跨临界二氧化碳系统循环在食品行业中的应用与(火用)分析

食品的杀菌与储存是食品加工工艺中必须的两个环节。本文利用第二定律的[火用]分析法对满足食品加工特定水温参数需求的冷热联供CO2热泵与传统锅炉冷水机组进行火用分析比较，分析结果表明冷热联供CO2热泵的[火用]效率高于传统冷水机组[火用]效率相当。最后阐述了冷热联供CO2热泵在食品行业的应用前景。     

取代基位置对羟基[60]富勒烯吡咯烷衍生物空间结构的影响

为进一步认识羟基[60]富勒烯吡咯烷衍生物的空间结构,借助密度泛函考察了羟基取代位置和取代基数量对羟基[60]富勒烯吡咯烷衍生物空间结构的影响。结果显示,5种羟基[60]富勒烯吡咯烷衍生物的LUMO均集中在[60]富勒烯上,羟基出现在邻位时其衍生物的LUMO和HOMO能量差ΔE最小,而羟基在间位时其ΔE最大。吡咯烷键长和键角并不随羟基数量的增加而呈规律性的变化,但羟基取代基位置对吡咯烷键长和键角的影响由大到小的顺序是:对位、间位、邻位。     

微波辐射下离子液体［RMIm］PF6（R=P, B, C6）的合成及其电导率研究

在微波辐射下,1-甲基咪唑分别与有机卤盐（1-溴丙烷、1-溴丁烷、1-溴己烷）在80℃回流加热10min,可制得咪唑类离子液体的中间体溴代1-丁基-3-甲基咪唑（[BMIm]Br）、溴代1-丙基-3-甲基咪唑（[PMIm]Br）、溴代1-己基-3-甲基咪唑（[C6MIm]Br）,进一步与HPF6在室温搅拌反应4h,制得憎水性的咪唑类离子液体[BMIm]PF6,[PMIm]PF6和[C6MIm]PF6。对这3种离子液体及其在不同有机溶剂如丙酮、甲醇、乙酸乙酯中的电导率进行测定,发现离子液体的电导率受咪唑上取代基种类、溶剂种类、浓度和温度的影响,取代基的链越长,体积越大,离子液体的电导率越小。并且随温度升高和浓度的增大,离子液体的电导率也增大。     

1,1,1,3,5,5,5-七甲基-3-[2-(三甲氧基硅烷基)乙基]三硅氧烷的合成与表征

以七甲基三硅氧烷(MDHM)、乙烯基三甲氧基硅烷(VTMS)为原料,氯铂酸的异丙醇溶液为催化剂,采用硅氢加成反应,在氮气保护下合成1,1,1,3,5,5,5-七甲基-3-[2-(三甲氧基硅烷基)乙基]三硅氧烷(β-HTEOs),并用气相色谱-色谱连用(GC-MS)、核磁共振谱(1H-NMR、29 Si-NMR)、傅里叶红外变化光谱(FT-IR)对合成产物进行表征;通过探讨反应温度、反应时间、原料配比以及催化剂浓度对硅氢加成反应的影响,得到β-HTEOs合成的最优化条件,采用视频接触角仪测定其在玻璃基材上润湿铺展情况,表明β-HTEOs在玻璃基材上完全铺展,具有较低的表面张力.     

光交联型液晶光控取向材料

液晶光控取向材料是近年来国际上的一个研究热点,其中光交联型材料因其稳定性强、取向效果好等优点被广泛研究。文中综述了肉桂酸酯类、香豆素类、苯乙烯基吡啶类、苯乙烯基苯并吡咯酮类、二苯基乙炔类光交联型液晶光控取向材料的研究进展,并对其光化学反应机理进行了分析。     

