Surface grafting density analysis of high anti-clotting PU-Si-g-P(MPC) films

Well-defined zwitterionic polymer brushes with good blood compatibility were studied, grafted from polyurethane (PU) substrate (PU-Si-g-P(MPC)) by surface-initiated reverse atom transfer radical polymerization (SI-RATRP). We found that the structure of polymer brushes and hence their properties greatly depend on the grafting density. To solve the problems of the normal method for grafting density measurement, i.e., more requirements for qualified and proficient instrument operator, we established an effective and feasible way instead of the conventional method of spectroscopic ellipsometer combined with gel permeation chromatograph (ELM/GPC) to calculate the grafting density of PU-Si-g-P(MPC) films by using a software named ImageJ 1.44e in combination with scanning electronic microscope (SEM) or atomic microscope (AFM). X-ray photoelectron spectroscopy (XPS), SEM and AFM were employed to analyze the surface topography and changes of elements before and after graft modification of the synthetic PU-Si-g-P(MPC) biofilms.     

新显色试剂1-(4-磺基苯)-3-(2-吡啶)-三氮烯的合成及其与镉(Ⅱ)的显色反应

合成了一种新三氮烯类显色剂1-(4-磺基苯)-3-(2-吡啶)-三氮烯(简称SPPT),并研究了在Triton X-100存在下,于pH为9.18的Na2B4O7-NaOH缓冲溶液中与镉的显色反应.结果表明,试剂与镉生成橙红色配合物.方法用于废水中微量镉的测定,结果令人满意.     

1-(4-硝基苯)-3-(2-吡嗪)-三氮烯的合成及与锌(Ⅱ)的显色反应

报道了1-（4-硝基苯）-3-（2-吡嗪）-三氮烯（NPPT）的合成及与锌（Ⅱ）的显色反应。在非离子表面活性剂TritonX-100存在下,于pH8.8的KCl,H3BO3-NaOH缓冲介质中,NPPT与锌（Ⅱ）形成4∶1的黄棕色络合物,在465nm处有一最大吸收,表观摩尔吸光系数为3.15×104L·mol-1.cm-1,10mL溶液中,锌（Ⅱ）量在0—0.56μg范围内符合比尔定律。方法用于葡萄糖酸锌口服溶液中微量锌的测定,测定结果与AAS法相符。     

1-(8-喹啉)-3-(2-苯并噻唑)三氮烯(QBTT)分光光度法测定微量钯(Ⅱ)

研究了新显色剂 1 - (8-喹啉 ) - 3- (2 -苯并噻唑 )三氮烯 (QBTT)分光光度法测定 Pd( )的条件。在 p H1 1 .0的 Na2 B4O7- Na OH缓冲介质 ,该试剂与 Pd( )形成摩尔比为 2∶ 1的绿色稳定络合物。其最大吸收波长在 6 40 nm处 ,表观摩尔吸光系数 ε为 7.85× 1 0 4L·mol-1 ·cm-1 ,Pd( )的浓度在 0— 1 .2 μg/ m L范围内符合朗伯 -比尔定律。对 30多种共存离子的影响实结果表明 ,大多数常见离子不干扰测定。方法具有较好的选择性 ,用其直接测定催化剂样品中的微量钯 ,结果满意     

(E)-3-(4一羟苯基)-1-(哌啶-1-基)丙-2-烯-1-酮衍生物核磁共振特征与构象分析

设计并合成了一系列(E)-3-(4-羟苯基)-1-(哌啶-1-基)丙-2-烯-1-酮衍生物. 通过一维和二维核磁共振实验完成了¹H和¹³C信号的指认. 通过ROESY、变温实验和分子模拟技术对这类化合物的构象进行了分析.     

