冠醚化合物做为晶体生长的物理成熟剂

本文在制备AgBr八面体乳剂初液中,加入一系列不同量的1,7,10,16-四氧-4,13-二硫代杂环十八烷(2S-18-C-6),结果由于(2S-18-C-6)与银离子产生了络合,降低了乳剂成核的过饱和度,所得乳剂的颗粒大小与加入2S-18-C-6的量成正比。由于所得乳剂颗粒大小分布产生了变化,而使乳剂的光化学性质以及介电损耗也产生了规律性的变化。同时还发现,在乳剂成熟过程中,加入含杂质原子不同的冠醚化合物1,4,7,10,13,16-六氧环十八烷(18-C-6),1,7,10,16-四氧-4,13-二氮代杂环十八烷(2N-18-C-6),N-对甲苯磺酰基-7-氮杂-1,4,10,13-四氧硫杂环十六烷(NTsTTH)对晶体的物理成熟作用有很大差异,2S-18-C-6是很好的物理成熟剂,2N-18-C-6、NTsTTH是AgBr的溶剂,18-C-6的成熟作用很弱,说明冠醚化合物对AgBr的溶解成熟作用与其环上所含杂原子有关。     

二环己基并-18-冠-6合成工艺的改进

报道了改进的二环己基并-18-冠-6(DCH-18-C-6)合成方法,并用该法实现了DCH-18-C-6的工业规模合成。对由二苯并-18-冠-6加氢合成DCH-18-C-6的反应中使用的Picher-钌催化剂进行了改性,用pH 3~5条件下新制备的Picher-钌催化剂,将反应温度提高并控制在130~140℃之间,可使氢化产率由文献报道的最高65%提高到85%以上,还显著提高了产物中DCH-18-C-6的立体异构体A(cis-syn-cis)含量。建立了用气相色谱法测定DCH-18-C-6异构体含量的方法,并用正庚烷进行结晶以实现A(cis-syn-cis)的提纯。     

多种结构手性化合物在键合纤维素-(4-甲基苯甲酸酯)手性固定相上的拆分比较

分别以4,4'-二苯基甲基二异氰酸酯和六亚甲基二异氰酸酯作为连接臂,采用6-位选择键合法,将纤维素衍生物分别键合到硅胶和氨丙基硅胶的表面,制备了4种键合型纤维素-(4-甲基苯甲酸酯)手性固定相,比较了10个手性样品在所得手性固定相上的拆分结果,考察了不同键合试剂、不同载体条件对所得固定相手性识别能力的影响;同时考察了在...     

十八烷基二甲基苄基氯化铵从碱性氰化液中固相萃取金的研究

基于十八烷基二甲基苄基氯化铵(BDMSAC)与Au(CN)-2络阴离子生成的离子缔合物可被C18反相键合硅胶固相萃取柱萃取、富集,建立了一种从碱性氰化液中高富集倍数固相萃取金的方法。该方法用于从碱性氰化液中固相萃取痕量金,萃取回收率可超过98%,同时研究了C18反向固相萃取金的机理,也创造性地提出了一种从碱性氰化液中提取金的新工艺。     

6种手性化合物在键合型直链淀粉苯基氨基甲酸酯类手性固定相上的拆分比较

自制了3种键合型直链淀粉苯基氨基甲酸酯类(苯基氨基甲酸酯IAT、3-氯苯基氨基甲酸酯IAC、3,5-二甲基苯基氨基甲酸酯IAD)手性固定相,比较了3种固定相对6种手性化合物的手性识别能力,同时也将商品柱Chiralcel OD-H、Chiralcel AD-H对6种手性化合物的拆分结果进行了比较。实验结果表明:所合成的键合型手性固定相对样品托儿格碱、2-羟基-3-(2-萘氧基)丙基-2',3'-二甲基苯基硒醚和戊唑醇表现出更好的手性识别能力,并且直链淀粉衍生物苯环上引入吸电子基团或给电子基团对固定相手性识别能力均有明显的影响。     

