层状前体镁铁水滑石及磁性材料的制备及表征

本文提出了利用镁铁水滑石作为磁性材料前体再经高温焙烧制备尖晶石型铁氧体的思路,深入研究了水滑石的制备工艺及结构性能并初步探讨了其焙烧后的磁学性能。由共沉淀法合成了Mg/Fe摩尔比为2,3,4,6的镁铁水滑石,XRD结果表明随镁铁比增大、晶化温度的升高及晶化时间的延长,水滑石的晶体结构规整性增强;热重-差热结果显示镁铁水滑石的分解有两个过程,随着镁铁比增大,水滑石的热稳定性提高。高温焙烧后的镁铁水滑石具有较好的磁学性能。     

MgZnAl-EDTA柱撑水滑石的制备及其对Pb(Ⅱ)的吸附

以共沉淀法合成的Mg2ZnAl-CO3水滑石为前体,采用离子交换插层组装方法制备了Mg2ZnAl-EDTA柱撑水滑石,并用XRD和IR进行表征。以水滑石前体和柱撑水滑石为吸附剂,用于废水中Pb2+的吸附。柱撑水滑石的吸附容量明显大于水滑石前体,柱撑水滑石的最佳吸附条件为:温度45℃,pH 5.5,吸附时间150min,Pb2+初始浓度100 mg·L-1。在最佳吸附条件下,柱撑水滑石对废水中Pb2+的饱和吸附量为183.51 mg/g。     

含钴铜镍类水滑石焙烧产物催化分解N2O的研究

 合成了含Co，Cu和Ni的M／Mg－Al－HTL类水滑石，并将其焙烧产物用于N2O催化分解反应．实验结果表明，Co／Mg－Al－HTL对N2O分解反应的催化活性明显高于Cu／Mg－Al－HTL和Ni／Mg－Al－HTL的活性．在保持样品中Al含量不变的条件下，催化活性随着Co含量的增加及Mg含量的减少而升高，各催化剂的活性顺序为：Co／Al－HTL＞Co／Mg－Al－HTL＞Cu／Mg－Al－HTL＞Ni／Mg－Al－HTL．在此基础上，进一步考察了Co／Al－HTL中Co／Al原子比调变对催化剂活性的影响．对含Co类水滑石及其焙烧产物进行了XRF，XRD和N2O－TPD表征．结果表明，含Co类水滑石具有典型的水滑石结构，其高温焙烧产物都含尖晶石相．由于尖晶石相中Co－O－Al活性中心的作用，含Co类水滑石对N2O分解反应表现出较高的催化活性．随着Co／Al原子比的增大，含Co类水滑石焙烧产物的尖晶石相特征更加突出，Co－O－Al活性中心数目随之增多，催化剂的活性也相应升高．     

Mg-Al水滑石催化甘油与碳酸二甲酯的酯交换反应简

报道了温和条件下甘油和碳酸二甲酯在一系列不同Mg/Al比（0.5-6）的Mg-Al水滑石催化下合成碳酸甘油酯（GC）的反应. 发现,Mg-Al水滑石对该反应具有很高的GC选择性,其中Mg/Al=2经400℃处理所得水滑石催化效率最高：70 ℃反应3 h甘油转化率达66.9%时,GC选择性维持在97%以上. 表征结果表明,水滑石样品的比表面积、孔径、结晶度和表面碱性对其催化活性影响很大.     

均匀沉淀法直接合成有机阴离子柱撑水滑石

以尿素为沉淀剂用均匀沉淀法直接合成有机阴离子柱撑水滑石(Layered Double Hydroxides，LDH)及CoAl水滑石等，并用XRD，FT—IR，TGA，TEM等分析手段对所合成的水滑石进行了表征．结果表明，尿素均匀沉淀法可以直接合成有机阴离子柱撑水滑石及CoAl水滑石等，并且可以方便地消除原料中阴离子的干扰，是合成有机阴离子柱撑水滑石及CoAl水滑石等的一个简便快速的新方法。     

阴离子柱撑磁性镍铝水滑石的制备及表征

将磁性基质与镍铝类水滑石组装制备磁性镍铝水滑石。研究了磁性基质含量、焙烧温度对水滑石磁学性能及结构的影响。并采用SEM、XRD、FT-IR、DSC-TG及VSM(vibrating sample magnetometer)等测试技术对制备的水滑石的结构和磁学性能进行了表征。结果表明,磁性基质的引入赋予镍铝类水滑石以超顺磁性,磁性基质含量对样品的磁性能起决定性作用,磁性镍铝水滑石的比饱和磁化强度随磁性基质含量的增加而增加;XRD分析结果表明,磁性基质的引入没有改变水滑石的典型层状结构且随着磁性基质含量的增多,磁性镍铝水滑石的特征衍射峰的衍射强度有所降低,n(Ni2 )/n(Fe2 )达到20时,XRD谱图中开始出现Fe3O4晶相的衍射峰;前驱体经1073K焙烧后出现尖晶石晶相;DSC-TG分析结果表明,磁性基质的引入没有改变水滑石2个阶段吸热的特征,这与XRD的检测结果一致。     

