红外光谱及其理论模拟在砷吸附过程中的应用

红外光谱技术具有分析速度快、分辨率高、灵敏度高、可以实时原位分析监测等优点。基于密度泛函理论对矿物吸附砷污染物体系红外光谱进行理论计算，分析对比红外光谱实测特征峰和理论计算特征峰，可以揭示砷吸附过程微观机制和表面化学形态。对红外光谱技术在水铁矿、赤铁矿、针铁矿等主要矿物吸附无机砷酸和有机胂酸的定性定量分析进行了综述，总结了红外光谱在无机和有机砷污染物吸附体系的定性定量研究及理论计算，为砷污染物精准检测分析和砷污染控制提供参考。     

恶臭假单胞菌与土壤矿物的界面反应及其对甲基对硫磷降解影响

研究了恶臭假单胞菌在蒙脱石、高岭石和针铁矿表面的吸附特征,探讨了细菌在不同粘粒矿物存在下的生长代谢活性,及对甲基对硫磷的降解动力学.结果表明, 三种矿物对细菌的吸附强度为针铁矿>高岭石>蒙脱石.当甲基对硫磷浓度较低时(10 mg/L), 游离菌的降解能力始终比固定菌强;在高浓度(20～40 mg/L)下, 固定菌对农药的降解能力起初(前9 h)高于游离菌, 随后渐渐低于游离菌.不同矿物固定的细菌, 其降解能力为蒙脱石>高岭石>针铁矿.蒙脱石对细菌的亲和力最弱, 但它对细菌的代谢活性有促进作用, 有利于农药的生物降解; 而针铁矿与细菌的结合强度最大, 细菌活性受到抑制, 不利于农药的降解.     

甲基对硫磷和西维因在粘土矿物表面的吸附解吸特性

研究了甲基对硫磷和西维因在蒙脱石、高岭石和针铁矿表面的吸附 解吸特征。结果表明,Langmuir方程能较好的描述甲基对硫磷和西维因在３种矿物表面的等温吸附过程,且蒙脱石对农药的最大吸附量大于高岭石和针铁矿。用动力学方程对2种农药的吸附过程进行拟合,Elovich方程、双常数方程和一级动力学方程均得到较好的结果,其中Elovich方程为最佳模型,相关系数（R²）在0.93～0.98之间,说明该吸附为非均相扩散过程。3种矿物对甲基对硫磷和西维因的吸附强度均为蒙脱石＞高岭石＞针铁矿。     

白云鄂博铁-稀土矿床的物质来源和成因理论问题

白云鄂博铁矿和稀土矿的物质来源迥异,具有壳源和幔源成矿作用的二重性。原生工业铁矿为表生沉积矿床。稀土矿是叠加于铁矿的地幔流体交代矿床,其形成和产出受大陆热点的控制。矿区白云岩属正常沉积的碳酸盐岩,它的碳、氧同位素组成排除了与国外岩浆碳酸岩对比的可能性。单矿物Sm-Nd等时线年龄显示稀土矿具有早-中元古代(1700±480Ma)和加里东(424—402 Ma)2次成矿高峰期。     

白云鄂博铁矿石中稀土的赋存状态研究

白云鄂博铁矿是一个富含有稀土资源的大型矿床,其中稀土元素不仅含量高、种类多,且储量居世界之最,在我国稀土产业的发展过程中具有极其重要的地位。通过电子探针,对白云鄂博含稀土铁矿石的赋存状态进行了分析研究。结果表明:磁铁矿、萤石以及稀土矿物是构成白云鄂博铁矿中主、东、西三个矿区的主要矿物,其中稀土矿物主要为氟碳铈矿和含钕单斜褐钇钶矿,微量的放射性元素钍以类质同象的形式存在于稀土矿物中。     

乙基黄原酸钾-甲基异丁酮萃取原子吸收法测定岩石矿物中微量铜、铅、钴、镍、银、镉

用酒石酸铵掩蔽岩石矿物中的Fe、Al、Ti、Ca、Mg等元素,在pN8.5以乙基黄原酸钾-甲基异丁酮萃取,用同一份有机相火焰原子吸收法测定岩石矿物中微Cu、Pb、Co、Ni、Ag、Cd。本法有较高的灵敏度和准确度,在没有用氘灯或塞曼效应扣背景的原子吸收分光光度仪上测定,能得到满意的结果。适用于化探试样和硅酸盐、铁矿等岩石矿物分析。曾用此法测定GSD-1-GSD-8八个化探标样,质量均符合规定要求。     