HPLC级二氧化硅微球的制备及其功能化

采用酸-碱催化的溶胶-凝胶法制备二氧化硅微球,系统探索了水用量、乙醇用量、旋蒸温度、搅拌速度和致孔剂种类对二氧化硅微球形态和粒径分布的影响。将制得的二氧化硅微球经简单沉降筛分及功能化后,获得了C18键合硅胶、亲水C18键合硅胶、氨丙基键合硅胶、乙二胺-N-丙基键合硅胶4种键合硅胶。结果表明:最佳的二氧化硅微球制备条件为,n(H2O)∶n[正硅酸乙酯(TEOS)]=6∶4,V(Et OH)∶V(TEOS)=3∶5,旋蒸温度为57℃,搅拌速度为2190 r/min,致孔剂为N,N-二甲基甲酰胺(DMF)。所制二氧化硅微球球形度好、粒径分布为3~10μm、比表面积为464.11 m2/g、孔体积为1.14 m3/g、平均孔径为9.81 nm,且孔径分布窄、硅羟基含量高达0.5450 mmol/g。C18键合硅胶和亲水C18键合硅胶的柱效分别为53474/m和86984/m(以甲苯计),且对分析物的分离良好。氨丙基键合硅胶和乙二胺-N-丙基键合硅胶的离子交换容量分别为1.44和1.22 mmol/g,对甲苯磺酸吸附量分别为240.8和217.6 mg/g。     

键合纤维素手性固定相的合成及手性拆分

合成了键合型纤维素-（二苯基甲基二氨基甲酸酯,苯基氨基甲酸酯）手性固定相,并用此键合柱在流动相正自己烷／异丙醇下对几种手性化合物进行了拆分,实验结果表明,此手性固定相具有一定的拆分能力。     

酸-碱催化法制备HPLC级二氧化硅微球及其十八烷基化和氨基化

采用酸-碱催化的溶胶-凝胶法制备二氧化硅微球,系统探索了水量、乙醇量、旋蒸温度、搅拌速度和致孔剂的种类对二氧化硅微球形态和粒径分布的影响,并采用显微镜、比表面积分析仪、滴定法和红外光谱法对二氧化硅微球结构进行了表征。将制得的二氧化硅微球经简单沉降筛分及功能化后,获得了四种填料C18键合硅胶、亲水C18键合硅胶、氨丙基键合硅胶、乙二胺-N-丙基键合硅胶。结果表明：最佳的二氧化硅微球制备条件为,n(H2O):n(TEOS)=6/4,V(EtOH):V(TEOS)=3/5,旋蒸温度为57 ℃,搅拌速度为2190 r/min,致孔剂为DMF。所制二氧化硅微球球形度好、粒径分布为3～10 μm、比表面积为464.11 m2/g、孔体积为1.14 m3/g、平均孔径为9.81 nm且孔径分布窄、硅羟基含量高达0.5450 mmol/g。C18键合硅胶和亲水C18键合硅胶的柱效分别为53474/m和86984/m（以甲苯计）,且对分析物的分离良好。氨丙基键合硅胶和乙二胺-N-丙基键合硅胶的离子交换容量分别为1.44和1.22 mmol/g,对甲苯磺酸吸附量分别为240.8和217.6 mg/g。     

固—固相储能材料的研究

研究了四氯合金属（Ⅱ）酸二正十八烷胺（n-C18H37NH3)2MCl4(M=Mn^2 、Cu^2 、Ee^2 、Cd^2 、Ni^2 和Co^2 )和二氯二正十八烷胺合铜（Ⅱ）（n-C18H37NH2)2CuCl2类化合物的合成、表征和固-固相转变的研究,并测定了该类化合物的热分解反应动力学参数。在350-390K温度区间,该类化合物具有80-100kJ/mol的固-固摩尔相变焓,是一类具有开发前途的的固-固相变低温储能材料。     

苯基键合硅胶萃取黄酮化合物的性能研究

以苯基三氯硅烷和硅胶为原料制得苯基键合硅胶固相萃取材料,采用扫描电镜、元素分析、比表面积/孔径分析、红外光谱等对其进行了结构表征。装填固相萃取小柱,以4个黄酮模型化合物为目标分析物,研究苯基键合硅胶的萃取性能。对上样体积、上样速度、上样pH、洗脱剂类型、洗脱体积、洗脱速度等萃取参数进行了优化,并建立了苯基键合硅胶富集萃取黄酮化合物的高效液相色谱分析检测方法。实验证实该方法具有宽的线性范围(1~200μg/L)、低的检出限(0.25μg/L),并成功应用于2种实际样品中黄酮化合物的富集检测。上述结果说明苯基键合硅胶是一种对黄酮化合物具有良好萃取性能的固相萃取材料。     