MgAl-PdCl4水滑石的合成与表征

以MgAl-NO3水滑石为前驱体,用离子交换法将PdCl42-作为客体插入水滑石的层间,通过XRD、IR、DTA、比表面积等表征制备的水滑石,探讨了Pd含量、插层时间、Mg/Al摩尔比以及焙烧温度对制备水滑石结构的影响.结果表明,插层产物中PdCl42-与NO3-共存于层间,PdCl42-的引入,减小了水滑石的层间距,PdCl42-引入量越多,层间距减少的越多.Mg/Al摩尔比在2～4均可以形成MgAl- PdCl4-HLTcs,但是其值增大时,水滑石的层间距逐渐降低.插层交换时间延长有利于PdCl42-插入层间,但从制备水滑石的角度看,晶化时间8 h,即可得到结晶良好的水滑石化合物.DTA分析结果显示,在较高的PdCl42-引入量,或较高的Mg/Al摩尔比时层间PdCl42-失去Cl-转化成PdO的温度在370 ℃左右,层间NO3-的脱除温度在410 ℃附近;在低的PdCl42-引入量,或低的Mg/Al摩尔比两个脱除过程一起进行,在500 ℃左右完成.随着层间PdCl42-的分解及NO3-的脱除,400 ℃时MgO-Al2O3-PdO物相开始形成,600 ℃时基本形成完全,比表面积也达到最大,进一步提高焙烧温度至800 ℃,由于金属氧化物的晶粒变大及出现少量的MgAl2O4尖晶石物相,其比表面积有所下降.     

MgAl-EDTA柱撑水滑石的制备及其应用

以MgAl-CO3型水滑石为前体,由离子交换法进行插层组装,合成了EDTA柱撑的MgAl-EDTA水滑石,并用X射线衍射、红外光谱对样品进行了表征。探讨了n(Mg)/n(Al)摩尔比、pH、反应温度、EDTA与前体水滑石配比对插层反应的影响,结果表明,当n(Mg)/n(Al)摩尔比为2～3、pH在4.5左右、反应温度控制在150℃以上、同时保证过量的EDTA时,EDTA可以插入MgAl-CO3水滑石层间,取代CO23-,形成结构完好的EDTA柱撑水滑石。MgAl-EDTA柱撑水滑石通过层间EDTA对Cu2+的螯合作用,可以在较短的时间内吸附溶液中的Cu2+,溶液中Cu2+的去除率在96%以上。     

乙二胺四乙酸柱撑镁锌铝三元水滑石的制备与表征

采用共沉淀法合成了Mg2ZnAl-CO3水滑石;以其为前驱体,利用离子交换法进行插层组装得到Mg2ZnAl-EDTA三元柱撑水滑石;采用X射线衍射仪和傅立叶变换红外光谱仪对产物进行了表征.结果表明,合成的Mg2ZnAl-CO3水滑石纯度高、晶型良好,其层间CO32-可被乙二胺四乙酸(EDTA)阴离子取代形成Mg2ZnAl-EDTA三元柱撑水滑石;柱撑水滑石的层间距离明显增加,EDTA阴离子在层间倾斜排列.     

层状前体镍铁水滑石及磁性材料的制备及表征

提出了利用镍铁水滑石作为磁性前体再经高温焙制备尖晶石型铁氧体思路，深 入研究了水滑石的制备工艺及结构性能并初步探讨了其焙烧后的磁学性能。由共沉 淀法合成了Ni/Fe摩尔比为2，3，4，6的镍铁水滑石，XRD结果表明镍铁比为3时晶 形较为理想，且随着晶化温度的升高及晶化时间的延长，水滑石的晶体结构规整性 增强。热重-差热结果显示镍铁水滑石的分解有两个过程，当镍铁比为3时，水滑石 的热稳定性相对最高。高温焙烧后的镍铁水滑石具有磁性。     

Molecular dynamics simulations of p-tert-butylcalix[4]arene with small guest molecules

Classical molecular dynamics simulations were used to study p-tert-butylcalix[4]arene inclusion compounds with xenon, nitrogen, hydrogen, methane, and sulfur dioxide guest molecules. The calixarene units were taken to be rigid and the intermolecular molecular interactions were modeled as a sum of the van der Waals interactions with parameters from the AMBER force field and electrostatic interactions. Simulations of the high-density alpha phase and low-density beta0 phase of p-tert-butylcalix[4]arene were used to test the force field. The predicted densities of the two phases were found to agree with experimental measurements at 173 K to within 5 %. Simulations were performed with guests placed inside the calixarene cages of the beta0 phase. Guest-host ratios of 1:1 to 1:4 were considered. Changes in the unit-cell volume and density of the phases with the addition of guest molecules and the inclusion energies for the guests were determined. Finally, the dynamics of the guest motion inside the cages were characterized by determining the root-mean-square displacements and velocity autocorrelation functions of the xenon and nitrogen guests.     

