Vibrational relaxation of OH and CH fundamentals of polar and nonpolar molecules in the condensed phase

Studies of vibrational energy flow in various polar and nonpolar molecules that follows the ultrafast excitation of the CH and OH stretch fundamentals, modeled using semiclassical methods, are reviewed. Relaxation rates are calculated using Landau-Teller theory and a time-dependent method, both of which consider a quantum mechanical solute molecule coupled to a classical bath of solvent molecules. A wide range of decay rates are observed, ranging from 1 ps for neat methanol to 50 ps for neat bromoform. In order to understand the flow rates, it is argued that an understanding of the subtle mixing between the solute eigenstates is needed and that solute anharmonicities are critical to facilitating condensed phase vibrational relaxation. The solvent-assisted shifts of the solute vibrational energy levels are seen to play a critical role of enhancing or decreasing lifetimes.     

Syntheses,Spectral, Thermal and Structural Characterization of 2‐Phenyl‐2‐(1‐hydroxyiminoethyl)‐1,2,3,4‐tetrahydroquinazoline and Its Novel Nickel(II) Complex

The 2‐phenyl‐2‐(1‐hydroxyiminoethyl)‐1,2,3,4‐tetrahydroquinazoline (HL) and its Ni^II complex have been prepared and characterized by spectral method (FT‐IR, NMR (¹³C and ¹H), UV‐vis.), elemental analysis, magnetic susceptibility and thermal analysis (TG, DTA) techniques. The crystal structures of HL and Ni^II complex were also determined by the single crystal X‐ray diffraction. The HL and Ni^II complex crystallizes in the monoclinic and triclinic, space groups P2₁/c and , respectively. The complex was occurred by the elimination of 1 mole of 2‐aminobenzylamine from the 2 moles of the HL after the ring opening reaction by the Ni^II attack. Crystallographic study reveal that Ni^II atom has a square planer geometry being coordinated by four nitrogen atoms of HL. Two thermal processes of the HL and Ni^II complex can occur in TG and DTA curves.     

Assessment of gross alpha and beta activity levels and element concentrations in spa waters from Siirt and Şırnak,Turkey

Gross α and β activity contents and element concentrations in well-known spa waters from the Siirt and the ??rnak cities were determined and assessed by MPC-9604 multi-detector α/β counting system and by wavelength dispersive X-ray fluorescence spectrometry. The 0.05–5.64 gross α and 0.06–2.76 Bq L^?1 gross β activity levels and element concentrations found in samples were compared with recommended values given by the World Health Organization, the US Environmental Protection Agency, Turkish Standards and literature results. Principal component and cluster analysis were also used to classify the spa waters due to element concentrations and three principal components calculated were about 91 % of the total variance in the data.     

Numerical Study of Heat Transfer in a Rectangular Channel with Porous Covering Obstacles

A numerical study is performed to analyze steady laminar forced convection in a channel in which discrete heat sources covered with porous material are placed on the bottom wall. Hydrodynamic and heat transfer results are reported. The flow in the porous medium is modeled using the Darcy–Brinkman–Forchheimer model. A computer program based on control volume method with appropriate averaging for diffusion coefficient is developed to solve the coupling between solid, fluid, and porous region. The effects of parameters such as Reynolds number, Prandtl number, inertia coefficient, and thermal conductivity ratio are considered. The results reveal that the porous cover with high thermal conductivity enhances the heat transfer from the solid blocks significantly and decreases the maximum temperature on the heated solid blocks. The mean Nusselt number increases with increase of Reynolds number and Prandtl number, and decrease of inertia coefficient. The pressure drop along the channel increases rapidly with the increase of Reynolds number.     

Novel segmented copolymers by combination of controlled ionic and radical polymerizations

Transformation of different living and non‐living polymerization mechanisms to controlled/“living” atom transfer radical polymerization (ATRP) in order to prepare block and graft copolymers is described. The synthesis and characterization of macroinitiators and the resulting segmented copolymers is discussed.     

Energy and exergy analysis of solar energy-integrated,geothermal energy-powered Organic Rankine Cycle

Journal of Thermal Analysis and Calorimetry - In this study, the energy and exergy analysis of the solar- and geothermal energy-powered Organic Rankine Cycle was made for different system...     