一步法合成富勒烯[60]-纳米银复合物

AgNO3乙腈溶液注入热的苯甲醛,一步法合成了不同形貌和粒径的纳米银颗粒;硝酸银的乙腈溶液注入热的C60-二甲苯和苯甲醛混合液中,一步原位合成了富勒烯[60]-纳米银复合物。用X射线衍射(XRD)、透射电镜(TEM)、元素分析、傅里叶变换红外光谱(FT-IR)分析证实了富勒烯[60]-纳米银复合物的形成。对纳米银晶粒形成过程和富勒烯[60]-纳米银复合物的形成进行了初步的解释。     

金红石TiO2基质中[MoO4]2-基团的上转换发光

在978nm激光二极管的激发下，Mo掺杂的TiO2材料表现出很强的宽带上转换发光，该发光来源于[MoO4]^2-基团的激发态3T1，3T2能级到基态1Al能级的电子跃迁．X射线衍射表明样品为金红石单一相，红外吸收光谱证实了[MoO4]2-的存在．由光电子能谱推测体系中还含有低价态的Mo离子，它们提供了上转换得以进行的中间态．高温下的氧化还原处理会改变低价Mo的数量，从而严重影响样品的发光行为。     

N-甲基-2-(3-羟基苯基)[60]富勒烯吡咯烷衍生物的合成研究

利用1,3-偶极环加成反应,合成分离得到了一种C60吡咯烷衍生物:N-基-2-(3-羟基苯基)[60]富勒烯吡咯烷,通过单因素方法,探讨了反应条件对产物产率的影响,并得到了最佳工艺条件:反应物摩尔比(C60:3-羟基苯甲醛:N-甲基甘氨酸)为1:2:4,反应温度90℃,反应时间2h,产物的产率可达82%(以消耗的C60计).同时用Uv-Vis、FT-IR、1H-NMR、MS等测试手段表征了产物的结构.     

具有对称结构的硫杂杯芳烃氮杂衍生物的合成与配合性能

在普通杯芳烃中引入硫原子可以改善了普通杯芳烃的配合性能。通过对叔丁基硫杂杯[4]芳烃与溴乙酸乙酯反应生成杯芳烃酯类衍生物2,继续在水合肼中肼解,得到硫杂杯[4]芳烃酰肼衍生物3,酰肼衍生物3与5,5-亚甲基二水杨酰基二水杨酰氯发生缩合反应,合成了具有对称桥连结构的硫杂杯[4]芳烃桥联氮杂衍生物5。所合成的新化合物的结构经1H NMR、元素分析、ESI-MS等证实。同时探讨了新型硫杂杯[4]芳烃衍生物5与系列-α氨基酸的配合性能。     

以跨临界CO_2-离子液体[bmim]PF_6为工质对的吸收式制冷循环性能分析

选择跨临界CO2-[bmim]PF6作为新型的吸收式制冷工质对,考察了CO2在离子液体[bmim]PF6中的溶解度和CO2-[bmim]PF6工质体系的热物性.计算了在给定工况下循环的制冷特性并对结果进行了分析与讨论.     

Synthesis of Several Pyrrolidinofullerenes Containing Structural Units of Natural Amino Acids

The paper reports on the investigation of reactivity of various imines prepared from esters of alanine, phenylalanine and tyrosine, and various aromatic aldehydes in reactions with [60]fullerene. Almost all imines studied were found not to undergo [2+3]cycloaddition reactions with C₆₀ under continuous reflux in 1,2-dichlorobenzene because of steric hindrances of the substrates. However, imines of pyridine-2-carboxaldehyde readily reacted with C₆₀ to form corresponding pyrrolidinofullerenes with moderate yields. The promoting effect of 2-pyridyl group in the [2+3]cycloaddition reactions was observed as a result of the formation of intramolecular hydrogen bonds in azomethine ylides formed.     

Progress in Fullerene Chemistry: From Exohedral Functionalization to Heterofullerenes

Various types of cycloaddition such as [2+1], [2+3], and Diels-Alder reactions have been investigated for the purpose of exohedral functionalization of [60]fullerene and also in few cases of [70]fullerene. Thermal and photochemical activation have been used and lead to a variety of new fullerene derivatives which may be further functionalizable. In addition, a new approach to aza-heterofullerenes has been developed starting from an exohedrally activated fullerene.     

