Optically active polymers containing side-chain photochromic moieties: Synthesis and chiroptical properties of copolymers of trans-4-(phenylazo)-1-naphthyl acrylate and trans-4-(1-naphthylazo)-phenyl acrylate with (?)-menthyl acrylate

The synthesis of photochromic optically active copolymers from trans-4-(phenylazo)-1-naphthyl acrylate (PANA), or trans-4-(1-naphthylazo)-phenyl acrylate (NAPA), and (?)-menthyl acrylate (MtA) is described. The copolymers prepared, having different contents of trans-phenylazonaphthalene moieties, have been characterized by IR, ¹H-NMR, UV, and GPC techniques. The chiroptical properties have been investigated by circular dichroism (CD) and the induced optical activity on the side-chain trans-phenylazonaphthalene chromophores discussed in terms of different conformational situations of the macromolecules in both the copolymer series. © 1994 John Wiley & Sons, Inc.     

Conformational Transformation Exhibited by the Peptide Extracted from Crystalline Region of Bombyx mori Silk Fibroin in Solid and Solution States

The conformational transformation of a 30-residue peptide H（Ala-Gly-Ser-Gly-AIa-Gly）5OH, i.e., （AGSGAG）5, extracted from highly crystalline region of Bombyx mori （B. mori） silk fibroin was described by using the high resolution solid state 13^C NMR, and CD spectroscopies. Based on the conformation-dependent 13^C NMR chemical shifts of the Ala, Gly and Ser residues and the line-shape analysis of the conformation sensitive Ala Cβ resonance, the peptide revealed a strong preference for silk Ⅱ structural form, i,e,, an antiparallel fl-sheet structure （φ= - 140±20°and ψ= 135±20°） in solid state. On the contrary, the CD spectra of this peptide in the two non-native hexafluorinated fibre spinning solvents, hexafluoroisopropanol （HFIP） and hexafluoroacetone （HFA）, exhibited the existence of an unusual tightly-folded conformation resembling 310-helix （φ=- 60±20° and ψ=-30±20°）, as judged from the R ratio of [θ]222/[θ]203 in HFIP solution, whereas a dynamically averaged unordered structure in HFA, Taken together, the information inclined to hypothesis that the primary structure of the highly crystalline regions of B. mori silk fibroin may be easily accessible to the large conformational changes, which in turn may be critical for facilitating the structural transformation from unprocessed silk fibroin （silk I form） to processed silk fiber （silk Ⅱform）.     

四面体型过渡金属配合物的构型与CD的关系

旋光性四面体型过渡金属配合物的圆二色光谱(CD)在d-d跃迁区的特征谱线反映了该类配合物的构型特征。从极化度的多级圆球不对称性模型出发,可将这类配合物的构型与CD在d-d跃迁区的特征谱线之间建立起直接的联系。     

Synthesis and spectral studies of 1,3-diketonate derivatives ofortho-palladated α-arylalkylamines

Synthesis of acetylacetonate derivatives of a series ofortho-palladated complexes based on secondary and tertiary -arylalkylamines was described. Their structures and stereochemistry were elucidated by IR, UV,¹H NMR, and CD spectra. Fragmentation processes of these complexes and some model compounds were studied by mass spectrometry (EI). An unusual rearrangement of a molecular ion involving migration of the hydrogen atom from the alkylaminoalkyl group to the palladium atom to form a hydride intermediate followed by the elimination of PdH was observed. The rearrangement occurs through isomerization of the ²-O,O-coordinated -diketonate ligand to the ¹-C-bonded diketonyl form to give the coordinationally unsaturated metal center.Translated fromIsvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 733–740. March, 1996.     

A Review on the Potential and Limitations of Recyclable Thermosets for Structural Applications

Abstract

The outstanding performance of conventional thermosets arising from their covalently cross-linked networks directly results in a limited recyclability. The available commercial or close-to-commercial techniques facing this challenge can be divided into mechanical, thermal, and chemical processing. However, these methods typically require a high energy input and do not take the recycling of the thermoset matrix itself into account. Rather, they focus on retrieving the more valuable fibers, fillers, or substrates. To increase the circularity of thermoset products, many academic studies report potential solutions which require a reduced energy input by using degradable linkages or dynamic covalent bonds. However, the majority of these studies have limited potential for industrial implementation. This review aims to bridge the gap between the industrial and academic developments by focusing on those which are most relevant from a technological, sustainable and economic point of view. An overview is given of currently used approaches for the recycling of thermoset materials, the development of novel inherently recyclable thermosets and examples of possible applications that could reach the market in the near future.     

