Synthesis,x-ray diffraction and spectral studies of the nitrone form of 3-methyl-4-nitro-2-oximino-3-thiolene-1,1-dioxide

Stabilization of the NH-nitrone grouping in oximino compounds is promoted by the inclusion of the conjugated system in the heterocycle. IR spectroscopy fails to distinguish between the oxime and nitrone forms of oximino compounds. The best evidence for the existence of the nitrone form is provided by x-ray diffraction examination of the monocrystals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2312–2319, October, 1989.     

Thermoreversible gelation of syndiotactic polystyrene: Effect of solvent type

The temperature-concentration phase diagrams of syndiotactic polystyrene (sPS)/benzene gels and sPS/toluene gels establish the existence of two polymer-solvent compounds in both systems. In particular it is found that the sto ichiometries of the compounds differ with the type of solvent: The stoichiometrics, expressed as solvent molecules/monomer are respectively for the benzene 4/1 and 1/1 and for the toluene 0.8/1 and 1/4. Neutron diffraction patterns allow us to confirm the existence of differents compounds in sPS/toluene gel and sPS/benzene gel.     

Smectic A phases with strings of interdigitated molecules in swallow tailed compounds

X-ray diffraction studies are reported of smectic A phases exhibited by swallow-tailed compounds. The special molecular shape consisting of regions having differing space filling requirements results in antiparallel packing of the molecules; this influences the conformations of the alkyl chains. The layer spacings show unusually good agreement with the molecular lengths and this is the case for molecules with long and short aliphatic chains. We have observed also an additional incommensurable structural element which we believe to be unique for non-polar, low molar mass compounds. The X-ray diffraction patterns provide evidence for the existence of strings of interdigitated molecules.     

Room Temperature Modulated Structure of Ca and K co-Doped LaMnO3

A series of perovskite compounds of La_1-x-yCa_xK_yMnO₃ was prepared by hydrothermal disproportionation reaction of MnO₂. The three oxidation states of manganese(Mn³⁺, Mn⁴⁺ and Mn⁵⁺) can stably exist in the compounds. Under room temperature conditions, twice and three times modulated structure produced by the charge ordering can be observed by X-ray diffraction(XRD), select area electron diffraction(SAED) and high resolution transmission electron microscopy(HR-TEM). The splits of the diffraction peaks of the single crystals confirmed by synchrotron X-ray diffraction experiment are in accordance with those of the powder sample. The existence of the different oxidation states of Mn³⁺, Mn⁴⁺ and Mn⁵⁺ can be considered to be the dominating reason of the complicated room temperature modulated structure.     

Achiral diacrylate with an anticlinic smectic phase

We present an achiral diacrylate that shows a phase transition from the synclinic smectic C phase (SmC) to the anticlinic smectic C (SmCalt). This last phase has been previously reported only for swallow-tailed or dimeric compounds. Our studies using differential scanning calorimetry, X-ray diffraction, polarizing optical microscopy and broad band dielectric spectroscopy suggest the existence of this mesophase in this bifunctional smectogen.     

Achiral diacrylate with an anticlinic smectic phase

We present an achiral diacrylate that shows a phase transition from the synclinic smectic C phase (SmC) to the anticlinic smectic C (SmCalt). This last phase has been previously reported only for swallow-tailed or dimeric compounds. Our studies using differential scanning calorimetry, X-ray diffraction, polarizing optical microscopy and broad band dielectric spectroscopy suggest the existence of this mesophase in this bifunctional smectogen.     

Paracetamol-propyphenazone interaction and formulation difficulties associated with eutectic formation in combination solid dosage forms

Polymorphic behaviours of paracetamol and propyphenazone and interaction between these two compounds were investigated using differential scanning calorimetry (DSC), X-ray powder diffraction and Fourier transform-infrared (FT-IR)-spectroscopy. Binary mixtures containing various ratios of the compounds were prepared as physical and fused mixtures and analysed by DSC to study their thermal behaviours. Phase diagrams obtained from the melting endotherms of the binary mixtures demonstrated formation of an eutectic mixture at a paracetamol-propyphenazone combination of about 35:65 (w/w) with an eutectic temperature of 56 degrees C. The FT-IR spectroscopy revealed no chemical interaction due to eutectic formation, and a lower degree of crystallinity of the eutectic mixture than individual substances was observed by X-ray powder diffraction analysis. The DSC and X-ray powder diffraction data demonstrated a polymorphic change in propyphenazone as a result of melting of the compound. Tablets, containing both paracetamol and propyphenazone in a combination formulation and prepared using standard wet granulation technology, were found to have physical instability when packed in either polyvinylchloride// aluminium or polyvinylchloride/polyvinyldienechloride// aluminium blisters and stored for one month at 40 degrees C with either 75% relative humidity or without any humidity control. The instability of the tablets was more apparent under the high humidity condition.     

