Synthesis, structure, and magnetic properties of the layered copper(II) oxide Na2Cu2TeO6

A new quaternary layered transition-metal oxide, Na2Cu2TeO6, has been synthesized under air using stoichiometric (with respect to the cationic elements) mixtures of Na2CO3, CuO, and TeO2. Na2Cu2TeO6 crystallizes in the monoclinic space group C2/m with a = 5.7059(6) A, b = 8.6751(9) A, c = 5.9380(6) A, beta = 113.740(2) degrees, V = 269.05(5) A3, and Z = 2, as determined by single-crystal X-ray diffraction. The structure is composed of infinity(2)[Cu2TeO6] layers with the Na atoms located in the octahedral voids between the layers. Na2Cu2TeO6 is a green nonmetallic compound, in agreement with the electronic structure calculation and electrical resistance measurement. The magnetic susceptibility shows Curie-Weiss behavior between 300 and 600 K with an effective moment of 1.85(2) muB/Cu(II) and theta(c) = -87(6) K. A broad maximum at 160 K is interpreted as arising from short-range one-dimensional antiferromagnetic correlations. With the aid of the technique of magnetic dimers, the short-range order was analyzed in terms of an alternating chain model, with the surprising result that the stronger intrachain coupling involves a super-superexchange pathway with a Cu-Cu separation of >5 A. The J2/J1 ratio within the alternating chain refined to 0.10(1), and the spin gap is estimated to be 127 K.     

A vertical heat pipe: an experimental and statistical study of the thermal performance in the presence of low-frequency vibrations

New experimental results present the effects of low-frequency vibrations in a vertical heat pipe. The thermal resistance was investigated under different heat transfer rates, filling ratios and frequencies, increase of which improved the thermal performance. The vibrations were effective 33.83 % on the performance, and the best performance was estimated using the L16 array of Taguchi method, and it was achieved with the thermal resistance 0.064 K/W in the frequency 30 Hz.     

Explicit Rate–Time Solutions for Modeling Matrix–Fracture Flow of Single Phase Gas in Dual-Porosity Media

One of the widely used methods for modeling matrix–fracture fluid exchange in naturally fractured reservoirs is dual porosity approach. In this type of modeling, matrix blocks are regarded as sources/sinks in the fracture network medium. The rate of fluid transfer from matrix blocks into fracture medium may be modeled using shape factor concept (Warren and Root, SPEJ 3:245–255, 1963); or the rate–time solution is directly derived for the specific matrix geometry (de Swaan, SPEJ 16:117–122, 1976). Numerous works have been conducted to study matrix–fracture fluid exchange for slightly compressible fluids (e.g. oil). However, little attention has been taken to systems containing gas (compressible fluid). The objective of this work is to develop explicit rate–time solutions for matrix–fracture fluid transfer in systems containing single phase gas. For this purpose, the governing equation describing flow of gas from matrix block into fracture system is linearized using pseudopressure and pseudotime functions. Then, the governing equation is solved under specific boundary conditions to obtain an implicit relation between rate and time. Since rate calculations using such an implicit relation need iterations, which may be computationally inconvenient, an explicit rate–time relation is developed with the aid of material balance equation and several specific assumptions. Also, expressions are derived for average pseudopressure in matrix block. Furthermore, simplified solutions (originated from the complex general solutions) are introduced applicable in infinite and finite acting flow periods in matrix. Based on the derived solutions, expressions are developed for shape factor. An important observation is that the shape factor for gas systems is the same as that of oil bearing matrix blocks. Subsequently, a multiplier is introduced which relates rate to matrix pressure instead of matrix pseudopressure. Finally, the introduced equations are verified using a numerical simulator.     

Diamagnetic contribution and substituent effects on 13C n.m.r. spectra

Correction of measured chemical shifts by subtracting the diamagnetic contributions caused by certain substituents on various carbons of a molecule leads to data that allow a reasonable interpretation of substituent effects on chemical shifts in ¹³C n.m.r. spectroscopy. It is shown that both paramagnetic and diamagnetic terms increase on all carbons of a molecule when the atomic number of a substituent increases down the same group of the periodic table. An explanation of α-, β-, and γ- effects for methyl substitution using the same procedure is attempted.     

Molecular modeling investigation of adsorption of Zolinza drug on surfaces of the B12N12 and Al12N12 nanocages

Structural Chemistry - In the current work, the adsorption of Zolinza (ZOL) drug on B12N12 and Al12N12 nanocages was investigated using density functional theory (DFT) and time-dependent DFT...     

Chiral micellar electrokinetic chromatography-atmospheric pressure photoionization of benzoin derivatives using mixed molecular micelles

In the present work we report, for the first time, the successful on-line coupling of chiral MEKC (CMEKC) to atmospheric pressure photoionization MS (APPI-MS). Four structurally similar neutral test solutes (e.g. benzoin (BNZ) derivatives) were successfully ionized by APPI-MS. The mass spectra in the positive ion mode showed that the protonated molecular ions of BNZs are not the most abundant fragment ions. Simultaneous enantioseparation by CMEKC and on-line APPI-MS detection of four photoinitiators, hydrobenzoin, BNZ, benzoin methyl ether, benzoin ethyl ether, were achieved using an optimized molar ratio of mixed molecular micelle of two polymeric chiral surfactants (polysodium N-undecenoxy carbonyl-L-leucinate and polysodium N-undecenoyl-L,L-leucylvalinate). The CMEKC conditions, such as voltage, chiral polymeric surfactant concentration, buffer pH, and BGE concentration, were optimized using a multivariate central composite design (CCD). The sheath liquid composition (involving %v/v methanol, dopant concentration, electrolyte additive concentration, and flow rate) and spray chamber parameters (drying gas flow rate, drying gas temperature, and vaporizer temperature) were also optimized with CCD. Models built based on the CCD results and response surface method were used to analyze the interactions between factors and their effects on the responses. The final overall optimum conditions for CMEKC-APPI-MS were also predicted and found in agreement with the experimentally optimized parameters.     

