离子液体预处理对羊毛蛋白酶水解性能的影响

利用一种新型绿色溶剂--离子液体1-丁基-3-甲基咪唑氯盐(1-butyl-3-methylimidazolium chloride,[BMIM]Cl)对羊毛进行预处理,从而提高蛋白酶对羊毛的水解效率.系统研究了[BMIM]Cl预处理对蛋白酶处理后羊毛减量率、碱溶解度、蛋白质释放速率、氨基酸组成的影响,并从表面形态、表面润湿性能和纤维晶体结构等方面探讨了[BMIM]Cl对蛋白酶水解的促进作用机理.结果表明:羊毛经过[BMIM]Cl处理后,纤维减量率从2.68%提高到4.47%,碱溶解度达到11.6%,水解液中蛋白质浓度的变化显示[BMIM]Cl预处理使得蛋白质释放速率快速增加;羊毛纤维中低硫和部分高硫氨基酸百分比的降低进一步证实[BMIM]Cl预处理对蛋白酶水解起到了全面促进作用.SEM、润湿接触角以及WAXD测试结果显示预处理破坏了纤维鳞片层,增加了表面润湿性能,并且使得纤维结晶度下降,从而提高了蛋白酶对纤维的可及度,有利于酶解速率的提高.     

2-氯烟酸绿色合成工艺

以烟酸为原料,经双氧水氧化制得N-氧化烟酸（2）; 2经氯化、水解并精制得2-氯烟酸,总收率76.8%,纯度≥99.5%,其结构经¹H NMR和¹³C NMR确证。     

荧光素的全合成

设计了一条新的萤火虫荧光素(6)的全合成路线.以对甲氧基苯胺为起始原料,经酰胺化、硫代、水解、铁氰化钾氧化等反应构筑苯并噻唑环得到6-甲氧基苯并噻唑-2-甲酸(2).首次采用一锅法对2进行酰氯-酰胺化后,经脱水制得关键中间体2-氰基-6-甲氧基-苯并噻唑(4);4经脱甲基、与D-半胱氨酸盐酸水合物反应合成了6,总收率20%,100%ee.其结构经UV,1H NMR,FT-IR和MS表征.     

电化学方法制备超细氧化铋粉末

超细氧化铋用途广泛。目前超细氧化铋的制备一般通过四个途径;一、机械粉碎法,可以获得粒径1μm的细粉,但在粉碎的过程中易混入杂质;二、熔融喷雾法,该法可以在短时间(45—48s)内获得超细Bi2O3,但均匀性差,氧化不易完全,生产过程有粉尘污染;三、通过水解氧化铋的     

一种有效的制备聚乙二醇修饰氧化石墨烯的方法

为提高氧化石墨烯(GO)的生物相容性从而扩展其在高性能生物材料制备中的应用,采用甲苯-2,4-二异氰酸酯作为桥联剂,制备了四臂星型聚乙二醇修饰氧化石墨烯(GO-TDI-sPEG),该产物在水中仍然可以稳定分散.采用傅里叶红外光谱(FTIR)、拉曼光谱(Raman)、X-射线衍射(XRD)、原子力显微镜(AFM)、透射电子显微镜(TEM)和热重分析(TGA)对接枝产物进行表征.产物在2861 cm-1和1093 cm-1处出现的特征红外吸收表明sPEG已接枝到GO上.产物的Raman光谱中D模与G模信号变弱,且ID/IG值变化不大,说明sPEG改性后的氧化石墨物理结构没有发生变化.XRD曲线上产物衍射峰消失,表明经聚合物修饰后氧化石墨被完全剥离.TGA数据表明原始GO在约160℃开始发生热失重,经修饰后,大约在260℃开始热失重,热稳定性增加了约100℃.由TEM图片可以观察到GO及改性石墨烯产物剥离程度较高,且片上分布有较多聚合物点.且AFM图片显示GO的平均厚度大约为0.85 nm,接上聚合物后部分厚度增加到约1.2 nm.     

