Meldrum's acid and its analogs

2-Substituted or 2,2-disubstituted 4,6-dioxo-1,3-dioxanes, which are analogs of Meldrum's acid and were obtained by reaction of malonic acid with acetic anhydride and the appropriate carbonyl compound in the presence of sulfuric acid, exist in solution preferably in a single form according to the PMR and ¹³C NMR spectral data. Fluctuation of the CH₂ group is not observed. The mass spectra are characteristic and are distinguished by splitting out of the carbonyl compound from the molecular ion or successive splitting out of CO₂ and ketene molecules. The Meldrum acid analogs do not affect plant growth but have a depressive effect on the central nervous system of animals and low toxicity.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1482–1486, November, 1975.     

4a,6,7,8a-Tetrahydro-1,3-dithiolo[4',5':5,6]-1,4-dithiino [2,3-b]-1,4-dithiine-2-thione as a precursor for synthesis of new organic π-donors

[2+4[-Cycloaddition of 2,3-dihydro-1,4-dithiine and oligomeric 1,3-dithiol-2,4,5-trithione results in the formation of 4a,6,7,8a-tetrahydro-1,3-dithiolo[4',5':5,61-[1,4[dithiino[2,3-b[1,4-dithiine-2-thione, which is a precursor for synthesis of new organic rz-donors.Translated fromIzvestiya Akademi Nauk Seriya Khimicheskaya No. 3, pp. 775–776, March, 1996.     

聚醚醚酮酮和含联苯聚醚醚酮酮共聚物的熔融热

根据Ｆｌｏｒｙ热力学统计理论和比容－熔融热作国法，由ＤＳＣ结果得到了不同联苯含量的聚醚醚酮酮－含联苯聚醚醚酮酮（ＰＥＥＫＫ－ＰＥＢＥＫＫ）共聚物的熔融热，两种方法获得的结果吻合。在此基础上给出了ＰＥＥＫＫ－ＰＥＢＥＫＫ共聚物不同联苯含量的熔点计算表达式。结果还表明，随着联苯含量ｎＢ，的变化，明显改变；当ｎＢ＝０．３５时，ＰＥＥＫＫＰＥＢＥＫＫ共聚物的值最小。     

EPR study of the mechanism of interaction of NO and NO2 molecules with zeolite surfaces

The adsorption of the paramagnetic molecules of NO and NO₂ by zeolites in the alkali and alkaline earth cationic forms has been studied by EPR and reflectance spectroscopic methods. The change in the EPR spectra of adsorbed nitric oxide with increase in the degree of covering of the surface of the alkali cationic form of the zeolites, and also the nature of the change in the spectra when oxygen is adsorbed on zeolites on which NO has previously been adsorbed, indicate the existence of two types of adsorption center. At low degrees of covering of the surface, on the order of 10¹⁸ g^–1, as can be judged from the EPR spectra, the adsorbed NO molecule is strongly polarized and the unpaired electron is almost completely localized on the oxygen atom. At high degrees of covering, for an appreciable proportion of the NO molecules, the bond with the surface is weaker. In this case, the EPR spectra show a hyperfine structure (HFS) with a constant which changes with change in the cation in the order Li⁺ Na⁺ K⁺. The replacement of the singly charged Na⁺ by the doubly charged Ca²⁺ produces a marked change in the adsorption properties of the zeolite. The adsorption of NO on CaA leads not only to polarization of the adsorbed molecule but also to transfer of the electron from the nitrogen atom to the atoms of the adsorbent; this is recorded in the EPR spectrum in the form of an F-center. On further adsorption, the NO molecules are adsorbed both on the nitrogen atom and on the oxygen atom of the first molecule; thus, NO₂ and N₂O are formed.     

Aqueous dispersions of single-wall and multiwall carbon nanotubes with designed amphiphilic polycations

Poor solubility of single-walled and multiwalled carbon nanotubes (NTs) in water and organic solvents presents a considerable challenge for their purification and applications. Macromolecules can be convenient solubilizing agents for NTs and a structural element of composite materials for them. Several block copolymers with different chemical functionalities of the side groups were tested for the preparation of aqueous NT dispersions. Poly(N-cetyl-4-vinylpyridinium bromide-co-N-ethyl-4-vinylpyridinium bromide-co-4-vinylpyridine) was found to form exceptionally stable NT dispersions. It is suggested that the efficiency of macromolecular dispersion agents for NT solubilization correlates with the topological and electronic similarity of polymer-NT and NT-NT interactions in the nanotube bundles. Raman spectroscopy and atomic force and transmission electron microcopies data indicate that the polycations are wrapped around NTs forming a uniform coating 1.0-1.5 nm thick. The ability to wind around the NT originates in the hydrophobic attraction of the polymer backbone to the graphene surface and topological matching. Tetraalkylammonium functional groups in the side chains of the macromolecule create a cloud of positive charge around NTs, which makes them hydrophilic. The prepared dispersions could facilitate the processing of the nanotubes into composites with high nanotube loading for electronic materials and sensing. Positive charge on their surface is particularly important for biological and biomedical applications because it strengthens interactions with negatively charged cell membranes. A high degree of spontaneous bundle separation afforded by the polymer coating can also be beneficial for NT sorting.     

带甲基侧基的环氧树脂增容剂对炭黑在丁苯橡胶中分散度的影响

用自制的带甲基侧基的环氧树脂(TMBP)作为界面增容剂, 从拉伸性能、键合胶含量、动态性能、扫描电镜和流变性能等方面, 研究了TMBP对炭黑在丁苯橡胶中分散度的影响, 并与市售通用双酚A型环氧树脂(E-51)和橡胶工业常用软化剂邻苯二甲酸二辛酯(DOP)进行了比较. 结果表明, 带甲基侧基的环氧树脂TMBP在提高炭黑分散性方面的效果远比E-51好， 其作用模式具有典型的增容特性.     

Layer-by-layer assembly of nacre-like nanostructured composites with antimicrobial properties

In a recent report, we have presented the layer-by-layer (LBL) assembly of a biomimetic nanostructured composite from Na(+)-montmorillonite clay nanosheets and poly(diallylmethylammonium chloride) (Tang, Z.; Kotov, N.; Magonov, S.; Ozturk, B. Nat. Mater. 2003, 2, 413). The structure, deformation mechanism, and mechanical properties of the material are very similar to those of natural nacre and lamellar bones. This fact prompts further investigation of these composites as potential bone implants. LBL assembly affords preparation of multifunctional composites, and here we demonstrate that not only mechanical strength, but also antibacterial activity, can be introduced in these implantable materials by alternating clay layers with starch-stabilized silver nanoparticles. The resulting composite showed excellent structural stability with no detectable levels of silver lost over a 1 month period. Evaluation of the antibacterial properties showed almost complete growth inhibition of E. coli over an 18 h period. The amount of silver eluted from the LBL composite over a 1 month period was determined to be only 0.5-3.0 microg/L. This concentration of silver did not prevent the growth of the mammalian tissue cultures. The LBL composite has shown biocompatibility with the human osteoblast cell line.     

Structure and Electrochemical Properties of Cation-Exchange Membranes Based on Partially Imidized Polyamidoacid

The transport of water molecules and the distribution of functional groups in polyamidoacid carboxyl-containing cation-exchange membranes based on pyromellitic acid are studied by NMR and ESR techniques. It is shown that the self-diffusion coefficients of water differ in the gel and intergel regions. Structural parameters of conducting channels in the gel regions are determined. In electrodialysis of one-component and binary solutions, polyamidoacid membranes possess higher transport numbers and separation coefficients of counterions that are less hydrated in solution.