Preparation of low-density 90Y microspheres consisting of mesoporous silica core/yttria shell: a potential therapeutic agent for hepatic tumors

A new low-density silica core/yttria shell microspheres was developed for medical purposes. For preparing the core of this material, sol-emulsion-gel method was used. It was then calcined at 1,000 °C to increase the strength of the mesoporous beads. After cooling, it was added into a solution containing the mixture of yttrium chloride and urea. Under these circumstances, yttrium chloride can decompose to yttrium basic carbonate particles by the gradual hydrolysis of urea. These particles are able to deposit on the surface of mesoporous silica beads. Different coated samples were prepared under various pH, temperature and stirring conditions. Samples were heated to convert yttrium basic carbonate to yttria. The resulting silica core/yttria shell microspheres was characterized by laser diffractometer, scanning electron and optical microscopy techniques. It was found the pH of silica sols, aging time and Span-80 play important role in the stage of mesoporous bead preparation. Furthermore, the findings showed the heating of core/shell microspheres was essential for the ultimate strength of the shell. The in vitro chemical durability tests showed the release of yttrium ion in two simulated body fluids at pH 6 and 7 was negligible after 4 weeks.     

Radioiodination of 4-benzyl-1-(3-iodobenzylsulfonyl)piperidine, 4-(3-iodobenzyl)-1-(benzylsulfonyl)piperazine and their derivatives via isotopic and non-isotopic exchange reactions

A mild and simple technique for preparing of 4-benzyl-1-(3-[¹²⁵I]iodobenzylsulfonyl)piperidine, 4-(3-[¹²⁵I]iodobenzyl)-1-(benzylsulfonyl)piperazine and their derivatives, as sigma-1 receptor ligands, with relatively high radiochemical yields via nucleophilic substitution reaction by means of isotopic and non-isotopic exchange reactions is described. Some factors affecting the radiochemical yield were commonly studied in presence of acidic medium at elevated temperature. Unfortunately, the radiochemical yields were weak. Some attempts were carried out in presence of polar aprotic solvents to enhance the radiochemical yield. N,N-Dimethylformamide was proved highly efficient for preparing of radioiodinated 4-benzyl-1-(3-iodobenzylsulfonyl)piperidine (4-B-[¹²⁵I]-IBSP, 70 ± 5.7 %) and 4-(3-iodobenzyl)-1-(benzylsulfonyl)piperazine (4-[¹²⁵I]-IBBSPz, 72 ± 6.0 %) at moderate temperature (100–105 °C) within 8 h. The specific activities of 4-B-[¹²⁵I]-IBSP and 4-[¹²⁵I]-IBBSPz (6,534.2 and 5,927.4 MBq/mmol) were obtained respectively.     

Packed-column capillary electrochromatography and capillary electrochromatography-mass spectrometry using a lithocholic acid stationary phase

The preparation and characterization of a novel lithocholic acid (LCA)-based liquid crystalline (LC) stationary phase (SP) suitable for application in packed-column CEC and CEC coupled to MS is described. The extent of bonding reactions of LCA-SP was assessed using 1H-NMR, 13C-NMR and elemental analysis. This characterization is followed by application of the LCA-SP for separation of beta-blockers, phenylethylamines (PEAs), polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Using the optimum mobile phase operating conditions (pH 3.0-4.5, 10 mM ammonium acetate, 85% v/v ACN), a comparison of the chromatographic ability of the aminopropyl silica phase vs. the LCA-bonded phase was conducted. The results showed improved selectivity for all test analytes using the latter phase. For example, the CEC-MS of beta-blockers demonstrated that the LCA-bonded phase provides separation of six out of seven beta-blockers, whereas the amino silica phase provides four peaks of several co-eluting beta-blockers. For the CEC-MS analysis of PEAs, the LCA-bonded phase showed improved resolution and different selectivity as compared to the aminopropyl phase. An evaluation of the retention trends for PEAs on both phases suggested that the PEAs were retained based on varying degree of hydroxyl substitution on the aromatic ring. In addition, the MS characterization shows several PEAs fragment in the electrospray either by loss of an alkyl group and/or by loss of H2O. Finally, the LCA-bonded phase displayed significantly higher separation selectivity for PAHs and PCBs as compared to the amino silica phase.     

Regioselective Synthesis of Fused Azo‐linked Pyrazolo[4,3‐e]pyridines Using Nano‐Fe3O4

A multicomponent reaction for the synthesis of fused azo‐linked pyrazolo[4,3‐e]pyridines from 3‐amino‐5‐methylpyrazole, indan‐1,3‐dione and synthesized azo‐linked aldehydes using nano‐Fe₃O₄ as an effective and reusable catalyst is reported. The present methodology offers several advantages, such as a simple procedure with an easy work‐up, short reaction times, high yields, and the absence of any volatile and hazardous organic solvents.