1-(6-羟基-2-嘌呤基)-3-[4-(苯基偶氮)苯基]- 三氮烯分光光度法测定微量镍

在pH=10.97的NaB4O7-NaOH缓冲溶液中,表面活性剂Tween-80存在下,1-(6-羟基-2-嘌呤基)-3-[4-(苯基偶氮)苯基]-三氮烯(HPAPT)与镍的显色反应,形成一种稳定的1∶2红色配合物,其最大吸收波长位于540nm,表观摩尔吸光系数ε540＝2.06×105L·mol-1·cm-1,Ni(Ⅱ)在0-15μg/25mL范围内符合比耳定律.结合萃取分离,应用于人发、大米和油菜中镍的测定,结果令人满意.     

二阶导数分光光度法测定微量锌

研究了在Tritonx-100体系中，以1-（2-吡啶偶氮）-2-萘酚（PAN）为显色剂，在PH8.7条件下，先用柠檬酸钠掩蔽大部分的铁，然后用二阶导数分光光度法消除残存的铁、铜、锰、钴的干扰，从而测定含铁络合物中微量锌。方法精密度和准确度均为满意。     

4-氟苯甲醛酪氨酸席夫碱的制备及其振动光谱的密度泛函理论和从头算理论计算的研究

4-氟苯甲醛酪氨酸席夫碱(4-FT)由4-氟苯甲醛和L-酪氨酸钾盐在室温条件下反应制得,4-FT的结构通过1HNMR,FTIR和Raman测试得到确认。分别用密度泛函(DFT,density functional theory)理论的B3LYP(Becke’s three-parameter exchange functional(B3)with Lee,Yang,Parr(LYP))方法和从头算(ab initio)理论的HF(Hartree-Fock)方法,选用标准的6-31G**和6-31G*基组对化合物4-FT的几何构型进行优化。同时分别在B3LYP/6-31G**,B3LYP/6-31G*,HF/6-31G**和HF/6-31G*水平下计算4-FT的振动波数。用密度泛函(DFT)的B3LYP方法计算并校正后的波长数据比用从头算(ab i-nitio)的HF方法计算的结果更与实验数据吻合。     

1-(6-硝基-2-苯并噻唑)-3-(4-硝基苯)-三氮烯与铜显色反应的研究及应用

在TritonX-100表面活性剂存在下,pH为10.0-11.0的Na2B4O7-NaOH缓冲溶液中,1-(6-硝基-2-苯并噻唑)-3-(4-硝基苯)-三氮烯(NBTNPT)与铜生成2:1配合物。配合物的最大负吸收峰是540nm,表观摩尔吸光系数为1.15×105L·mol-1·cm-1。Cu2 的质量浓度在0-360μg/L符合比耳定律。测定铝合金样品中的微量铜,结果满意。     

胶束增敏导数分光光度法测定微量铜

本文研究了在非离子型胶束Ｔｒｉｔｏｎ Ｘ－１００体系中，以１（２－吡啶偶氮）２－萘酚为显色剂，用二阶导数分光光度法消除镉的干扰，与乙醇介质比较，测定灵敏度提高，测定镉样中微量铜，结果较为满意。     

Fabrication and characterization of superparamagnetic and thermoresponsive hydrogels based on oleic-acid-coated Fe3O4 nanoparticles, hexa(ethylene glycol) methyl ether methacrylate and 2-(acetoacetoxy)ethyl methacrylate