Intramolecular electrophilic rearrangements in saturated acyclic systems. Reactivity of the zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate with respect to different types of electrophiles

The reactions of the zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate with mercuric chloride and aryl isothiocyanates containing Cl atoms in the ortho positions of the benzene ring follow an unusual pathway because this zwitterion represents latent triisopropylphosphine due to the reversibility of the reaction of triisopropylphosphine with ethyl 2-cyanoacrylate. The molecular structures of the adducts of triisopropylphosphine with 2,6-dichloro- and 2,4,6-trichlorophenyl isothiocyanates were confirmed by X-ray diffraction study. Protonation of the adduct of triisopropylphosphine with 2,6-dichlorophenyl isothiocyanate occurred at the nitrogen atom, whereas methylation with methyl trifluoromethanesulfonate afforded an S-methylation product. The results of X-ray diffraction study of the resulting compounds are presented.     

Synthesis and optical properties of new inorganic phosphate matrices

We have developed the chemical conditions to prepare highly concentrated mixtures of different metallic chlorides (Sn, Al, Cr) and phosphoric acid. We let them dry at room temperature for bulk materials, but for films the temperature of drying can reach 400°C. The structure of bulk compounds have been examined through elastic neutron diffraction experiments correlated with X ray diffraction at large angle. These compounds are amorphous and we observed, using the differential scanning calorimetry at low temperature, that T _g values can be determined at more than 100 K below room temperature. This material could be considered as a liquid glass at room temperature. Several other metallic elements are under progress to determine if this behavior is depending on the nature of the element.Bulk materials have been codoped with a dye (oxazine) and trivalent erbium ion. By UV excitation of the dye we observed the absorption spectrum Er³⁺ in the emission band of oxazine, that is an evidence of the energy transfer effect.Films made by spin coating technique have been doped with Dispersed Red 1 (DR 1). We studied the effect of organic additives (hydrosolubles polymers like PVP) on the kinetics of photoisomerisation of DR 1.Films are also used as waveguide. Several modes have been observed and their refractive index values determined.     

Phase relationships in the Ce-Pd-In system

The interaction of cerium with palladium and indium was studied, and the 773°C isothermal section of the Ce-Pd-In phase diagram was plotted using physicochemical methods: X-ray powder diffraction, single-crystal X-ray diffraction, and electron probe microanalysis. The existence of 12 ternary intermetallic phases in the title system was confirmed, and three new phases were discovered. Crystal structure was determined for seven intermetallic compounds. A single-crystal X-ray diffraction study of CePdIn was carried out for the first time. A high-temperature phase CePdIn₄ was found, and its crystal structure was solved.     

Interdigitated smectic A and B mesophases in higher homologues of the 5O.m series

We report the synthesis, characterization and structural studies of the higher homologues of N(4-n-pentyloxybenzylidene)4-n-alkylaniline compounds, viz. 5O.12, 5O.14 and 5O.16 by thermal microscopy, differential scanning calorimetry and X-ray diffraction. The compounds exhibit N-S_A-S_B, N-S_A-S_B and N-S_A phase sequence variants, respectively. The X-ray results reveal the existence of an interdigitated smectic A phase in 5O.16 and smectic B phase in 5O.14. Results are discussed in light of the available data on the nO.m series     

Structural characterization of organosiloxane liquid crystals with a transverse or longitudinal dipole

In this work we report the characterization of two organosiloxane liquid crystalline compounds by means of DSC, polarizing optical microscopy and X-ray diffraction. These compounds can be used for dye guest-host ferroelectric displays. We focus this investigation on the molecular organization of the SmC phases of the two pure compounds to help elucidate the physical behaviour of mixtures with different concentrations of the dye and the guest host. The existence of longitudinal and transverse dipoles in the molecules of the dye and the chiral guest-host respectively are responsible for the different molecular organizations in the SmC mesophases of each compound. Taking into account the experimental results and the complexity of the molecules, we present coherent models to explain the molecular arrangements in the mesophases of both compounds.     