冠醚化合物对乳剂晶体外延生长的调变作用

本工作研究了冠醚化合物在外延乳剂生长过程中的调变作用。结果表明，１，４，７，１０，１３，１６－六氧杂环十八烷对ＡｇＢｒ八面体乳剂无侵蚀作用，对非同晶系晶体之间的外延不起调变作用。１，７，１０，１６－四氯－４，１３－二氮代杂环十八烷均使ＡｇＢｒ八面体乳剂的棱角产生了不同程度的侵蚀，可充当不同晶系晶体外延生长的调变剂，对晶体的溶解侵蚀能力依２Ｓ－１８－Ｃ－６，２Ｎ－１８－Ｃ－６，１８－Ｃ－６的次序降低     

Synthesis of crosslinked chitosan-crown ethers and evaluation of these products as adsorbents for metal ions

Two new crosslinked-crown ethers (CCTS-N=CH-B-15-C-5 and CCTS-N=CH-B-18-C-6) were synthesized by the reaction of crosslinked chitosan (CCTS-NH₂) with 4`-formyl benzo-15-crown-5 and 4`-formyl benzo-18-crown-6. Their structures were confirmed with elemental analysis, infrared spectra analysis, solid-state ¹³C NMR analysis, X-ray diffraction analysis, and differential scanning calorimetry thermogram analysis. In the infrared spectra of CCTS-N=CH-B-15-C-5 and CCTS-N=CH-B-18-C-6, the characteristic peak of C=N stretch vibration appeared at 1650 cm⁻¹. The X-ray diffraction analysis showed that the peak at 2θ = 20° decreased greatly in CCTS-N=CH-B-15-C-5 and CCTS-N=CH-B-18-C-6. In the ¹³C NMR spectra of CCTS-N=CH-B-15-C-5 and CCTS-N=CH-B-18-C-6, the characteristic peak of aromatic carbon appeared at 128-ppm, the characteristic peak of carbon in the C=N group appeared at 151 ppm. The adsorption and selectivity properties of CCTS-N=CH-B-15-C-5 and CCTS-N=CH-B-18-C-6 for Ag⁺, Pd²⁺, Pb²⁺, Cd²⁺, and Cr³⁺ were studied. The experimental results showed that the two crosslinked chitosan-crown ethers have not only good adsorption capacities for Ag⁺ and Pd²⁺, but also high selectivity for the adsorption of Ag⁺ or Pd²⁺ with the coexistence of Pb²⁺ and Cr³⁺. The selectivity coefficients of CCTS-N=CH-B-15-C-5 and CCTS-N=CH-B-18-C-6 were respectively. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 501–506, 1998     

中性冠醚载体在乳化液膜技术中的应用

在大环多元醚应用方面,实现了以DB-18-C-6为载体,乳化液膜法分离钾、钠离子的工艺.实验结果表明,内水相试剂、外水相中阴离子的性质、膜相溶剂以及冠醚与金属阳离子的匹配均对乳化液膜的提取效果有极大的影响.扩散控制的传质模型与实验结果有较好的一致性.     

Influence of various cations on redox behavior of I and I3 and comparison between KI complex with 18-crown-6 and 1,2-dimethyl-3-propylimidazolium iodide in dye-sensitized solar cells

In this paper, we studied the influence of different cations on redox behavior of I⁻ and I₃⁻ by cyclic voltammetry and electrochemical impedance spectroscopy. It was demonstrated that increasing cation size tends to give rise to higher reductive activity of I⁻ and lower diffusion coefficient of I₃⁻ in these cations, alkylimidazolium, [Na ⊂ 15-C-5]⁺ and [K ⊂ 18-C-6]⁺. Moreover, we measured the performance of dye-sensitized solar cells (DSCs) with electrolyte containing [K ⊂ 18-C-6]I or 1,2-dimethyl-3-propylimidazolium iodide (DMPII). It was found that dye-sensitized solar cells (DSCs) with [K ⊂ 18-C-6]I give a little higher short-circuit photocurrent density and a little lower fill factor than DSCs with DMPII.     

FPEX γ‐Radiolysis in the Presence of Nitric Acid

Abstract

The solvent formulation known as FPEX (Fission Product Extraction) contains calix[4]arene‐bis‐(tert‐octylbenzo‐crown‐6) (BOBCalixC6) for Cs extraction; 4,4′,(5′)‐di‐(t‐butyldicyclohexano)‐18‐crown‐6 (DtBuCH18C6) for Sr extraction; 1‐(2,2,3,3,‐tetrafluoropropoxy)‐3‐(4‐sec‐butylphenoxy)‐2‐propanol (Cs‐7SB) modifier and trioctylamine (TOA) to aid in Cs stripping, all in an Isopar L diluent. This formulation has favorable extraction efficiency for Cs and Sr from acidic solution, and was investigated here for γ‐radiation stability. When FPEX was irradiated in contact with aqueous nitric acid, the extraction efficiency decreased only slightly when irradiated to absorbed doses as high as 200 kGy. The color of the organic phase changed to a deep yellow‐orange, and several new peaks related to radiolysis of the Cs‐7SB modifier were detected by GC‐ECD analysis. This had little effect on the solvent extraction distribution ratios. Possible reasons for this unexpected robustness under conditions of high radiation and acidity are discussed.     

