用于pH测定的光化学敏感膜

以二醋酸纤维素做基质采用包埋法将刚果红固定, 制备成一种平均厚度为5μm的光化学pH敏感膜(CCM)。利用紫外可见光谱仪探讨了pH响应性能。结果表明, 该膜对pH在2. 50 ~4. 76范围内的变化呈线性响应,其热力学常数pKa为3. 61±0. 03,响应时间在10s以内,同时也考察了该膜的重现性、稳定性以及电解质对该膜的光吸收性质的影响。     

以罗丹明B为指示剂的pH敏感膜

PVC敏感膜;以罗丹明B为指示剂的pH敏感膜     

键合法制备高亲水性光化学pH传感器敏感膜及性能研究

采用丙烯酰胺为偶合剂,以Fe2+/H2O2为引发剂,将邻甲酚红通过表面接枝聚合固定于交联聚乙烯醇膜表面,制备了一种可用于光化学pH传感器的pH敏感膜。性能测试表明,此膜具有pH响应范围宽(pH7.97～12.26)、响应时间快(<25s)、耐盐性好、可逆重复性及光和贮存稳定性良好,制备方法简单的优点。实验表明,此膜可用于光化学pH传感器。     

pH值与湿度的光纤传感器研究

本文采用溶胶凝胶法和包埋法分别将对pH值和湿度敏感的指示剂修饰在光纤纤芯表面,制成了具有较宽检测范围的光纤pH传感器和光纤湿度传感器。通过X射线能谱仪(EDX)对所制备的pH和湿度敏感膜的表面成分进行了分析,并采用光功率计对敏感膜进行了光学检测。结果表明:当pH值在4.5~13的范围内变化时,光输出功率与pH值近似呈线性变化规律;当相对湿度(RH)在25%~80%的范围内变化时,光输出功率与RH值近似呈线性变化规律,并且二者在其检测范围内均具有良好的可逆性。     

磷钼杂多酸-L-半胱氨酸自组装超分子pH敏感膜电位传感器

自组装超分子膜;pH电位传感器;磷钼杂多酸-L-半胱氨酸自组装超分子pH敏感膜电位传感器     

载银二氧化钛纳米管表面pH敏感膜构建及其抑菌特性

采用表面涂覆硅烷偶联剂KH550、两步光接枝、阳极氧化等方法,在钛表面成功制备出一种pH型敏感膜覆盖的载银二氧化钛（TiO₂）纳米管阵列。利用扫描电镜（SEM）、透射电镜（TEM）、能谱分析（EDS）、原子吸收光谱（AAS）对该pH敏感膜覆盖的载银TiO₂纳米管阵列理化性能进行了表征,采用抑菌环实验定性考察了样品的抗菌特性,并计算其抑菌率。结果表明,含银离子溶液在毛细管力作用下大量进入TiO₂纳米管中,并在pH型敏感膜的调控下,使银离子在不同pH环境下具备不同的释放行为,从而达到良好的控释效果;载银TiO₂纳米管的抑菌率与银离子负载量成正比,且抗菌性能持久。     

载银二氧化钛纳米管表面pH敏感膜构建及其抑菌特性

采用表面涂覆硅烷偶联剂KH550、两步光接枝、阳极氧化等方法,在钛表面成功制备出一种pH型敏感膜覆盖的载银二氧化钛(TiO2)纳米管阵列。利用扫描电镜(SEM)、透射电镜(TEM)、能谱分析(EDS)、原子吸收光谱(AAS)对该pH敏感膜覆盖的载银TiO2纳米管阵列理化性能进行了表征,采用抑菌环实验定性考察了样品的抗菌特性,并计算其抑菌率。结果表明,含银离子溶液在毛细管力作用下大量进入TiO2纳米管中,并在pH型敏感膜的调控下,使银离子在不同pH环境下具备不同的释放行为,从而达到良好的控释效果;载银TiO2纳米管的抑菌率与银离子负载量成正比,且抗菌性能持久。     

刚果红交联聚乙烯醇薄膜／K^＋交换玻璃光波导检测氯化氢气体

用环氧氯丙烷为交联剂合成了刚果红(CR)交联聚乙烯醇(PVA)CR-PVA敏感试剂.用匀胶机将其做成薄膜固定在钾离子交换玻璃光波导表面,研制出一种光波导氯化氢气体传感器.CR-PVA薄膜碱式结构的最大吸收波长在600 nm以下,对波长为632.8 nm的激光吸收很弱;薄膜与酸性气体发生反应后强烈吸收波长在632.8 nm附近的导波或消失波;检测输出光强度的变化,即能够测出酸性气体浓度.测试结果表明,本传感器对低浓度HCl气体有快速响应,且对1.6～192 mg/m3范围内有良好的线性响应;SO2、NO2气体的浓度大于18000 mg/m3时才有响应,而对于高、低浓度H2S气体均无响应.     

NiFe2O4对刚果红的光催化降解性能研究

采用水热法合成了尖晶石型NiFe₂O₄,并利用X射线粉末衍射仪对其物相进行了表征,利用紫外-可见分光光度计对其光催化降解刚果红的性能进行了研究。以刚果红为光催化降解底物,探究了刚果红初始浓度、催化剂用量、溶液pH、不同光源等因素对NiFe₂O₄光催化降解刚果红活性的影响。结果表明,当刚果红溶液浓度为20 mg/L、催化剂NiFe₂O₄的用量为0.065 g、pH 2~10、在太阳光下照射480 min时,刚果红的降解率高达99%以上,催化剂性能稳定,适合处理刚果红类有机污染物。     

可生物降解的pH敏感水凝胶的合成及其溶胀性能研究

采用明胶和聚乙烯醇为原料,制备了戊二醛交联、明胶／聚乙烯醇配比不同的水凝胶,并用FTIR和SEM对产物进行了表征。研究了凝胶的溶胀动力学,结果表明,原料配比对各种凝胶的溶胀速率影响不大,而对平衡溶胀比与原料配比有关,室温下凝胶的平衡溶胀比在300％～500％之间。pH敏感性研究表明,几种凝胶均表现出明显的pH响应性,当溶胀介质的pH值在明胶等电点附近时,水凝胶的溶胀比达到最小值,凝胶的溶胀-消溶胀动力学曲线呈“W”形,即该凝胶具有形状记忆功能。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.