Stimuli-responsive hydrogel nanocomposites comprised of swollen polymer networks, in which magnetic nanoparticles are embedded, are a relatively new class of “smart” soft materials presenting a significant impact on various technological and biomedical applications. A novel approach for the fabrication of hydrogel nanocomposites exhibiting temperature- and magneto-responsive behavior involves the random copolymerization of hexa(ethylene glycol) methyl ether methacrylate (HEGMA, hydrophilic, thermoresponsive) and 2-(acetoacetoxy)ethyl methacrylate (AEMA, hydrophobic, metal-chelating) in the presence of preformed oleic-acid-coated magnetite nanoparticles (OA·Fe₃O₄). In total, two series of hydrogel nanocomposites have been prepared in two different solvent systems: ethyl acetate (series A) and tetrahydrofuran (series B). The degrees of swelling (DSs) of all conetworks were determined in organic and in aqueous media. The nanocrystalline phase adopted by the embedded magnetic nanoparticles was investigated by X-ray diffraction (XRD) spectroscopy. The obtained diffraction patterns indicated the presence of magnetite (Fe₃O₄). Deswelling kinetic studies that were carried out at ∼60 °C in water demonstrated the thermoresponsive properties of the hydrogel nanocomposites, attributed to the presence of the hexaethylene glycol side chains within the conetworks. Moreover, thermal gravimetric analysis (TGA) measurements showed that these materials exhibited superior thermal stability compared to the pristine hydrogels. Further to the characterization of compositional and thermal properties, the assessment of magnetic characteristics by vibrational sample magnetometry (VSM) disclosed superparamagnetic behavior. The tunable superparamagnetic behavior exhibited by these materials depending on the amount of magnetic nanoparticles incorporated within the networks combined with their thermoresponsive properties may allow for their future exploitation in the biomedical field.     

Si(001)-(2*2*1):H表面O2吸附的密度泛函理论研究

建立了一种计算Si(001)-(2×2×1):H表面O2吸附的理论模型．在周期性边界条件下,采用基于密度泛函理论广义梯度近似的超软赝势法对Si(001)-(2×2×1):H表面O2吸附进行了第一性研究．通过占位能的计算,得到了Si(001)-(2×2×1):H表面O2的最佳吸附位置．计算结果表明吸附后的反应产物应为Si=O和H2O,从理论上支持了D．Kovalev等人提出反应机制．     

光谱法研究2-(4-二甲氨基苯基)-5-氟-6-吗啉-1-氢-苯并咪唑与小牛胸腺DNA的相互作用

研究了2-(4-二甲氨基苯基)-5-氟-6-吗啉-1-氢-苯并咪唑(1)在不同pH条件下的紫外-可见吸收光谱,采用非线性最小二乘法得出分子1的三级加质子常数lgβ₁, lgβ₂, lgβ₃分别为4.96±0.03, 5.72±0.07和7.95±0.10。当pH 3.40时,分子1主要以一价离子状态存在,紫外-可见吸收光谱及荧光光谱表明该条件下分子与小牛胸腺DNA存在明显的相互作用,并得出分子1与DNA的结合常数K_b为(2.30±0.10)×104 mol-1·L。当分子浓度为10-8～1.2×10-6 mol·L-1时,荧光强度随DNA含量的增加而线性增强,分子1是一种潜在的测定DNA的定量试剂。     

Spectroscopic Elucidation of the Coordination Ability of 2-Oxo-2H-Chromene-3-Phosphonic Acid with Pt(II)

The coordination ability of 2-oxo-2H-chromene-3-phosphonic acid with Pt(II) both in solution and in solid state is elucidated by means of conventional and linear-polarized IR spectroscopy of oriented colloid suspensions in nematic liquid crystal, ¹H-, ¹³C-, and ³¹P-NMR, UV-Vis spectroscopy, positive and negative mass spectrometry (ESI and FAB), and TGV and DSC methods. A comparison with the spectroscopic data of ammonium salt of 2-oxo-2H-chromene-3-phosphonic acid is carried out as well.     

2-(2-喹啉偶氮)-1,5-苯二酚分光光度法测定烟草样品中的钙

在 p H为 8.0的柠檬酸钠 -氢氧化钠缓冲介质中 ,Triton X- 10 0存在下 ,2 - (2喹啉偶氮 ) - 1,5苯二酚(QADHB)与钙反应生成 1∶ 1稳定配合物 ,λmax=5 5 5 nm,ε=4 .18× 10 4L· mol-1· cm-1。钙含量在 0 .1—2 5μg/ 2 5 m L的范围内符合比耳定律 ,方法用于烟草中钙含量的测定 ,结果令人满意。     

