The Use of Laser Induced Breakdown Spectroscopy (LIBS) to Study Catalyst Deactivation of V2O5/γ‐Al2O3 as Compared to Inductively Coupled Plasma Optical Emission Spectrometry

Laser Induced Breakdown Spectroscopy (LIBS) method is introduced as a novel approach in this work to study catalyst deactivation of V₂O₅/γ‐‐Al₂O₃ for gas‐phase dehydration of glycerol and producing acrolein. The LIBS results of V₂O₅/γ‐Al₂O₃ samples are compared with those data that are obtained by Inductively Coupled Plasma Optical Emission Spectrometry (ICP‐OES). Experimental data of LIBS data specify that line intensities of vanadium are decreased by deactivation of V₂O₅/γ‐Al₂O₃ catalyst. A comparison between the results of LIBS test as well as ICP‐OES analysis shows that the amount of vanadium is decreased in the catalyst. Moreover, coke formation changes the surface of the catalyst. The results of deactivation of V₂O₅/γ‐Al₂O₃ are also compared with Pd/C catalyst deactivation.     

Design and Synthesis of Imidazole and Triazole Pyrazoles as Mycobacterium Tuberculosis CYP121A1 Inhibitors

The emergence of untreatable drug-resistant strains of Mycobacterium tuberculosis is a major public health problem worldwide, and the identification of new efficient treatments is urgently needed. Mycobacterium tuberculosis cytochrome P450 CYP121A1 is a promising drug target for the treatment of tuberculosis owing to its essential role in mycobacterial growth. Using a rational approach, which includes molecular modelling studies, three series of azole pyrazole derivatives were designed through two synthetic pathways. The synthesized compounds were biologically evaluated for their inhibitory activity towards M. tuberculosis and their protein binding affinity (K_D). Series 3 biarylpyrazole imidazole derivatives were the most effective with the isobutyl ( 10 f ) and tert-butyl ( 10 g ) compounds displaying optimal activity (MIC 1.562 μg/mL, K_D 0.22 μM ( 10 f ) and 4.81 μM ( 10 g )). The spectroscopic data showed that all the synthesised compounds produced a type II red shift of the heme Soret band indicating either direct binding to heme iron or (where less extensive Soret shifts are observed) putative indirect binding via an interstitial water molecule. Evaluation of biological and physicochemical properties identified the following as requirements for activity: LogP >4, H-bond acceptors/H-bond donors 4/0, number of rotatable bonds 5–6, molecular volume >340 ų, topological polar surface area <40 Ų.     

13C NMR of indazoles

The carbon-13 chemical shifts and some selected coupling constants of 183 indazoles are reported. The main conclusions of the original references are briefly summarized.Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1159–1179, September, 1995.     

Theoretical study on interaction of different coordination modes of BH4 ligand with transition metal in [TM(BH4)(CO)4] (TM = Cr, Mo)

Density functional calculations were performed on bonding and structural features of [(ηⁿ-BH₄)TM(CO)₄]⁻ (n = 1, 2, 3; TM = Cr, Mo) complexes. Calculations show that the ground state is bidentate which is in good agreement with experimental results. It has been found that the bridge and terminal hydrogen atoms will interchange by two pathways: (i) twist of BH₄ about one of the bridge B-H and (ii) twist of BH₄ about one of the terminal B-H. The molecular orbital calculations and natural bond orbital methodologies for different isomers of these complexes have been evaluated. The final results indicate that case (i) is more preferable relative to another case.     

Honeycomb nets with interpenetrating frameworks involving iminodiacetato-copper(II) blocks and bipyridine spacers: syntheses, characterization, and magnetic studies

Three coordination polymers of copper(II), viz. ([Cu(ida)(4,4'-bipyH)]ClO(4))( proportional, variant ) (1), ([Cu(2)(ida)(2)(micro-4,4'-bipy)].2H(2)O)( proportional, variant ) (2), and [Cu(2)(ida)(2)(bpa)]( proportional, variant ) (3) have been synthesized by the process of self-assembly using Cu(ida) [ida = iminodiacetate(2-)] as the building block and 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane (bpa) as linkers. Crystals of 1 are orthorhombic, of space group Pna2(1), with a = 13.8956(12) A, b = 16.3362(16) A, c = 7.3340(12), and Z = 4. Both compounds 2 and 3 crystallize in monoclinic space group P2(1)/a with a = 10.1887(8) A (9.6779(10) A for 3), b = 8.0008(11) A (9.1718(10) A), c = 11.6684(9) A (12.9144(12) A), beta = 98.307(11) degrees (102.796(18) degrees ), and Z = 2 (2). Compound 1 has a zigzag chain structure with an extensive hydrogen-bonded network while compounds 2 and 3 are honeycomb (6,3) nets with interpenetrating structures. Variable temperature (2-300 K) magnetic study indicates the presence of weak antiferromagnetic interactions (J = 0.82 +/- 0.01 cm(-)(1)) in 1 and ferromagnetic in 2 (J = -0.45 +/- 0.05 cm(-)(1)) and 3 (J = -0.21 +/- 0.02 cm(-)(1)). The extent of planarity of the bridging "Cu-O-C-O-Cu" moiety, acting as the super-exchange pathway between the neighboring copper centers, probably controls the sign of the magnetic exchange coupling in these compounds.     