白云鄂博矿中深部弱磁尾矿中稀土的赋存状态研究

运用化学分析、场发射扫描电镜、X射线能谱仪及AMICS自动矿物分析系统等分析方法对白云鄂博中深部矿石弱磁尾矿中稀土的赋存状态进行研究,研究结果表明:中深部弱磁尾矿中稀土品位为9.66%,稀土矿物主要是氟碳铈矿和独居石,且二者的比例随着开采深度的增加由原来的7∶3~6∶4逐渐变化为3∶1,氟碳铈矿的比例明显增大。元素含量种类较多,矿物的组成非常复杂,嵌布粒度很细,稀土矿物在38μm粒度以下累积量超过了90%。稀土矿物主要是与铁矿物、萤石连生,解离度较高,利于稀土矿物分选。氟碳铈矿和独居石主要以单体存在,呈微细粒状、断续或者连续条带状分布于石英、闪石、铁矿物、萤石、磷灰石、霓石、方解石中。此研究结果对白云鄂博矿中深部弱磁尾矿中稀土的高效综合利用具有重要的指导意义。     

交流示波极谱滴定在矿石分析中的应用——Ⅰ.用EGTA滴定钙

将交流示波极谱滴定应用于矿石中钙的EGTA滴定。在实验条件下,Mg、Fe、Al、Ti、Ni、Pb、Mn、P等元素不干扰钙的滴定。用于硅酸盐、碳酸盐、铁矿、磷矿、锰矿等岩石矿物分析,终点清晰,方法快速、准确。     

As(V)浓度和环境因子对硫酸盐绿锈转化的影响及其机制

绿锈与As（V）可共存于土壤、沉积物和地下水等缺氧环境,但As（V）如何影响绿锈转化过程和机制了解甚少.本工作通过溶液化学和光谱学方法,系统研究了As（V）浓度、pH、温度和空气流速对硫酸盐绿锈（GR）转化的影响.GR转化过程中通过吸附和共沉淀作用对As（V）有极强的去除能力,同时As（V）增强了GR的稳定性,显著影响转化产物的结晶度、矿物类型和生成机制.随As（V）浓度增加,GR氧化转化由溶解-氧化-沉淀机制向固态氧化机制过渡,产物由针铁矿和纤铁矿混合相向纯纤铁矿向纤铁矿、水铁矿和高铁绿锈混合相转变;高As（V）浓度时形成无定形FeAsO₄表面沉淀.Fe/As=24时,pH 6.5~9、温度（5~45℃）和空气流速（0~0.05 m³/h）条件下纤铁矿均为主要产物,随pH和空气流速增加或温度减小纤铁矿结晶度逐渐减弱;高pH或高空气流速或低温有利于高铁绿锈和水铁矿形成,高温有利于针铁矿形成.上述结果对深入理解环境中各种铁氧化物的形成转化机制和As（V）的环境行为有重要意义.     

基于拉曼Mapping与AMICS研究稀土矿物分布特征和取向相位

采用拉曼Mapping及光学显微镜与AMICS技术相结合,对白云鄂博矿霓石型铁稀土矿石分布特征、矿物结构及晶体取向等方面进行研究。结果表明：稀土矿物产状多种多样,独居石颗粒明显比早期大,氟碳铈较多呈细粒状,部分呈板状或不规则形状,稀土总品位高达9.84%;铁矿物中含TiO2量为1.35%,具有第二代磁铁矿特征;利用拉曼Mapping成像技术开发一种矿物晶体取向成像方法,由独居石466cm^-1/970 cm^-1峰位与氟碳铈280 cm^-1/1090 cm^-1峰位面积之比,绘制出三种不同生长取向的独居石颗粒与延同一方向上生长氟碳铈矿物颗粒,在矿物结晶形态可以判定独居石可能先于氟碳铈矿物经多期热液交代成矿;该技术在硅酸盐、碳酸盐类矿物晶体取向鉴定方面具有独特明显优势,在矿物学分析中具有广阔的应用价值。     

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.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.