Structural characterization of organosiloxane liquid crystals with a transverse or longitudinal dipole

In this work we report the characterization of two organosiloxane liquid crystalline compounds by means of DSC, polarizing optical microscopy and X-ray diffraction. These compounds can be used for dye guest-host ferroelectric displays. We focus this investigation on the molecular organization of the SmC phases of the two pure compounds to help elucidate the physical behaviour of mixtures with different concentrations of the dye and the guest host. The existence of longitudinal and transverse dipoles in the molecules of the dye and the chiral guest-host respectively are responsible for the different molecular organizations in the SmC mesophases of each compound. Taking into account the experimental results and the complexity of the molecules, we present coherent models to explain the molecular arrangements in the mesophases of both compounds.     

用离子交换法合成谷氨酸/锌铝层状双氢氧化物纳米复合材料研究

采用离子交换法实现了谷氨酸(Glu)插层到ZnAl层状双氢氧化物(ZnAl-LDH)中而形成Glu/ZnAl-LDH纳米复合材料,并用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱、透射电子显微镜(TEM)以及热失重-差热(TG-DTA)分析等测试技术,研究了交换时间对Glu/ZnAl-LDH纳米复合材料结构的影响。 发现当交换时间为1 d时,Glu/ZnAl-LDH纳米复合材料粒子的结晶度好,Glu分子均以垂直形式插入,此时Glu在层间达到交换平衡。 当交换时间为2 d时,部分Glu开始以水平方式插入ZnAl-LDH纳米材料层间。 但当交换时间进一步延长时,ZnAl-LDH纳米材料的结构发生部分坍塌,而且ZnAl-LDH纳米材料在微酸性的Glu溶液中发生部分溶解而使其六边形的结构出现破损。 由于Glu插入ZnAl-LDH纳米复合材料层间后,其稳定性得到提高,因此,ZnAl-LDH纳米材料可以作为优良的生物分子的载体和储存器。     

Synthesis and antibacterial evaluation of New N-acylhydrazone derivatives from dehydroabietic acid

A series of new N-acylhydrazone derivatives were synthesized in good yields through the reactions of dehydroabietic acid hydrazide with a variety of substituted arylaldehydes. The structures of the synthesized compounds were confirmed by IR, 1H- and 13C-NMR, ESI-MS, elemental analysis and single crystal X-ray diffraction. From the crystal structure of compound 4l, the C=N double bonds of these N-acylhydrazones showed (E)-configuration, while the NMR data of compounds 4a-q indicated the existence of two rotamers for each compound in solution. The target compounds were evaluated for their antibacterial activities against four microbial strains. The result suggested that several compounds exhibited pronounced antibacterial activities. Particularly, compound 4p exhibited good antibacterial activity against Staphylococcus aureus and Bacillus subtilis comparable to positive control. The possible antibacterial metabolism and the strategy for further optimization of this compound were also discussed.     

两种蓝矾衍生物的合成、结构及光谱性质研究

溶剂热体系下采用咪唑（im）、2,2’-联吡啶（bpy）为配体与硫酸铜合成了2种蓝矾衍生物：[Cu(im)4SO4]n (1)和[Cu(bpy)(H2O)2SO4]n (2),产率分别为67%和82%。重点考察了体系酸度对结构形成的影响,体系中加入的硝酸量分别控制在0.35–0.6 mmol和1.2–1.45 mmol时,得到纯相的1和2。通过元素分析、红外光谱、热重、电感耦合等离子体发射光谱、粉末X射线衍射及X射线单晶衍射测试技术对其结构及性质进行了表征。晶体结构解析表明,化合物1和2均属单斜晶系,C2/C空间群,具有蓝矾结构特征,但由于配体的空阻效应,1呈一维“之”字链状结构,2为一维“一”字链。通过紫外－可见漫反射对其性质进行了测试,结果表明2个化合物在近紫外区有一定的红移,可见光区发生蓝移。     