Physical Chemical Properties of Shea/Cocoa Butter Blends and their Potential for Chocolate Manufacture

Cocoa butter (CB) is the preferred fat for chocolates and confections. However, for technological and economic reasons, there have been strong efforts for partially replacing it. As shea butter (SB) has become an important natural source of symmetrical stearic-rich triacylglycerols (TAG), the aim of this work was to study physical chemical behavior of blends of CB and SB and the dynamic mechanical and polymorphic behaviors of chocolates prepared with these systems as added fat. The compatibility of SB and CB blends was studied using the isosolid diagram. Data showed that softening occurred due to both dilution effects and a slight eutectic formation. Chocolates formulated with a fat phase consisting in CB, or SB, or blends with 10, 20, or 30 wt.% SB in CB showed different polymorphic behaviors during storage. The polymorphic transition from β₂ to β₁ occurred to a greater extent with increasing content of SB in formulation. Dynamic mechanical analysis (DMA) results agree with X-ray findings. E′ modulus significantly increased during storage most likely due to formation of β₁ form. As shown by Grazing incidence wide-angle X-ray scattering (GIWAXS) studies, crystals preferred growing on the chocolate surface than on bulk chocolate. However, even after a year at 18°C, chocolates had good appearance indicating that SB was a good CB extender.     

超声波合成法制备二苯并-18-冠-6

采用超声波合成法,以邻苯二酚和二甘醇二(对甲基苯磺酸)酯为原料,二甲基亚砜为溶剂,氢氧化钾为催化剂兼模板,合成二苯并-18-冠-6,通过IR和HNMR鉴定,收率达到41.67%。较之传统方法具有操作简单、反应时间短、反应条件温和等优势。     

Carbon black nanoparticle instillation induces sustained inflammation and genotoxicity in mouse lung and liver

Background

Widespread occupational exposure to carbon black nanoparticles (CBNPs) raises concerns over their safety. CBNPs are genotoxic in vitro but less is known about their genotoxicity in various organs in vivo.

Methods

We investigated inflammatory and acute phase responses, DNA strand breaks (SB) and oxidatively damaged DNA in C57BL/6 mice 1, 3 and 28 days after a single instillation of 0.018, 0.054 or 0.162 mg Printex 90 CBNPs, alongside sham controls. Bronchoalveolar lavage (BAL) fluid was analyzed for cellular composition. SB in BAL cells, whole lung and liver were assessed using the alkaline comet assay. Formamidopyrimidine DNA glycosylase (FPG) sensitive sites were assessed as an indicator of oxidatively damaged DNA. Pulmonary and hepatic acute phase response was evaluated by Saa3 mRNA real-time quantitative PCR.

Results

Inflammation was strongest 1 and 3 days post-exposure, and remained elevated for the two highest doses (i.e., 0.054 and 0.162 mg) 28 days post-exposure (P < 0.001). SB were detected in lung at all doses on post-exposure day 1 (P < 0.001) and remained elevated at the two highest doses until day 28 (P < 0.05). BAL cell DNA SB were elevated relative to controls at least at the highest dose on all post-exposure days (P < 0.05). The level of FPG sensitive sites in lung was increased throughout with significant increases occurring on post-exposure days 1 and 3, in comparison to controls (P < 0.001-0.05). SB in liver were detected on post-exposure days 1 (P < 0.001) and 28 (P < 0.001). Polymorphonuclear (PMN) cell counts in BAL correlated strongly with FPG sensitive sites in lung (r = 0.88, P < 0.001), whereas no such correlation was observed with SB (r = 0.52, P = 0.08). CBNP increased the expression of Saa3 mRNA in lung tissue on day 1 (all doses), 3 (all doses) and 28 (0.054 and 0.162 mg), but not in liver.

Conclusions

Deposition of CBNPs in lung induces inflammatory and genotoxic effects in mouse lung that persist considerably after the initial exposure. Our results demonstrate that CBNPs may cause genotoxicity both in the primary exposed tissue, lung and BAL cells, and in a secondary tissue, the liver.