Synthesis,Crystal Structure and Thermal Behavior of Gadolinium Dicyanamide Dihydrate Gd[N(CN)2]3 · 2 H2O

Gadolinium dicyanamide dihydrate Gd[N(CN)₂]₃ · 2 H₂O was prepared by ion exchange in aqueous solution followed by evaporation of the solvent at room temperature. Gd[N(CN)₂]₃ · 2 H₂O was characterized by single‐crystal structure analysis, FTIR spectroscopy and DSC analysis. In the crystal there are three crystallographically independent [N(CN)₂]^? ions and Gd³⁺ which are coordinated by six N atoms from six different [N(CN)₂]^? ions and two O atoms from two water molecules forming an irregular quadratic antiprism. Four H bonds have been identified in the structure of Gd[N(CN)₂]₃ · 2 H₂O, two of them running to terminal N atoms and two to the bridging N atoms of dicyanamide ions (Gd[N(CN)₂]₃ · 2 H₂O: P2₁/n (no. 14), a = 7.4845(15) Å, b = 11.529(2) Å, c = 13.941(3) Å, β = 93.98(3)°, Z = 4, 1948 reflections, 175 parameters, R1 = 0.0493). The DSC analysis indicates that Gd[N(CN)₂]₃ · 2 H₂O looses the crystal water at temperatures around 130 – 140 °C forming anhydrous Gd[N(CN)₂]₃, the structure of which has been refined by the Rietveld method based on X‐ray powder diffraction data. Gd[N(CN)₂]₃ was found to be isotypic with Ln[N(CN)₂]₃ (Ln = La, Ce, Pr, Nd, Sm and Eu) which previously have been described in the literature.     

Structurally and chemically heterogeneous nanofibrous nonwovens via electrospinning

Homogeneous nonwovens composed of polymer nanofibers of a given diameter are characterized by structural parameters such as the average pore sizes and internal surfaces as well as by transport properties, which are strongly correlated to the fiber diameter at a given porosity. Such nonwovens are used among others for filter applications, protective clothing or as scaffolds for tissue engineering. A frequent requirement is that, to be able to prepare nonwovens optimised for the specific application, one has to find ways to disrupt this strong correlation allowing independent modification of pore diameter, transport properties and internal surface or to induce local chemical and structural heterogeneities within the nonwoven. The route explored in this paper is based on the electrospinning of heterogeneous nonwovens composed of nanofibers with two different average diameters (by a ratio of up to 10 and more) on the one hand and/or different chemical nature on the other hand. Spinning parameters have been optimised to achieve this goal. In addition, nonwovens composed of fibers with circular cross-section and with ribbon-like cross-section have been prepared.     

The chemistry of (1-azabuta-1,3-diene)tricarbonyliron(0) complexes

In this review, an overview of synthetic and structural aspects of 1-azabuta-1,3-diene complexes of iron is given and the reactivity of these complexes is discussed with regard to inorganic, organometallic, organic and stereochemical aspects of their chemistry. Their application in the synthesis of organic and organometallic target compounds, or as transfer reagents of the tricarbonlyiron(0) moiety is demonstrated.     

Pre-irradiation induced grafting of styrene into crosslinked and non-crosslinked polytetrafluoroethylene films for polymer electrolyte fuel cell applications. II: Characterization of the styrene grafted films

Crosslinked and non-crosslinked polytetrafluoroethylene films (RX-PTFE and V-PTFE films, respectively) were irradiated by γ-ray and then grafted with styrene in liquid phase. Microscope FT-IR spectroscopy, TGA, solid state ¹³C CP/MAS and high resolution HS/MAS NMR spectroscopy, wide-angle X-ray diffraction (WAXD) study were used to get the structural information of the styrene grafted RX-PTFE and V-PTFE films. From microscope FT-IR spectra of the grafted RX-PTFE films, the “grafting front mechanism” was proved. TGA analysis showed that the grafted films have a small degradation step and two main degradation steps. In the ¹³C CP/MAS NMR spectra of the non-grafted films, there are no signal due to the absence of the hydrogen atom. While in the spectra of the grafted films, there are signals attributed to the polystyrene grafts. In the ¹³C HS/MAS NMR spectra of the grafted films, the relative intensity of the peaks attributed to the polystyrene grafts increased while the relative intensity of the peak attributed to PTFE matrix decreased with the increase in the DOG. From WAXD patterns, the intensity of the crystalline peak decrease with the increase in the DOG. The grafted films were sulfonated by chlorosulfonic acid and the results of highest IEC value exceeded 3.0. Those results will be reported in the near future.     