Chemometric models for the quantitative descriptive sensory analysis of Arabica coffee beverages using near infrared spectroscopy

Mathematical models based on chemometric analyses of the coffee beverage sensory data and NIR spectra of 51 Arabica roasted coffee samples were generated aiming to predict the scores of acidity, bitterness, flavour, cleanliness, body and overall quality of coffee beverage. Partial least squares (PLS) were used to construct the models. The ordered predictor selection (OPS) algorithm was applied to select the wavelengths for the regression model of each sensory attribute in order to take only significant regions into account. The regions of the spectrum defined as important for sensory quality were closely related to the NIR spectra of pure caffeine, trigonelline, 5-caffeoylquinic acid, cellulose, coffee lipids, sucrose and casein. The NIR analyses sustained that the relationship between the sensory characteristics of the beverage and the chemical composition of the roasted grain were as listed below: 1 - the lipids and proteins were closely related to the attribute body; 2 - the caffeine and chlorogenic acids were related to bitterness; 3 - the chlorogenic acids were related to acidity and flavour; 4 - the cleanliness and overall quality were related to caffeine, trigonelline, chlorogenic acid, polysaccharides, sucrose and protein.     

Determination of Diazepam and Clonazepam in Natural Water – a Voltammetric Study

The differential pulse adsorptive cathodic stripping voltammetry (DP‐AdsCSV) employing the hanging mercury drop electrode (HMDE) was used towards the determination of two psychotropic drugs in environmental samples. Voltammetric and experimental conditions to Clonazepam (CLO) and diazepam (DIAZ) were optimized and the methods were in‐house validated. Accumulation potentials were −0.3 V to CLO and −0.6 V to DIAZ at 120 s of accumulation time. Pulse amplitude, pulse time and scan rate were 80 mV, 20 ms and 25 mV s⁻¹ to CLO and 100 mV, 20 ms and 40 mV s⁻¹ to DIAZ, respectively. Recovery tests were done in three different concentrations to evaluate methods’ accuracy and the results were from 88±6 to 120±13 %. In precision tests, standard deviations were lower than 15 % for both methods. Goods limits of quantification 0.65 and 0.27 μg L⁻¹ to CLO and DIAZ respectively were achieved without pre‐concentration steps such as SPE, etc. Voltammetry employing HMDE was first used for the determination of CLO and DIAZ in natural water. Natural samples were spiked and recovery tests confirmed the applicability of the methods developed. Nine samples from Parana state, Brazil, were analyzed and CLO and DIAZ values were below the limits of detection in all samples.     

蛋白质组学技术筛选与鉴定癫痫疾病的差异蛋白质

应用蛋白质组学双向凝胶电泳(Two-dimensional gel electrophoresis, 2DE)和质谱技术, 定量分析和鉴定了癫痫组(n=3)和正常组(n=3)脑组织的差异表达蛋白, 以从蛋白质水平上揭示癫痫病的发机制. 结果表明, 凝胶图谱可辨识2500~3000个蛋白点, 对21个显著差异表达蛋白点进行质谱鉴定和SwissProt数据库检索, 得到17个癫痫差异蛋白, 其中2个蛋白在癫痫组织中表达上调, 15个蛋白表达下调. 部分蛋白与癫痫的关系属首次报道. 这些蛋白与癫痫的发生发展相关, 可能成为癫痫的分子标志物和药物治疗的靶向蛋白.     

基于纳升电喷雾-轨道阱超高分辨质谱对完整单克隆抗体药物进行分子量测定及糖型鉴定的条件探究

整体分子量测定和糖型鉴定是抗体药物研发及生产中不可或缺的表征内容,而在完整蛋白层面进行测定可获得最为直接的测定结果。实现此类测定有赖于可提供较高分辨能力及质量精度的仪器;测定中涉及的相对复杂的参数设置可能受多种条件的干扰而产生误导性结果。该研究考察了利用纳升电喷雾离子源-轨道阱质谱仪以非变性质谱方式测定完整单克隆抗体药时,仪器分辨率、源内裂解、碰撞诱导碎裂、溶液组成等条件对单克隆抗体药物分子量及糖型测定结果的影响,以期为此类质谱分析提供有益的借鉴。     