白酒基酒中酮类物质的近红外光谱检测方法

应用近红外光谱技术建立了白酒基酒中2,3-丁二酮和3-羟基-2-丁酮的快速检测模型。从洛阳杜康酒厂选取182个白酒基酒样品为材料,运用气相色谱法测得两种物质的化学值,同时采集其在12 000~4 000 cm-1范围内的光谱数据,采用偏最小二乘法(PLS)结合内部交叉验证建立校正模型。通过对比不同光谱预处理下PLS模型效果对其进行优化,确定2,3-丁二酮和3-羟基-2 丁酮的最佳预处理方法分别为一阶导数+多元散射校正和二阶导数,最佳光谱区间分别为9 403.2~7 497.9 cm-1和9 403.2~7 497.9 cm-1+6 101.7~5 449.8 cm-1。优化后2,3-丁二酮和3 羟基-2-丁酮校正集样品的化学值和近红外预测值的决定系数(R2)分别为0.960 2和0.963 2,交叉验证均方根误差(RMSECV)分别为0.39、0.22 mg/100 mL;通过外部检验,验证集样品的R2分别为0.957 6和0.957 8,预测均方根误差(RMSEP)分别为0.40、0.24 mg/100 mL。结果表明,应用近红外光谱技术结合化学计量学方法所建立的模型有较高的准确度,能够满足白酒生产中酮类物质的快速检测需要。     

新型3-氯-1-(3-氯-2-吡啶)-1H-吡唑甲酰胺类化合物的合成

2,3-二氯吡啶肼解后与马来酸二乙酯成环,再经氯代、氧化、水解制得3-氯-1-(3-氯-2-吡啶)-1H-吡唑-5-甲酸(6);6经二氯亚砜酰氯化、环胺酰胺化合成了13个新型3-氯-1-(3-氯-2-吡啶)-1H-吡唑甲酰胺类化合物,其结构经1HNMR和MS表征。     

BaF2/La2O3催化剂上甲烷氧化偶联反应活性氧物种的原位红外光谱

用原位红外光谱研究了BaF2/La2O3催化剂上甲烷氧化偶联反应的活性氧物种.结果表明,催化剂经O2预吸附后,在1 108~1 118 cm-1处出现超氧物种O2-的O-O键伸缩振动峰.经18O2同位素交换实验后,原1 108~1 118 cm-1处谱峰的强度减弱,同时在1 086和1 051 cm-1处出现(O18O)-物种和18O2-物种的吸收峰.同位素交换实验进一步确证了1 108~1 118cm-1处谱峰确为O2-物种的吸收峰.在700℃下,O2-物种能够活化CH4生成C2H4,而且O2-物种的消耗量和C2H4的生成量呈很好的消长对应关系.超氧物种O2-是BaF2/La2O3催化剂上甲烷氧化偶联反应的活性氧物种.     

离子液体预处理的纤维素酶解糖化

利用离子液体氯化1-丁基-3-甲基-咪唑([C4mim]Cl)对纤维素进行预处理.结果表明,纤维素经离子液体预处理后聚合度下降,糖化速度随预处理温度增加呈现先增大后下降的趋势,在90℃出现最大值11 77 g/(L·h). 延长预处理时间和采用乙醇作为沉淀剂,可促进酶解糖化,糖化速度比未处理的纤维素提高70%. 根据扫描电子显微镜(SEM)观察,纤维素出现了明显的解聚.     

光化学氧化对多孔硅稳定性及SO2传感性能影响

采用光化学氧化方法对多孔硅进行后处理,获得具有良好稳定性的氧化多孔硅;采用SEM、AFM、FT-IR进行表征;通过SO2传感实验,评价其光致发光谱的变化。结果表明,采用电化学阳极氧化制备的新鲜多孔硅在空气中稳定性较差,SEM图表明其膜层分布有120×40μm的长方形小块,光化学氧化后使该长方形小块进一步分裂变细;AFM图表明,新鲜制备的多孔硅经稳定化处理后,表面硅柱宽度由700～750 nm变为300～350 nm,高度由50～58 nm变为40 nm;出现Si—O键(1 114 cm-1)和OSi—H键(2 249 cm-1)的振动峰;该氧化多孔硅在SO2介质中呈可逆的荧光猝灭特征,荧光峰的位置不随SO2浓度变化而发生移动,稳定性较好。     