苯、甲苯、一氯代苯对含水卵磷脂液晶结构影响的SAXS研究

苯及其衍生物甲苯,一氯代苯都是重要的有机试剂和化工原料,也是对人体有害的有机物。为了了解这些有机试剂对处于生物液晶态的生物膜毒害的机理,我们以含水卵磷脂组成的液晶体系作为人工模型用小角X射线散射(SAXS)方法探讨这些有机试剂对它们结构的影响。关于苯或其它非极性有机介质与含水卵磷脂形成液晶体系及其结构模型前人有一些报导。     

A DFT study of lithium battery materials: application to the β-VOXO4 systems (X=P, As, S)

VOXO₄ systems have been considered as potential lithium battery electrodes. They mainly present two distinct structural types: the tetragonal “α” type with a two-dimensional framework, and the three-dimensional orthorhombic “β”. DFT calculations were performed on this latter system for several β-Li_xVOXO₄ compounds (x=0, 1; X=P, As, S). They allowed to propose structural models for VOAsO₄ and LiVOSO₄, not fully crystallographically well described yet. Based on an experimental model of two-phase processes, these calculations led also to a good simulation of electrochemical potential values. A density of states analysis put in evidence the “inductive effect” and the role played by (XO₄)ⁿ⁻ groups inside the host frameworks on these potentials.     

The structure and spectra of 1,1-bis(trimethylsilylethynyl)-cyclopropane: a priori calculated force field and vibrational effects

The molecular structure of 1,1-bis(trimethylsilylethynyl)cyclopropane has been studied by the gas electron diffraction method, by vibrational spectroscopic methods and by ab initio calculations at the RHF and MP2 levels. A scaled quantum-chemical force field was used for band assignment in the experimental IR (4000-100 cm⁻¹) and Raman (4000-200 cm⁻¹) spectra. The root-mean-square vibrational amplitudes and harmonic shrinkage corrections were calculated taking into account non-linear relations between Cartesian and internal vibrational coordinates at the level of first-order perturbation theory (h1) and with the use of the traditional scheme (h0).     

Struktur‐ und magnetochemische Untersuchungen an KCuGaF6

Structural and Magnetochemical Studies on KCuGaF₆ The crystal structure of KCuGaF₆ was determined on the base of X‐ray single crystal data (wR₂ = 0.084 for 2476 independent reflections). The compound crystallizes with a = 728.56(4), b = 989.51(6), c = 676.27(3) pm, β = 93.120(5)°, Z = 4 in space group P2₁/c of the pyrochlore related KCuCrF₆ type. The octahedral coordinations [GaF₆] and [CuF₆] are slightly resp. strongly distorted (mean values Ga‐F: 188.2 pm resp. Cu‐F: 188.2/200.1/227.6 pm). The longest distances Ga‐F and the shortest ones Cu‐F are found within octahedral chains of these two kinds of atoms, running along [100] and [001], resp., and being mutually bridged as well (M‐F‐M in between 114 and 145°). The magnetic mole susceptibilities measured at powders and at a single crystal follow the isotropic Heisenberg model for S = ¹/₂, if effects of chain disrupture are considered in the form of some paramagnetic portion. No indication of threedimensional magnetic order is observed down to T = 2 K and low magnetic fields H < 100 G. KCuGaF₆ (J/k = —71 K for the powder) is distinguished this way from the chain structure compounds KCuAlF₆ und Na₂CuScF₇ (J/k = —76 resp. —59 K) which were also magnetically studied and yield similar antiferromagnetic exchange constants J/k.     

尼龙6与半芳香性非晶尼龙原位共混物的结构与性能

一种半芳香的非晶尼龙共聚物溶解于熔融的己内酰胺中,引发后者负离子开环聚合原位制备尼龙6与非晶尼龙的共混物.与纯尼龙6相比较,此原位共混物的强度与模量显著提高.非晶区呈现单一的玻璃化转变,表明共混物为均相体系,其组分的相容性源于负离子聚合过程中链交换反应引起的共聚.与纯尼龙6相比较,此共混物的熔点与结晶度显著降低.此外,与纯尼龙6只存在α晶不同,共混物中伴生有大量的γ晶.当非晶尼龙含量为20 wt%时,绝大部分晶体为γ晶.然而,共混物中球晶仅有一定程度细化.共混物强度和模量的提高被认为主要源于非晶区分子活动能力降低以及γ晶相对含量的提高.     

Genome-inspired search for new antibiotics. Isolation and structure determination of new 28-membered polyketide macrolactones, halstoctacosanolides A and B, from Streptomyces halstedii HC34

During the search for polyketide synthase (PKS) in the genome of Streptomyces halstedii HC34, we found clustered new genes which appeared to encode typical Type 1 PKSs beyond the cluster harboring the genes for the biosynthesis of antitumor antibiotic vicenistatin. The deduced domain configuration of these putative PKS genes allowed to predict a corresponding partial structure of polyketide, which was in turn materialized by isolation of new polyketide macrolactone halstoctacosanolides A and B from the fermentation broth of S. halstedii HC34. The structures of these metabolites were determined by spectroscopic means to have a novel 28-membered macrolactone structure. The partial structure deduced from the genetic data was completely compatible to the structures of halstoctacosanolides A and B. This success clearly demonstrates the present new approach of genome-inspired search for new antibiotics promising. Halstoctacosanolides A and B showed moderate antimicrobial activity against several microorganisms.