Scale-up synthesis of zinc borate from the reaction of zinc oxide and boric acid in aqueous medium

Synthesis of zinc borate was conducted in a laboratory and a pilot scale batch reactor to see the influence of process variables on the reaction parameters and the final product, 2ZnO·3B₂O₃·3.5H₂O. Effects of stirring speed, presence of baffles, amount of seed, particle size and purity of zinc oxide, and mole ratio of H₃BO₃:ZnO on the zinc borate formation reaction were examined at a constant temperature of 85 °C in a laboratory (4 L) and a pilot scale (85 L) reactor. Products obtained from the reaction in both reactors were characterized by chemical analysis, X-ray diffraction, particle size distribution analysis, thermal gravimetric analysis and scanning electron microscopy. The kinetic data for the zinc borate production reaction was fit by using the logistic model. The results revealed that the specific reaction rate, a model parameter, decreases with increase in particle size of zinc oxide and the presence of baffles, but increases with increase in stirring speed and purity of zinc oxide; however, it is unaffected with the changes in the amount of seed and reactants ratio. The reaction completion time is unaffected by scaling-up.     

Enhancement of catalytic activity by increasing surface area in heterogeneous catalysis

The use of nanoclusters in systems with confined void spaces such as inside mesoporous or microporous solids appears to be an efficient way of preventing aggregation of nanoclusters in their catalytic application. Zeolite-Y is considered as a suitable host providing highly ordered supercages with a diameter of 1.3 nm. Intrazeolite metal(0) nanoclusters were prepared at room temperature by ion-exchange of metal cations with the extra framework Na⁺ ions in Zeolite-Y, followed by the reduction of the metal cations in the cavities of Zeolite-Y with sodium borohydride in aqueous solution, whereby the Zeolite-Y is reloaded with Na⁺ ions. Hence, host framework remains intact as shown by using a multi-prong approach. Intrazeolite transition-metal(0) nanoclusters were isolated by suction filtration and drying in vacuum at room temperature and characterized by a combination of analytical methods. Intrazeolite metal(0) nanoclusters were tested as catalyst in the hydrolysis of sodium borohydride and ammonia-borane, both of which have been considered as a promising hydrogen storage materials. High catalytic activity and the outstandingly long lifetime of intrazeolite transition-metal(0) nanoclusters catalyst in the hydrogen generation from the hydrolysis of both sodium borohydride and ammonia-borane is demonstrated. The results are attributed to the small size of the nanoclusters within the zeolite cages as well as prevention of agglomeration of the nanoclusters.     

Diffusion-weighted magnetic resonance imaging in differentiation of postobstructive consolidation from central lung carcinoma

Purpose

To prospectively evaluate diffusion-weighted (DW) magnetic resonance (MR) imaging for differentiation of postobstructive consolidation from centrally located lung carcinomas by using apparent diffusion coefficients (ADCs).

Materials and Methods

An institutional review board approved this study; informed consent was obtained from patients. Forty-nine consecutive patients (3 women, 46 men; mean age, 63.6 years; age range, 42–85 years) with lung carcinoma underwent DW MR imaging. Forty patients had central and nine patients had peripheral lung carcinomas. ADC of each lung carcinoma was calculated from DW MR images obtained with two different b values (0, 1000 s/mm²).In the final study group including 27 patients with central lung carcinoma accompanying distal lung consolidation (mean age, 67.2 years; 3 women, 24 men), ADCs of lung carcinomas were statistically compared among cytologic/histologic types and accompanying postobstructive consolidations. Unpaired t test was used for measurable variables with normal distribution, and Kruskal–Wallis variance analysis and Mann–Whitney U tests were used for the measurable variables without normal distribution.

Results

There was no significant difference between mean ADC values of all types of carcinomas (P=.302) and also between mean ADC values of central (1.91 ± 0.7×10⁻³ mm²/s) and peripheral carcinomas (1.58 ± 0. 6×10⁻³ mm²/s) (P=.224). The mean ADC value for the masses of central lung carcinoma with postobstructive consolidations was 1.83 ± 0.75×10⁻³ mm²/s, and for consolidation was 2.50 ± 0.76×10⁻³ mm²/s. ADC of central carcinoma masses was significantly lower than that of postobstructive consolidations (P=.003).