Prediction of Nematic Mesomorphism. Compounds with Disclike Molecules

Molecular parameters for 136 compounds with disclike molecules and known phase diagrams were calculated and analyzed by a procedure proposed previously in order to improve the method for predicting possible types of mesomorphism from molecular characteristics. A correlation between the value of the molecular parameter M _m and the existence of a nematic liquid crystal is established. An analysis of calculated values of M _m for 27 new molecules of similar structure yielded compounds that are likely to form nematic liquid crystals. To verify the prediction, one of these compounds — 1,3,5cyclohexanebenzoatebenzene — was synthesized and its phase diagram was studied. The prediction results agree with experimental data: the range of existence of a nematic mesophase was established (130.5–134.5°). Rapid cooling followed by prolonged storage of samples at room temperature without mechanical deformation led to vitrification of the samples ith preserved mesophase texture. Mechanical deformation of vitrified samples resulted in their transition to the crystal phase.     

Lipophilicity assessment of basic drugs (log P(o/w) determination) by a chromatographic method

A previously reported chromatographic method to determine the 1-octanol/water partition coefficient (log P(o/w)) of organic compounds is used to estimate the hydrophobicity of bases, mainly commercial drugs with diverse chemical nature and pK(a) values higher than 9. For that reason, mobile phases buffered at high pH to avoid the ionization of the solutes and three different columns (Phenomenex Gemini NX, Waters XTerra RP-18 and Waters XTerra MS C(18)) with appropriate alkaline-resistant stationary phases have been used. Non-ionizable substances studied in previous works were also included in the set of compounds to evaluate the consistency of the method. The results showed that all the columns provide good estimations of the log P(o/w) for most of the compounds included in this study. The Gemini NX column has been selected to calculate log P(o/w) values of the set of studied drugs, and really good correlations between the determined log P(o/w) values and those considered as reference were obtained, proving the ability of the procedure for the lipophilicity assessment of bioactive compounds with very different structures and functionalities.     

Volatile compounds and odor preferences of ground beef added with garlic and red wine,and irradiated with charcoal pack

Irradiation is the most efficient non-thermal technology for improving hygienic quality and extending the shelf-life of food products. One of the adverse effects of food irradiation, however, is off-flavor production, which significantly affects the sensory preferences for certain foods. In this study, garlic (5%, w/w) and red wine (1:1, w/w) were added to ground beef to increase the radiation sensitivity of pathogens and improve meat odor/flavor. Samples were irradiated at 0 or 5 kGy in the presence of charcoal pack. SPME-GC–MS analysis was performed to measure the changes in the volatile compounds and sensory characteristics of the samples. The amount of total volatile compounds produced from ground beef was greater when the sample was irradiated. When garlic and red wine were added to the ground beef, the amount of volatile compounds significantly increased, and the amount of volatile compounds increased even further after irradiation. However, when the samples were irradiated with charcoal pack, the amount of volatile compounds decreased significantly. Sensory evaluation indicated that charcoal pack significantly increased the odor preferences for both irradiated and non-irradiated ground beef added with garlic. These results indicated that addition of charcoal pack to ground beef could reduce off-odor problems induced by irradiation, and this effect was consistent even when certain additives such as garlic and red wine were added.     

Polysubstituted triphenylenes with active groups. Molecular parameters, synthesis, structure, and mesomorphism

Molecular parameters of hexaalkoxytriphenylenes with different substituents on the periphery of the triphenylene nucleus of known and hypothetical structures are calculated. The probability of a discophase for compounds of this series is estimated from molecular parameters. Several compounds of this series having polar groups (NO₂, NH₂) in the 1 position of the triphenylene nucleus have been synthesized. The compounds synthesized were investigated by thermopolarizing microscopy and X-ray diffraction analysis. The data on the mesomorphism of the new compounds are in good agreement with our prediction that alkoxytriphenylenes with polar groups have a discophase. It is established that introduction of an electron-accepting group at position 1 of the triphenylene nucleus expands the temperature range of existence of the discophase to room temperature. On the contrary, introduction of an electron-donating group narrows this interval. Compounds of this series presumably have a hexagonal columnar structure. Ivanovo State University. Warsaw University. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 3, pp. 464–472, May–June, 1998. This work was supported by RFFR grant No. 96-02-19036.