Thermoanalytical characterisation of modified keratin fibres

In the wool textile industry, several processes serve to improve the commercial properties of the fibres such as fineness, softness, length, strength and lustrous. For example, wool is chemically treated with reductive agents then stretched and set. This leads to modifications of the original protein structure causing changes in thermal behaviour, dyeing, colouristic and wet resistance properties. A multidisciplinary approach was used to investigate treated and untreated wools, with the aim of exploiting the nature of the structural changes. SEM and TEM revealed changes on the cuticle and cortical cell morphology; structure modification were studied by FT-IR and DSC. This revised version was published online in August 2006 with corrections to the Cover Date.     

Age estimation of old carpets based on cystine and cysteic acid content

A method for the evaluation of the age of wool carpets and textiles was developed based on the age dependent alteration of amino acid composition of proteins. Samples of 23 wool carpets and textiles of known age, obtained from the Hungarian Museum of Industrial Arts and the Hungarian National Museum were analysed for amino acid content. Results were compared with data obtained for contemporary, untreated wool and wool carpet. The cysteic acid content of wool increases with age. The contemporary wool carpet contained 0.31 g of cysteic acid in 100 g of protein. Comparable figures were 1.87 g for a 550-year old carpet and 4.01–4.39 g for the 1600–1750 year old wool carpets. The cystine content decreased with age, the corresponding figures being 7.88, 3.12 and 1.19-0.97 g/100 g, respectively. Corresponding contents of methionine were 0.43, 0.21 and 0.20-0.00 g/ 100 g and for tyrosine 3.07, 2.11 and 0.20-0.00 g/100 g. Prediction equations were developed as linear regressions of the age of wool on cysteic acid, cystine and tyrosine contents. The 95% confidence intervals of estimates for two samples of unknown age were estimates plus or minus 30 and 38 years.     

Grafting Vinyl Monomers onto Wool Fibers: Graft Copolymerization of Methyl Methacrylate onto Wool Using Ferric Acetylacetonate Complex

The graft copolymerization of methyl methacrylate (MMA) onto native and reduced Indian Chokla wool fibers was studied in aqueous solution using an acetylacetonate complex of Fe(III). Perchloric acid was found to catalyze the reaction. The rate of grafting was investigated by varying the concentration of the monomer and the complex, the acidity of the medium, and the solvent composition of the reaction medium. The graft yield increases with increasing concentration of the initiator and with increasing temperature. An increase of monomer concentration up to 0.5634 mol/L and of the HClO4 concentration up to 0.01 mol/L increases the graft yield. Reduced and oxidized wools were found to be better substrates than untreated, esterified, cross-linked, and trinitrophenylated wools. Among the various monomers studied, MMA was found to be the most active. A suitable kinetic scheme is proposed. From the activation energy data, average molecular weight, and spectral studies, the reactivity of -SH groups, and the extent of chain transfer is ascertained.     

Sheep Wool Humidity under Electron Irradiation Affects Wool Sorptivity towards Co(II) Ions

The effect of humidity on sheep wool during irradiation by an accelerated electron beam was examined. Each of the samples with 10%, 53%, and 97% relative humidity (RH) absorbed a dose of 0, 109, and 257 kGy, respectively. After being freely kept in common laboratory conditions, the samples were subjected to batch Co(II) sorption experiments monitored with VIS spectrometry for different lapses from electron beam exposure. Along with the sorption, FTIR spectral analysis of the wool samples was conducted for cysteic acid and cystine monoxide, and later, the examination was completed, with pH measuring 0.05 molar KCl extract from the wool samples. Besides a relationship to the absorbed dose and lapse, the sorptivity results showed considerable dependence on wool humidity under exposure. When humidity was deficient (10% RH), the sorptivity was lower due to limited transformation of cystine monoxide to cysteic acid. The wool pre-conditioned at 53% RH, which is the humidity close to common environmental conditions, demonstrated the best Co(II) sorptivity in any case. This finding enables the elimination of pre-exposure wool conditioning in practice. Under excessive humidity of 97% RH and enough high dose of 257 kGy, radiolysis of water occurred, deteriorating the sorptivity. Each wool humidity, dose, and lapse showed a particular scenario. The time and humidity variations in the sorptivity for the non-irradiated sample were a little surprising; despite the absence of electron irradiation, relevant results indicated a strong sensitivity to pre-condition humidity and lapse from the start of the monitoring.     