Chiroptical detection. Novel possibilities of its application to enantiomers

Summary Polarimetric and/or circular dichroic detection of enantiomers after liquid chromatography on optically active sorberts has been used for the following purposes: determination of enantiomeric purity in spite of peak overlap, investigation of enantiomerization during chromatography, monitoring of racemizations and recording of circular dichrograms without preparative enrichment of enantiomers. Novel examples for all applications are give. The general prospects for chiroptical detection are discussed.     

Circular dichroism spectra of the inclusion complexes of phlorizin in cyclodextrins

Two aromatic rings of a phlorizin molecule form inclusion complexes with -CD and -CD. Induced circular dichroism spectra of these complexes have been measured to estimate the orientation of the two aromatic rings in the hydrophobic space of CDs. Apparent complex formation constants have been also estimated for each complex. It is concluded that phlorizin forms a stronger inclusion complex with -CD than with -CD.     

Helical poly(3-methyl-4-vinylpyridine)/amino acid complexes: preparation, characterization, and biocompatibility

Helical poly(3-methyl-4-vinylpyridine) (P3M4VP)/amino acid complexes have been prepared via acid-base reaction of the achiral polymer with D and L amino acids: alanine, leucine, valine, serine and phenylalanine. The circular dichroism (CD) spectra of P3M4VP/D- and L-alanine complexes in CH(3)OH/H(2)O show opposing (near mirror image) Cotton effect signals at 278.4, 274.8 and 270.8 nm, indicating the formation of enantiomeric secondary structures. The formation of the enantiomeric structures is supported by observed [alpha](D)(25) values of -3.0 and +3.0 for the P3M4VP/D-alanine and P3M4VP/L-alanine complexes, respectively. The preparation of helical P3M4VP/amino acid complexes has been carried out in CH(3)OH and H(2)O at pH 1.8 and 2.7. The intensities of the Cotton effect signals were good. For example, for the P3M4VP/L-alanine complexes in CH(3)OH/H(2)O and H(2)O (pH 1.8), the second Cotton effect signal around 275-277 nm show [theta;] values of 49 980 and 79 210 deg . cm(2) . dmol(-1), respectively. The formation of the helical secondary structure is rapid. The acid-base reaction between P3M4VP and L-alanine in CH(3)OH/H(2)O, in 10 min, show a CD spectrum with Cotton effect signals at 274 and 272 nm with [theta] values of 27,000 deg . cm(2) . dmol(-1) and -36,000 deg . cm(2) . dmol(-1), respectively. P3M4VP permits ready conformational reorientation on complexation with amino acids, but once the helical P3M4VP/amino acid complexes are formed, it is stable at room temperature. P3M4VP is not compatible with HeLa ovarian cancer cells, but the helical P3M4VP/amino acid complexes are compatible with HeLa cells. The complexes minimally interfere with the adhesion and growth of HeLa cells on complex surfaces. Helical poly(3-methyl-4-vinylpyridine)/D- and L-alanine complexes support the attachment and growth of HeLa cells. The micrographs shows HeLa cells after three days: left panel: on P3M4VP/L-alanine complex; right panel: on P3M4VP/D-alanine complex.     

卟啉超分子化合物在分子器件中的应用

分子电子器件已成为近年来的一个研究热点，卟啉类化合物因为光敏性好、性能稳定、易于修饰等优点成为分子器件研究的理想模型化合物。本文着重介绍了它在分子器件中的最新应用进展。     

稀土金属离子与人血清白蛋白的相互作用

本文用荧光光谱、紫外-可见吸收光谱法和循环伏安法研究了稀土金属离子Eu(Ⅲ)、Pr(Ⅲ)与人血清白蛋白(HSA)的相互作用。实验发现：Eu(Ⅲ)和Pr(Ⅲ)对HSA有较强的荧光猝灭作用。用Stern-Volmer方程分别对实验数据进行处理，结果发现：HSA与Eu(Ⅲ)、Pr(Ⅲ)发生反应生成了新的复合物，发生了分子内的非辐射能量转移。Eu(Ⅲ)、Pr(Ⅲ)对HAS的荧光猝灭作用，属于静态荧光猝灭。荧光猝灭图表明：Eu³⁺和Pr³⁺在HSA分子中至少有两类结合位点，Eu³⁺与HSA形成2.76∶1的复合物，结合常数lgK分别为12.03和9.05；Pr³⁺与HSA形成2.2∶1的复合物，结合常数lgK分别为9.89和6.97。同时用圆二色谱及同步荧光光谱法探讨了 Eu(Ⅲ)和Pr(Ⅲ)对HSA构象的影响。