2(水杨醛缩苯胺)-(1,10-邻菲罗啉)合钙的光谱特性

合成了一种新型的蓝光发射材料2(水杨醛缩苯胺)-(1,10-邻菲罗啉)合钙,并利用红外光谱、X射线衍射谱、DSC热分析、UV-vis吸收谱、荧光激发光谱和荧光发射光谱研究了其结构、晶态、热稳定性以及光学特性,分析了它的能态结构和发光机理。结果表明,2(水杨醛缩苯胺)-(1,10-邻菲罗啉)合钙的热稳定性较高,是一种多晶粉末发光材料,禁带宽度2.93eV,在紫外光的激发下,固态荧光发射峰在449.7nm处,在乙醇溶液体系中的荧光发射峰在491nm处,均为蓝色荧光,色纯度高,荧光量子效率高,其荧光发射主要来源于长波吸收带,最大波长吸收带对荧光发射贡献最大。     

Surface modification of hydroxyapatite with poly(methyl methacrylate) via surface-initiated ATRP

This article describes the fabrication of hydroxyapatite (HAP) nanocomposites grafted with poly(methyl methacrylate) (PMMA). Surface-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was carried out from hydroxyapatite particles derivatized with ATRP initiators. The structure and properties of the nanocomposites were investigated by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), differential scanning calorimeter (DSC) measurements, and contact angle analyses. TGA was used to estimate the grafting density of ATRP initiators (0.49 initiator/nm²) and the amount of grafted PMMA on the HAP surface. The contact angle analyses indicated that grafting PMMA onto the HAP surface dramatically increased the hydrophobicity of the surface. Moreover, the HAP nanocomposites showed excellent dispersibility in both aqueous solution and organic solvent.     

1-(4-安替比林)-3-(8-喹啉)-三氮烯的合成及其分析应用

报道了新试剂1-(4-安替比林)-3-(8-喹啉)-三氮烯(APQT)的合成及其与镉(Ⅱ)的显色反应研究.在Triton X-100存在下,pH 10.5的Na2B4O7-NaOH的缓冲溶液中,试剂与镉(Ⅱ)形成2:1型的橙红色络合物,最大吸收波长为525nm,表观摩尔吸光系数为2.25×105L·mol-1·cm-1,镉含量在0-15μg/25mL范围内遵守比耳定律.     

2(8-羟基喹啉)-2(苯酚)合锆薄膜的制备与性能研究

设计合成了一种新型的有机电致发光材料2(8-羟基喹啉)-2(苯酚)合锆(Zr(OPh)₂q₂),制备了Zr(OPh)₂q₂薄膜,并利用红外光谱、差热-热重谱、扫描电镜、X射线衍射谱、UV吸收谱和荧光光谱等方法研究了其晶态、热稳定性、能带结构以及光致发光机理。结果表明,Zr(OPh)₂q₂的熔点为381.2 ℃,分解温度为467.1 ℃,具有非常高的热稳定性,利用真空热蒸镀方法很容易在经过净化处理的玻璃基底上形成高质量、无定形纳米级薄膜,在390 nm紫外光的激发下,Zr(OPh)₂q₂薄膜产生发光峰为525 nm、半峰宽度为107.6 nm的强黄绿色荧光,其粉体产生强黄色荧光,是一种性能优良的电致发光材料。     

4-[(E)-2-(3, 4-二甲氧基苯基)乙烯基]苯氧基乙酸乙酯的合成及其NMR研究

以对硝基甲苯、3, 4-二甲氧基苯甲醛为起始原料,经过缩合,还原,重氮化水解,亲核取代反应,最终合成了新的化合物4-[(E)-2-(3, 4-二甲氧基苯基)乙烯基]苯氧基乙酸乙酯,用¹H 和¹³C NMR及多种二维核磁共振谱确定了该化合物的结构,完成了¹H 和¹³C NMR的归属,给出了分子中各氢,碳原子的准确化学位移.