氮气笼型水合物的激光拉曼光谱

在253K和16MPa的压力下,于实验室内合成了氮气水合物,用显微共焦拉曼光谱对其N-N和O-H键伸缩振动的光谱特征进行了研究．结果表明,氮气水合物中的N-N和O—H键的拉曼峰分别为2322．4和3092．1cm^-1,与天然的空气水合物中的数据十分接近．另外,还测定了液氮和溶解于水中的氮分子中N—N键的拉曼峰值,分别为2326．6和2325．0cm^-1．氮气笼型水合物分解的拉曼谱图表明,氮分子同时进入水合物的大笼和小笼中,但由于氮分子在大、小笼中的环境氛围十分接近,其拉曼位移相差不大,故拉曼谱图只能显示N—N键伸缩振动一个峰．     

Procedure for testing inertness of inserts and insert packing materials for GC injectors

The inertness of injector inserts and insert packing materials, such as glass or fused silica wool, is tested by a procedure based on split injection and rapid isothermal chromatography. Resulting sharp peaks sensitively reveal peak deformation resulting from adsorptivity, acid/base interaction, and excessive retention power. Degradation of labile components is detected by loss of material and degradation products. Adsorptivity was no problem on injecting 300 ng amounts. Degradation only occurred for raw wools; however, the retention power of some wools seemed unnecessarily high. On injection of smaller quantities, degradation remained similar, but adsorptivity increased significantly.     

Improvement of Phase Change Materials (PCM) Used for Solar Process Heat Applications

The high intermittency of solar energy is still a challenge yet to be overcome. The use of thermal storage has proven to be a good option, with phase change materials (PCM) as very promising candidates. Nevertheless, PCM compounds have typically poor thermal conductivity, reducing their attractiveness for commercial uses. This paper demonstrates the viability of increasing the PCM effective thermal conductivity to industrial required values (around 4 W/m·K) by using metal wool infiltrated into the resin under vacuum conditions. To achieve this result, the authors used an inert resin, decoupling the specific PCM material selection from the enhancement effect of the metal wools. To ensure proper behavior of the metal wool under standard industrial environments at a broad range of temperatures, a set of analyses were performed at high temperatures and an inert atmosphere, presenting a thorough analysis of the obtained results.     

Sorption properties of sheep wool irradiated by accelerated electron beam

Electron beam (EB) irradiated wool was examined for sorption of chromic ions. Sorption increased with the adsorbed dose non-monotonously, which is a result of the generation of S-oxidized groups, secondary structure variation, and the breaking of the keratin backbone. For a dose of 400 kGy, an increase by 120 % was observed at the cystine dioxide and cysteine acid amounts. Examining sorption of unexposed wool and that irradiated with doses of 25 kGy and 40 kGy for basic, methylene blue (MB), or acidic, pyrogallol red (PR) dyes revealed that such low doses have no effect on the carboxylic or amino groups of keratin. Sorption of MB is independent of the EB treatment and is identical for both samples due to the interaction of MB amino groups with the carboxylic groups of wool; however, the sorption capacity for PR is a function of the EB treatment. The sample irradiated with the dose of 25 kGy showed higher PR sorption than that with the EB dose of 40 kGy, which was equal to that of unexposed wool. While the 25 kGy sample provided more active sites for PR interaction compared with the unexposed one, the 40 kGy sample contained already enough active sites to generate intra- and intermolecular interactions inside wool. Thus, PR adherence to the 40 kGy sample was restricted and comparable to the level of unexposed wool.     

Electrochemical flow-through detector for the determination of cystine and related compounds

An electrochemical double cell for the detection of cystine in aqueous liquid streams is described. A column electrode of amalgamated silver powder is used to reduce cystine quantitatively to cysteine, which is detected amperometrically at a mercury electrode. The double cell is applied to the detection of cystine, cysteine and penicillamine in high-pressure liquid chromatography and to the selective determination of cystine and cysteine by flow-injection analysis.