6,6'-二甲基-2,2'-联吡啶-4,4'-二甲酸甲酯的合成与表征

以6-甲基-2-羟基吡啶-4-甲酸甲酯为起始原料,经酯化反应制备2-甲基-6-(对甲苯磺酰氧基)吡啶-4-甲酸甲酯,使其在过渡金属镍络合物催化作用下自身偶联合成6,6'-二甲基-2,2'-联吡啶-4,4'-二甲酸甲酯,通过改变投料比例、反应温度及投料顺序获得最佳反应条件,收率77%。经核磁共振、红外光谱、质谱及差示扫描热量法等对分子结构进行了表征,验证了合成方法的可靠性。该结构能够满足均相时间分辨荧光免疫分析螯合剂中间体的需求。目前,它已成功用于均相时间分辨荧光免疫分析。     

电感耦合等离子体质谱(ICP-MS)法测定土壤中的有效钼

准确快速测定土壤中的有效钼,是评价土壤肥力的重要指标,对指导作物生产有重大意义。本文采用草酸-草酸铵溶液浸提土壤样品,待测浸提液稀释5倍后通过电感耦合等离子体质谱法在氦气模式下测定土壤中有效钼的含量,建立了土壤中有效钼高灵敏度分析的检测方法。选择103Rh为内标元素,校正仪器在测定过程中引起的信号飘移。对两种前处理方式进行比较,确定了震荡30 min、放置过夜的浸提方法浸提效果更好且更利于大批量样品的分析。使用震荡30 min、放置过夜的浸提方法对5个土壤标准物质有效钼进行前处理,其测定值均在标准值范围内;分别在无气体模式和氦气模式下比较了浓度为0mg/L、1mg/L、2mg/L、5mg/L、10mg/L、50mg/L的Mn对5ug/L 95Mo测定浓度的影响,结果表明氦气模式下的动能歧视可有效去除95Mo测定过程中的多原子离子的干扰,氦气模式测定有效钼明显优于无气体模式;分别对待测溶液稀释5倍和未稀释的内标回收率趋势进行监测,发现未稀释的样品内标回收率随着测量样品数的增多呈下降趋势,而稀释5倍对基体干扰的消除有显著效果。对5个土壤样品分别重复测定6次,其RSD均小于4.1%;线性相关系数为1.0000;方法检出限为0.0012 mg/kg。综上,该方法测定土壤有效钼结果准确,重现性好,灵敏度高,且适合大批量样品的分析。     

超高效液相色谱-电雾式检测器测定福建产绞股蓝中绞股蓝皂苷XLVI和LVI北大核心CSCD

该研究利用超高效液相色谱-电雾式检测器(UHPLC-CAD)建立了福建产绞股蓝中绞股蓝皂苷XLVI和LVI含量的测定方法。首先利用超高效液相色谱-四极杆-飞行时间质谱(UHPLC-Q-TOF/MS)结合UHPLC-CAD鉴定了福建产绞股蓝的主要成分,其中绞股蓝皂苷XLVI、LVI以及二者相应的含丙二酰基酸性皂苷为其主成分,因此在含量测定时先进行碱水解预处理将酸性皂苷转化为对应的去丙二酰基中性皂苷,再利用UHPLC-CAD测定碱水解后绞股蓝皂苷XLVI和LVI的含量。将绞股蓝样品粉末在乙醇-水-氨水(50∶46∶4,v/v/v)和料液比1∶150(g∶mL)条件下超声提取30 min,静置24 h后,在Waters ACQUITY UPLC BEH C18色谱柱(100 mm×2.1 mm,1.7μm)上分离,采用0.1%(v/v)甲酸水溶液和乙腈作为流动相进行梯度洗脱,流速0.5 mL/min,柱温40℃,电雾式检测器检测。结果表明,绞股蓝皂苷XLVI和LVI分别在9.94~318.00μg/mL和12.78~409.00μg/mL范围内具有良好的线性关系,相关系数(r)分别为0.9993和0.9995。方法精密度、重复性和24 h稳定性试验的相对标准偏差(RSD)均小于2.0%(n=6),绞股蓝皂苷XLVI与LVI的加标回收率分别在100.2%~107.2%与97.9%~104.2%范围内,RSD值分别为2.4%与2.6%。16批绞股蓝样品含量测定结果显示:绞股蓝皂苷XLVI含量占0.57%~2.57%,绞股蓝皂苷LVI含量占0.66%~2.99%。该方法灵敏度高,重复性好,可用于福建产绞股蓝的质量研究和质量控制。     

超导体YB6和LaB6的电子结构研究

本文使用准确的第一原理方法,对超导体YB6和LaB6进行了电子结构比较研究,为进一步的实验研究提供理论参考.     

