Microwave-assisted synthesis and characterization and theoretical calculations of the first example of free and metallophthalocyanines from salen type Schiff base derivative bearing thiophen and triazole heterocyclic rings

Novel metal-free and metallophthalocyanine complexes of Co, Ni, Cu, and Zn have been synthesized by exposure to microwave irradiation and reflux conditions and the products purified by several techniques. The newly prepared compounds have been characterized by elemental analyses, IR, ¹H NMR, MS and UV-Vis spectroscopy. Furthermore, theoretical calculations of metallophthalocyanines CuPc, NiPc, ZnPc and CoPc were carried out to comparatively describe the molecular structures, molecular orbital and UV-Vis spectra of metallophthalocyanine complexes by the HF theory. A comparison between the different molecules for the geometry, molecular orbitals was made. The simulated order of the sizes of the central hole was CoPc > NiPc < CuPc < ZnPc, which is in complete accord with the experiment. Moreover, the HOMO-LUMO gaps were varied in order of CoPc > NiPc > ZnPc > CuPc. The calculated structures, electronic absorption spectra of metallophthalocyanine complexes are in good consistency with the experimental results.     

Synthesis,characterization, and thermal decomposition of fluorinated salicylaldehyde Schiff base derivatives (salen) and their complexes with copper(II)

Trifluoromethoxy functionalized copper(II) Schiff base complexes N,N′-bis(5-trifluoromethoxysalicylaldehyde)cyclohexanediiminatodiaquacopper(II) and N,N′-bis(5-trifluoromethoxysalicylaldehyde)phenylenediiminatocopper(II) were synthesized and characterized. Thermal decompositions of the synthesized complexes were studied by thermogravimetry in order to evaluate their thermal stability and thermal decomposition pathways. Three similar decomposition steps occurred for the two copper complexes. Mass losses and evolved gasses were characterized by TG/DTA-MS. Kinetic parameters were calculated and the results showed that the values obtained are comparable.     

Diffusion-weighted imaging evaluation of subtle cerebral microstructural changes in intrauterine fetal hydrocephalus

OBJECTIVE: Hydrocephalus is an important etiological factor in neurological decline. With the advent of fetal ultrasound, fetal hydrocephalus is now more frequently detected than in the past. Ultrasonography (USG) provides information on general morphology, but microstructural changes that may play a prognostic role are beyond the resolution of that technique. These changes may theoretically be revealed by diffusion-weighted magnetic resonance imaging (DW-MRI). In this study, our preliminary findings of DW-MRI on the hydrocephalic fetuses are presented. MATERIALS AND METHODS: Twelve fetuses with fetal USG diagnosis of hydrocephalus were investigated using a 1.5-T MR scanner. In addition to conventional techniques, DWI was performed. It was obtained using a single-shot echo-planar imaging sequence (TR/TE: 4393/81 ms; slice thickness: 5 mm; interslice gap: 1 mm; FOV: 230 mm; matrix size: 128x256; b values: 0 and 1000 s/mm2). Apparent diffusion coefficient (ADC) values were measured in the white matter of the periventricular frontal and occipital lobes, basal ganglia, thalamus, centrum semiovale and cerebrospinal fluid in the lateral ventricle. These values were compared with the normal prenatal ADC values from a radiological study published in the literature. RESULTS: All fetuses had moderate or severe bilateral supratentorial ventricular dilatation that was compatible with hydrocephalus. On conventional T1- and T2-weighted imaging, cerebral parenchyma had normal signal pattern and ADC values were significantly lower than those reported for fetuses with normal brain. These values were lower in hydrocephalic fetuses with statistical significance (P<.05-.01). CONCLUSION: DWI is a sensitive technique to investigate cerebral microstructure. The reduction in cerebral blood flow and alterations in cerebral energy metabolism in cases with hydrocephalus have been shown before. Changes in cerebral blood flow and energy metabolism, as a consequence of cerebral compression, may occur in hydrocephalus. Elevated ventricular pressure may cause cerebral ischemia. The anaerobic glycolysis seen in the hydrocephalic brain tissue by increasing the lactate concentration and intracellular fluid flux may be the reason for the reduced ADC values in hydrocephalic fetuses. However, long-term prospective trials on the correlation of ADC values and neurological outcome are necessary to exploit the full benefit of that novel technique.     

Atomic layer deposited HfO2 based metal insulator semiconductor GaN ultraviolet photodetectors

A report on GaN based metal insulator semiconductor (MIS) ultraviolet (UV) photodetectors (PDs) with atomic layer deposited (ALD) 5-nm-thick HfO₂ insulating layer is presented. Very low dark current of 2.24 × 10⁻¹¹ A and increased photo to dark current contrast ratio was achieved at 10 V. It was found that the dark current was drastically reduced by seven orders of magnitude at 10 V compared to samples without HfO₂ insulating layer. The observed decrease in dark current is attributed to the large barrier height which is due to introduction of HfO₂ insulating layer and the calculated barrier height was obtained as 0.95 eV. The peak responsivity of HfO₂ inserted device was 0.44 mA/W at bias voltage of 15 V.     

A first-principles studies on TlX (X=P, As)

We present an ab initio study of the structural, electronic and thermodynamic properties of TlX(X=P,As). The plane-wave pseudopotential approach to the density-functional theory within the LDA and GGA approximations implemented in VASP (Viena Ab-initio Simulation Package) is used. The calculated lattice parameter, elastic constants, and band structures are compared with other available theoretical results, and good agreement is obtained. In addition, we have calculated the transition pressure (P _t ) from zinc-blende (ZB) to (rock-salt) NaCl structures, and have examined some thermodynamic properties.      

Weighted Rogers–Ramanujan partitions and Dyson crank

In this paper, we refine a weighted partition identity of Alladi. We write formulas for generating functions for the number of partitions grouped with respect to a partition statistic other than the norm. We tie our weighted results as well as the different statistics with the crank of a partition. In particular, we prove that the number of partitions into even number of distinct parts whose odd-indexed parts’ sum is n is equal to the number of partitions of n with non-negative crank.