Solid phase extraction of nitrate and nitrite anions using naturally and available sorbent

Radioactive waste contains nitrate and nitrite as well as radioactive fission products. Nitrate and nitrite anions are two of the major components of nuclear waste streams and contribute to environmental release hazards. The removal of nitrate and nitrite is a necessary step for the further treatment low-level radioactive wastes. The focus of the research is to evaluate the adsorption potential of solid phase derived from rice straw for nitrate and nitrite anions in single- and binary-component systems due to the fact that the rice straw is a very abundant and by-product material. The removal was accomplished under the optimize conditions of temperature, concentration, pH, contact time and quantity of adsorbent as these parameters are some of the main factors influencing the uptake of two solutes at the solid–solution interface. Batch-mode kinetic and equilibrium studies have been carried out. The experimental data was analyzed using equilibrium isotherm and kinetic models. The thermodynamic parameters (?G°, ?H°, and ?S°) were also determined using the equilibrium constant value obtained at different temperatures. Results show that this adsorbent is effective and much better or even superior than many sorbents for removal of nitrate and nitrite. The prepared sorbent as solid-phase extractant was successfully applied for the extraction of nitrate from actual water samples.     

An efficient one-pot multi-component synthesis of 3,4,5-substituted furan-2(5H)-ones catalyzed by tetra-n-butylammonium bisulfate

A facile one-pot synthesis of 3,4,5-substituted furan-2(5H)-one derivatives from a three-component reaction of aniline derivatives, dialkylacetylenedicarboxylates and aromatic aldehydes under mild conditions using tetra-n-butylammonium bisulfate as a catalyst has been developed.     

Catalytic behaviors of Co-Mn/TiO2 catalysts for Fischer-Tropsch synthesis

The 15%(Co-Mn)/TiO₂,(Co/Mn=1/6) catalyst was prepared using fusion procedure and studied for the conversion of synthesis gas to C_2~4 olefins. The effects of calcination conditions and operation conditions such as the H₂/CO molar feed ratio at different temperatures, gas hourly space velocity (GHSV) and total reaction pressure on the catalytic performance of catalyst were investigated. The stability of the catalyst during 150 h at optimal operation conditions (t=250 ℃ H₂/CO=2/1, GHSV=1 500 h^-1 and p=0.3 MPa) has been investigated. It is found that this catalyst is high stable for production C_2~4 olefins. Characterizations of both precursors and calcined catalysts by powder X-ray diffraction, scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) specific surface area measurement and thermal analysis methods such as thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) show that the different preparation method influences the catalyst precursor structure and morphology.     

Uranium recovery from UCF liquid waste by nanoporous MCM-41: breakthrough capacity and elution behavior studies

Adsorption and recovery of uranium by nanoporous MCM-41 from aqueous solutions (synthetic solution and uranium conversion facility liquid waste) were investigated by use of a fixed-bed column (1.2 cm diameter and 3.0 cm height). Adsorption was carried out at flow rates 0.2 and 0.5 mL min^?1, which correspond to retention times of 10 and 6 min. The maximum breakthrough capacity for uranium ions was achieved by use of nanoporous MCM-41 at the optimum pH of 3.6 and flow rate 0.2 mL min^?1 (61.95 μg g^?1). The Thomas and Yan models were applied to the experimental data, by use of linear regression, to determine the characteristics of the column for process design. The breakthrough curves calculated from the models were in good agreement with the experimental data. The elution behavior of uranium on nanoporous MCM-41 was studied with different eluents; the results showed that 0.1 M HCl is good eluent for uranium recovery. The regenerated column could be used in a multitude of adsorption–desorption cycles.     

Intramolecular hydrogen bonding in chemoselective synthesized 2-substituted pyrrole stable phosphorus ylide: GIAO, AIM, and NBO approaches

The chemoselectivity of geometrically ylide compounds is often hard to assign from experimental techniques, particular system with intramolecular hydrogen bonding (IHB) are even more challenging. Herein, theoretical calculations were performed to investigate whether theoretical results would provide consistent evidence for the existence of IHB to confirm experimental data and to evaluate strength of the N–H···O IHB from geometrical synthesized 2-substituted pyrrole stable phosphorus ylide (dimethyl 2-(1H-pyrrol-2-yl)-3-(triphenylphosphoranylidene) butanedioate in a single chemoselective compound. Topological parameters at the bond critical points (BCP) of intramolecular hydrogen bonds from Bader’s atoms in molecules (AIM) theory and Winhold’s natural bond orbital (NBO) calculations were analyzed at the B3LYP/6-311++g** level in details. A series of gage-including atomic orbital chemical shift (GIAO c.s.) calculations at the HF and DFT levels of theory were carried out to assign the ¹H NMR chemical shifts. The best prediction of the experimental ¹H NMR values was obtained at the mPW1PW91 levels using the 6-31G** basis set. Theoretical results, in agreement with the experimental data, were confirmed the N–H···O IHB was caused the deshielding of the proton to lower field. The barriers in double bond and single bond rotation were theoretically estimated in detailed and the AIM and NPA approaches were confirmed the loss of charge of the hydrogen atom involving in intramolecular N–H···O hydrogen bonding. The geometrical and topological parameters from AIM and NBO analyses were indicated the medium N–H···O IHB.