed the existence of ordered mesoporous structure with uniform pore diameter and large surface area. The adsorptivity of PA-SBA-15 for U（VI） from aqueous solution was investigated using batch sorption technique under different experimental conditions. The preliminary results show that the U（VI） sorption by PA-SBA-15 is very quick with equilibrium time of less than 1 h, and the U（VI） uptake is as large as 373 mg/g at pH 5.5 under 95℃. The sorption isotherm has been successfully modeled by the Langmuir isotherm, suggesting a monolayer homogeneous sorption of U（VI） in PA-SBA-15. The sorption is pH-dependent due to the pH-dependent charge of sorbent in the aqueous solution. The thermodynamics research shows that the sorption is a feasible and endothermic process. Based on these results, PA-SBA-15 could be a promising solid phase sorbent for highly-efficient removal of U（VI） ions from waste water and enrichment of U（VI） from a solution at a very low level.

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。

含氨基酸结构的磺酰胺衍生物合成与生物活性

采用分子杂交策略设计合成了15个氨基酸结构的磺酰胺衍生物,对其进行了抗菌活性评价。首先,苯磺酰氯与氨基酸反应制得了苯磺酰氨基酸(中间体Ⅰ);然后,以芳香醛、亚磷酸酯、乙酸铵和三氟甲磺酸铝为原料,一锅法制得了α-氨基膦酸酯(中间体Ⅱ);最后,中间体Ⅰ与Ⅱ缩合制得目标物。经^(1)HNMR、^(13)CNMR和MS确认结构。结果表明,该类化合物对大肠杆菌(E.coli)和耐氟喹诺酮大肠杆菌(FREC)活性最为显著。其中,化合物Ⅲb[{(2-氟苯基)[2-(苯基磺酰氨基)苯丙酰氨基]甲基}膦酸二乙酯]、Ⅲc[{(4-氟苯基)[2-(苯基磺酰氨基)苯丙酰氨基]甲基}膦酸二乙酯]、Ⅲh[{(2-氟苯基)[2-(苯基磺酰氨基)异戊酰氨基]甲基}膦酸二乙酯]和Ⅲm[{(苯基)[2-(苯基磺酰氨基)乙酰氨基]甲基}膦酸二乙酯]对E.coli的最小抑菌质量浓度(MIC)均为16μg/L,化合物Ⅲn[{(2-氟苯基)[2-(苯基磺酰氨基)乙酰氨基]甲基}膦酸二乙酯]对E.coli的MIC为8μg/L,抗菌活性不低于对照药苯唑西林;化合物Ⅲb、Ⅲh、Ⅲm和Ⅲn对FREC的MIC分别为32、32、32和16μg/L,优于对照药苯唑西林和诺氟沙星。

Design,synthesis and in vitro evaluation of mono(2,2,2-trifluoroethyl)esters,mono L-amino acid ester prodrugs of acyclic nucleoside phosphonates as anti-HBV agents

A series of novel mono（2,2,2-trifluoroethyl） esters,mono L-amino acid ester prodrugs of acyclic nucleoside phosphonates was synthesized and their in vitro anti-HBVactivity was evaluated in HepG 2 2.2.15 cells.Compound 1d exhibited more potent anti-HBV activity and lower cytotoxicity than those of adefovir dipivoxil and alamifovir（MCC-478） with EC_（50） and CC_（50） values of 0.01μmol/L and 8000μmol/L respectively.

A Highly Efficient Catalyst FeCl3 in the Synthesis of α-Amino Phosphonates via Three-component Reactions

Three-component reactions of aldehydes, amines, and diethyl phosphite catalyzed by FeCl3 in EtOH or under solvent-free and mild conditions afforded the corresponding α-amino phosphonates in excellent yields.

Synthesis of N-(alkoxycarbonyl or alkoxycarbonyl-methyl-alkoxyphosphonyl)-α-amino-O,O-diphenyl phosphonates and their bioactivities

<正> With phosphoric formic acid (PFA) and its analog,phosphonoacetic acid (PAA),as the lead compounds,α-amino phosphonates were introduced into PFA and PAA.The derivatives oi N-( alkoxycarbonyl-aikoxyphosphonyl)-α-arnino phosphonates (Ⅰ) and N-(alkoxycarbonyl-methyt-alkoxyphosphonyl)-α-amino phosphonates (Ⅱ) with the N-terminal of amino phosphonates bonding to phosphorus atom of PFA and PAA were synthesized via the reaction of the corresponding phosphonyl chloride with a-amino phosphonates in the presence of a base.The 31P NMK spectra of Ⅰ and Ⅱwere determined.It is found that the coupling constants 3Jpp with R3 being alkyl group were lower than those with R3 being (substituted) phenyl,and this result was discussed.The preliminary bioassay showed that some of the compounds Ⅰ and Ⅱhave better activities against tobacco mosaic virus (TMV).The inhibitory was higher than that of DHT (2,4-dioxyhexahydro-1,3,5-triazine).In addition,some of the compounds showed the activity against cancer cells.

ATMP对晶圆中TSV结构Ta基阻挡层的Ta和Cu去除速率选择比的影响

为了提高晶圆中硅通孔(TSV)阻挡层材料化学机械抛光(CMP)中Ta和Cu的去除速率选择比,在工作压力为3 psi(1 psi=6895 Pa)、抛光头转速为87 r/min、抛光盘转速为93 r/min、抛光液体积流量为300 m L/min的条件下,研究了氨基三甲叉膦酸(ATMP)作为络合剂对Ta和Cu的去除速率以及去除速率选择比的影响。通过电化学方法探究了ATMP对Ta和Cu的络合机制,利用原子力显微镜对比了抛光前后的表面质量。研究结果显示:在ATMP质量分数为1.5%时,Ta和Cu的去除速率分别为157.96和58.6 nm/min,验证了ATMP对提高Ta和Cu的去除速率选择比具有明显效果,Ta和Cu抛光前后的表面粗糙度分别由4.2 nm降低至0.284 nm以及由1.31 nm降低至0.51 nm,表面质量得到明显改善,证明了ATMP适合用于TSV晶圆阻挡层材料抛光。

氨基膦酸树脂对铅的吸附性能及机理

研究了Pb2 + 在氨基膦酸树脂上的吸附行为 ,结果表明 :树脂的静态饱和吸附容量为 82 2mg/ g ;用 0 .5mol/L的HCl和 0 .2～ 0 .3mol/L的EDTA洗脱 ,洗脱率分别为 97%和 99%以上。测得吸附热力学参数分别为 :ΔH =9.0 4kJ/mol,ΔG =- 3.99kJ/mol,ΔS =43.7J/ (mol·K)。等温吸附服从Freundlich经验式 ;表观活化能Ea=13.8kJ/mol;表观速率常数k2 98=2 .2 8× 10 -5s-1;树脂功能基与Pb2 + 的配位比为 2∶3。用化学和红外光谱的方法探讨了树脂对Pb2 + 的吸附机理。