对Maron理论处理高分子稀溶液的一点修改

近年来应用Maron溶液理论处理高分子溶液的一系列关于溶剂的热力学性貭,得到满意的結果。現有的例子都属高分子-良溶剂溶液。对稀溶液渗透压数据的处理,作者等巳指出可用π/c(1+qc)对c(1+qc)的作图法,得到直线关系,其中(符号均按Maron的写法,参阅文献[4])     

Determination of risedronate in rat plasma samples by ion-pair high-performance liquid chromatography with UV detector

In the present work, an analytical method for determination of risedronate, a member of bisphosphonates, is described for the routine analysis in rat plasma. Sample pre-treatment involves protein precipitation, co-precipitation with calcium at alkaline pH, hydrolysis of possible derivatives of pyrophosphate and reprecipitation. A good separation was obtained by using a reversed-phase column (Hypersil ODS-2 C₁₈, 4.6 mm × 250 mm, 5 μm). The mobile phase was an aqueous solution of buffer (contained 1.5 mM EDTA-2Na, 1 mM sodium etidronate, 11 mM sodium phosphate and 5 mM tetrabutylammonium bromide as ion-pair reagent) - methanol (88:12, v/v) adjusted to pH 6.75 using 1 M NaOH. The flow rate was 1 ml min⁻¹. UV detection (λ = 262 nm) was used to quantitate risedronate in the concentration range of 10-500 ng ml⁻¹. The limit of detection and quantitation for risedronate were 7 and 10 ng ml⁻¹, respectively. The method was applied successfully to plasma samples from Wistar rats undergoing oral administration of risedronate mini-pills. Precision, extraction recoveries, as well as accuracy results, were satisfactory and no interference was found at the retention time of risedronate. Hence, the method is suitable for monitoring risedronate in rat plasma.     

A capacitive sensor based on molecularly imprinted polymers and poly(p-aminobenzene sulfonic acid) film for detection of pazufloxacin mesilate

A novel capacitive sensor for pazufloxacin mesilate (pazufloxacin) determination was developed by electropolymerizing p-aminobenzene sulfonic (p-ABSA) and molecularly imprinted polymers (MIPs), which was synthesized through thermal radical copolymerization of metharylic acid (MAA) and ethyl-ene glycol dimethacrylate (EGDMA) in the presence of pazufloxacin template molecules, on the gold electrode surface. Furthermore, 1-dedecanethiol was used to insulate the modified electrode. Alter-nating current (ac) impedance experiments were carried out with a Model IM6e to obtain the capaci-tance responses. Under the optimum conditions, the sensor showed linear capacitance response to pazufloxacin in the range of 5 ng·mL-1 to 5 μg·mL-1 with a relative standard deviation (RSD) 5.3% (n=7) and a detection limit of 1.8 ng·mL-1. The recoveries for different concentration levels of pazufloxacin samples varied from 94.0% to 102.0%. Electrochemical experiments indicated the capacitive sensor exhibited good sensitivity and selectivity and showed excellent parameters of regeneration and stabil-ity.     

Adsorption and coordination of tartaric acid enantiomers on Cu(111) in aqueous solution

Chiral modifiers have gained much attention because they can induce high enantioselectivity on reactive metal surface in heterogeneous enantioselective catalysis. The high enantioselectivity is attributed to that the chirality of modifiers is bestowed onto the metal surface upon adsorption. Much study on the adsorption of modifiers on metal surface has been performed in an ultrahigh vacuum. In this paper, the adsorption of tartaric acid on Cu(111) has been studied by electrochemical scanning tunneling microscopy (STM) in aqueous solution. It is found that (R,R)-tartaric acid and (S,S)-tartaric acid can form a well-ordered adlayer on the Cu(111) surface with a (4 x 4) symmetry. A dimeric structure is proposed in the temporary model from STM observation.     

ASPECTS OF THERMODYNAMICS OF POLYMER MIXTURES

In this brief review article some aspects of the thermodynamics of polymer mixtures are discussed, mainly based on the author's research. The studies of poly (methyl methacrylate)/chlorinated polyethylene (CPE), poly (butyl acrylate)/CPE and CPE/CPE (different chlorine content) mixture verify the "dissimilarity" and "similarity" principles for predicting miscibility of polymer mixtures. The sign of heat of mixing of oligomeric analogues is not sufficient in predicting the miscibility. The Flory equation of state theory has been applied to simulate the phase boundaries of polymer mixtures. The empirical entropy parameter Q_(12) plays an important role in the calculation, this reduces the usefulness of the theory. With energy parameter X_(12)≠0 and Q_(12)≠0 the spinodals so calculated are reasonable compared to experiments. A hole model was suggested for the statistics of polymer mixtures. The new hole theory combines the features of both the Flory equation of state theory and the Sanchez lattice fluid theory and can be reduced to them under some conditions.