Catena-Poly[[[2,4-dichloro-6-{[(2-hydroxyethyl)imino]methyl}phenolato-κ3N,O,O']-copper(II)]-μ-chlorido]monohydrate]: Synthesis,structural, spectroscopic and luminescent properties

A new chloride bridged polymeric Cu(II) complex, [Cu(HL)(μ-Cl).H₂O]_n, 1, (H₂L = 2,4-dichloro-6-{[(2-hydroxyethyl)imino]methyl}phenol) has been synthesized and characterized by elemental-spectral analysis, crystal structure analysis and photoluminescence measurements. The Copper(II) atom is five-coordinate in a slightly distorted square-pyramidal geometry (τ = 0.085), with one N and two O atoms of the Schiff base ligand and one Cl atom defining the basal plane and a symmetry-related Cl atom occupying the apical position. The bridging Cl atom lies in apical position for one Cu(II) ion and basal for the other, and it makes this structural arrangement unusual. The linked moieties form polymeric zigzag chains running along the c axis. This zigzag chains connect each other with intramolecular and intermolecular O–H···O hydrogen bonds, which form 3D structure through π?π interactions. Furthermore, the photoluminescence properties of H₂L and 1 were investigated, they exhibit unique bright green visible emissions in the solid state, under the excitation of 349 nm UV light. The strong luminescence emission of them makes 1 a potentially useful photoactive material in photo-physical chemistry.     

A rapid LC-MS/MS method for determination of urinary EtG and application to a cut-off limit study

Ethyl glucuronide (EtG) is a metabolite and a specific marker of alcohol consumption that can be detected days after the complete elimination of alcohol after drinking. A rapid, simple, and sensitive LC-ESI-MS/MS method for the determination of urinary ethyl glucuronide was developed and fully validated in accordance with analytical standards, using the C₁₈ column. The whole process including sample preparation and LC-MS/MS lasted 10 min. A comprehensive validation including HorRat, measurement uncertainty, system suitability and intermediate precision calculations among analysts, and a cut-off limit study was performed. The method was applied to real samples and a cutoff limit determination study. The LOD and LOQ (using the IUPAC and Eurachem methods) were determined as 104.21 ng mL^?1 and 165.00 ng mL^?1. A cut-off limit of ≈ 818 ng mg^?1 (normalised to creatinine) was found for urinary EtG. The results showed that the cut-off limits currently in use should be re-considered in further studies and standardised on a global scale. Normalisation to creatinine is important because of the risk of the dilution of urine intentionally or with a change of diet. The concentrations of real samples from subjects who had consumed alcohol were successfully predicted using this method, after zero HS-GC/MS results of urine alcohol concentration.     

Na3[BN2] and Na2K[BN2]: A Known and a Novel Alkali Metal Dinitridoborate Obtained via Mild Thermal Dehydrogenation

Na₃[BN₂] and Na₂K[BN₂] were obtained as white polycrystalline powders from the reaction of the respective binary mixtures NaNH₂:NaBH₄ and NaNH₂:KBH₄ in molar ratio 2:1 at 873 K and 683 K, respectively, in an argon stream. According to the results of thermal analysis measurements, both compounds are thermally stable only up to 954 K (Na₃[BN₂]) and 712 K (Na₂K[BN₂]), respectively, decomposing under evolution of alkali metal and nitrogen to yield hexagonal BN as final residue, which was identified from powder patterns. The crystal structure of Na₃[BN₂] {β‐Li₃[BN₂] type; P2₁/c (No. 14); Z = 4} was confirmed and the unit cell parameters redetermined: a = 5.724(1) Å, b = 7.944(1) Å, c = 7.893(1) Å, β = 111.31(1)°. According to X‐ray powder data, Na₂K[BN₂] crystallizes isotypic to Na₂KCuO₂ in the tetragonal space group I4/mmm (No. 139) with a = 4.2359(1) Å, c = 10.3014(2) Å and Z = 2. The crystal structure of Na₂K[BN₂] is composed of linear [N–B–N]^3– anions centering elongated M₁₄ rhombic dodecahedra, which are formed by 8 sodium and 6 potassium atoms. The [BN₂]@Na_8/4K_6/6 polyhedra are stacked along [001] and condensed via common tetragonal faces to generate a space‐filling 3D arrangement. The B–N bond lengths for the strictly linear [N–B–N]^3– units are 1.357(4) Å. Vibrational spectra of the title compounds were measured and analyzed based on D_∞h symmetry of the relevant [N–B–N]^3– groups taking into account the site symmetry effects for Na₃[BN₂]. Both the wavenumbers, as well as the calculated valence force constants f(B–N) = 7.29 N · cm^–1 (Na₃[BN₂]) and 7.33 N · cm^–1 (Na₂K[BN₂]), respectively, are in good agreement with those of the known alkali and alkaline earth dinitridoborates.