Nanoencapsulation of [60]Fullerene with the Cavitand Cucurbit[7]uril

Novel supramolecular nanocapsules consisting of [60]fullerene and the macrocycle cucurbit[7]uril via self-assembly are reported. The nanocapsules, which were synthesized in a two-phase reaction at room temperature, were obtained in good yields. The stoichiometry of the product was found to be 1:2.     

Progress in Fullerene Chemistry: From Exohedral Functionalization to Heterofullerenes

Abstract

Various types of cycloaddition such as [2+1], [2+3], and Diels-Alder reactions have been investigated for the purpose of exohedral functionalization of [60]fullerene and also in few cases of [70]fullerene. Thermal and photochemical activation have been used and lead to a variety of new fullerene derivatives which may be further functionalizable. In addition, a new approach to aza-heterofullerenes has been developed starting from an exohedrally activated fullerene.     

Synthesis of Calix[4, 5, 6] Resorcinarenes Using Fullerene C60 as Template

We present a new use of fullerene C₆₀ as a template for the synthesis of cyclic resorcinarenes, The cyclocondensation of 2-methyl-resorcinol with benzaldehyde and hexanal in THF, catalyzed by AlCl₃, in the presence of 1%, 5%, and 10% fullerene C₆₀, produces calix[4], [5], and [6] resorcinarenes, with the pentamer and hexamer as the major products. The resorcinarenes were characterized by ¹H, ¹³C NMR, FTIR, FAB⁺ mass spectrometry, and elemental analysis.     

The Solid-State Mechanochemical Reaction of Fullerene C60

The solid-state mechanochemical reaction of fullerene C₆₀ by the use of a high-speed vibration milling technique has been applied to the nucleophilic addition of an organozinc reagent to C₆₀, [4+2] cycloaddition of C₆₀ with condensed aromatic hydrocarbons, 1,3-dipolar addition of C₆₀ with organic azides, and dimerization of C₆₀.     

The Solid-State Mechanochemical Reaction of Fullerene C60

Abstract

The solid-state mechanochemical reaction of fullerene C₆₀ by the use of a high-speed vibration milling technique has been applied to the nucleophilic addition of an organozinc reagent to C₆₀, [4+2] cycloaddition of C₆₀ with condensed aromatic hydrocarbons, 1,3-dipolar addition of C₆₀ with organic azides, and dimerization of C₆₀.     

Studies on Protein–[60]Fullerene Interactions: The Lysozyme–[60]Fullerene Model System

Abstract

A lysozyme–[60]fullerene adduct was synthesized and isolated for the first time. This adduct was water‐soluble and showed strong interaction between lysozyme and [60]fullerene and was characterized by UV‐VIS and fluorescence energy transfer technique. Keeping possible biomedical applications of [60]fullerene in view, the protein–[60]fullerene interactions were studied taking lysozyme as a model protein.     

Hydrogen Bonding Self-Assembly of Functionalized [60]Fullerene with a Barbituric Acid Derivative

A new supramolecular system of functionalized [60]fullerene bearing one 2,6-diaminopyridine moiety with a barbituric acid derivative was constructed through six-point hydrogen-bonding interaction. The self-assembly systems were studied by ¹H NMR, UV-Vis spectra, and a SEM image.     

Synthesis of Calix[4, 5, 6] Resorcinarenes Using Fullerene C60 as Template

Abstract

We present a new use of fullerene C₆₀ as a template for the synthesis of cyclic resorcinarenes, The cyclocondensation of 2‐methyl‐resorcinol with benzaldehyde and hexanal in THF, catalyzed by AlCl₃, in the presence of 1%, 5%, and 10% fullerene C₆₀, produces calix[4], [5], and [6] resorcinarenes, with the pentamer and hexamer as the major products. The resorcinarenes were characterized by ¹H, ¹³C NMR, FTIR, FAB⁺ mass spectrometry, and elemental analysis.