Identification of hydroquinone and catechol as impurities in reagent-grade phenol using high performance liquid chromatography with ultraviolet and electrochemical detectors

Several impurities which were suspected to be present in commercial reagent-grade phenol were separated using high performance liquid chromatography following sample concentration by steam distillation. A reverse-phase, microparticulate column and 5 solvent systems containing 5% to 25% methanol in 0.05 M phosphoric acid were used. A variable wavelength ultraviolet detector and an electrochemical detector were connected in series, in that order, to the column. Capacity factors (?) for pyrogallol, hydroquinone, resorcinol, catechol, orcinol and phenol were determined in the 5 solvent systems and compared to ?-values of impurities present in the residue remaining from the steam distillation of phenol. Co-chromatography of standards suspected as contaminants and possessing ?-values similar to those of impurities were carried out in 3 solvent systems to confirm identical retention characteristics. Detector response ratios of contaminants and suspected standards, using various wavelengths and voltage potential settings, were utilized as major identification parameters. Two of the several contaminants separated were identified as hydroquinone and catechol.     

电感耦合等离子体质谱(ICP-MS)法测定玻纤滤筒中金属元素本底值的预处理方法探讨

探讨了不同预处理方法对国产玻纤滤筒本底值的降低效果,便于废气样品的分析测定。分别对空白滤筒、热硝酸、硝酸+硫酸和硝酸+EDTA、HCl处理后的滤筒进行分析,测得滤筒中金属元素的含量;对处理效果较好的一批滤筒进行空白加标,考察加标回收率,全程用电感耦合等离子体质谱(ICPMS)法对样品进行测定,结果发现空白滤筒中部分金属元素含量较高;热硝酸处理后,滤筒本底中铅含量有所降低,但其它元素去除效果不显著;硝酸+硫酸处理后,滤筒中铅含量剧增;硝酸+EDTA处理滤筒,铅可以得到较好的去除效果,大部分金属元素含量有了明显降低;基于HCl对金属有较好的溶出效果,浸泡可较好地降低滤筒中金属元素的含量,但大量氯离子存在对ICP-MS法测定的干扰较大。对硝酸+EDTA处理后的滤筒进行空白加标,大部分金属元素加标回收率75%。故以硝酸+EDTA处理玻纤滤筒可以使国产玻纤滤筒适用于废气样品的分析。     

Dynamic and Equilibrium Studies on Adsorption of Cu(II) Ions onto Biopolymeric Cross-Linked Pectin and Alginate Beads

Binary biopolymeric beads of alginate and pectin were prepared and characterized by FTIR spectra. On to the surfaces of the prepared beads were performed static and dynamic adsorption studies of Cu(II) ions at fixed pH and ionic strength of the aqueous metal ion solutions. The adsorption data were applied to Langmuir and Freundlich isotherm equations and various adsorption parameters were calculated. The influence of various experimental parameters such as effect of time, pH, temperature, solid to liquid ratio, and the presence of salts were investigated on the adsorption of copper ions.     

Preparation and properties of polyurethane networks based on α,ω-difunctional poly(hexafluoropropylene oxide)

Poly(hexafluoropropylene oxide), poly(HFPO), networks were prepared from functional polymers by end linking via urethane groups. The prepolymers were characterized by NMR spectroscopy and GPC. The networks were characterized by determination of the number of network chains from the shear modulus, and were snown to contain both trifunctional crosslinks and difunctional links. The properties of the networks were investigated by a range of techniques. Compared with fully-fluorinated networks formed via triazine cross-links, investigated previously, the urethane-linked networks were more readily prepared but were poorer elastomers, were less thermally stable, and were less resistant to swelling by common polar solvents. © 1995 John Wiley & Sons, Inc.     

Shear-precipitated chitosan powders,fibrids, and fibrid papers: Observations on their formation and characterization

Chitosan powders and fibrids were prepared by shear precipitation of dissolved chitosan in a coagulating solution of sodium hydroxide. Following neutralization by washing and an alcohol dehydration step, the white to off-white powders were fine and free flowing. The dried fibrids had a highly oriented, ribbon-like shape that in bulk gave a lofty appearance and soft hand. Chitosan fibrids were readily converted to sheet structures by typical paper-making procedures. The resulting chitosan papers were either smooth, flexible, and largely translucent when pressed dry from the moist mat, or were soft and opaque white when the moist mat was soaked in alcohol before drying. X-ray diffraction, SEM, and optical microscopy were used to characterize the different chitosan powders, fibrids, and papers. Chitosan fibrid papers were found to have tensile properties comparable to that of cellulosic papers, though the wet strength and water sorption of chitosan fibrid papers was higher than that of the cellulose controls. ©1995 John Wiley & Sons, Inc.