Conclusions

ADC values of central lung carcinoma masses appear to be lower than accompanying postobstructive consolidations. ADC values could be considered useful as a differentiating parameter among central lung carcinomas and accompanying postobstructive consolidations.     

Synthesis and characterizations of N,N,N′,N′-tetrakis (diphenylphosphino)ethylendiamine derivatives: Use of palladium(II) complex as pre-catalyst in Suzuki coupling and Heck reactions

Oxidation of N,N,N′,N′-tetrakis(diphenylphosphino)ethylendiamine (1) with elemental sulfur and selenium gives the corresponding sulfide and selenide, respectively, [(Ph₂P(E))₂NCH₂CH₂N(P(E)Ph₂)₂] (E: S 1a, Se 1b). Complexes of 1 [(M₂Cl₄){(Ph₂P)₂NCH₂CH₂N(PPh₂)₂}] (M: Ni(II) 1c, Pd(II) 1d, Pt(II) 1e) were prepared by the reaction of 1 with NiCl₂ or [MCl₂(COD)] (M = Pd, Pt). The new compounds were characterized by NMR, IR spectroscopy and elemental analysis. The catalytic activity of Pd(II) complex 1d was tested in the Suzuki coupling reaction and Heck reaction. The palladium complex 1d catalyses the Heck reaction between styrene and aryl bromides as well as Suzuki coupling reaction between phenylboronic acid and arylbromides affording stilbenes and biphenyls in high yield, respectively.     

Catalytic methanolysis of hydrazine borane: a new and efficient hydrogen generation system under mild conditions

Safe and efficient hydrogen storage is a major obstacle for using hydrogen as an energy carrier. Therefore, intensive efforts have been focused on the development of new materials for chemical hydrogen storage. Of particular importance, hydrazine borane (N(2)H(4)BH(3)) is emerging as one of the most promising solid hydrogen carriers due to its high gravimetric hydrogen storage capacity (15.4 wt%) and low molecular weight. Herein, we report metal catalyzed methanolysis of hydrazine borane (N(2)H(4)BH(3), HB) as a fast hydrogen generation system under mild conditions. When trace amounts of nickel(ii) chloride (NiCl(2)) is added to the methanol solution of hydrazine borane ([HB]/[Ni] ≥ 200) the reaction solution releases 3 equiv. of H(2) with a rate of 24 mol H(2) (mol Ni min)(-1) at room temperature. The results reported here also includes (i) identification of the reaction products by using ATR-IR, DP-MS, (1)H and (11)B NMR spectroscopic techniques and the establishment of the reaction stoichiometry, (ii) investigation of the effect of substrate and catalyst concentrations on the hydrogen generation rate to determine the rate law for the catalytic methanolysis of hydrazine borane, (iii) determination of the activation parameters (E(a), ΔH(#), and ΔS(#)) for the catalytic methanolysis of hydrazine borane by using the temperature dependent rate data of the hydrogen generation.     

Photochemische reaktionen von übergangsmetall-olefin-komplexen: XI. [4+ 6]-cycloaddition von tricyclo[6.3.0.02,7]undeca-3,5-dien antricarbonyl-η6-1,3,5-cycloheptatrien-chrom(0)

The photochemical reaction of tricarbonyl-η⁶-1,3,5-cycloheptatriene-chromium(0) (I) with tricyclo[6.3.0.0^2,7]undeca-3,5-diene (II) in n-pentane at 248 K yields the [4 + 6]-cycloadduct tricarbonyl-η⁶-pentacyclo[7.6.2.1^10,15.0^2,8.0^3,7]octadeca-11,13,16-triene-chromium(0) (III). Detachment of the pentacyclic triene ligand from chromium can be achieved with trimethylphosphite. The constitutions of complex III and of the pentacyclic hydrocarbon IV were determined by spectroscopic means.     

Preparation and characterization of a new CdS–NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/reduced graphene oxide photocatalyst and its use for degradation of methylene blue under visible light irradiation

In this paper, CdS nanoparticles as a visible light active photocatalyst were coupled by NiFe₂O₄ and reduced graphene oxide (rGO) to form CdS–NiFe₂O₄/rGO nanocomposite by facile hydrothermal methods. The CdS–NiFe₂O₄/rGO nanocomposite shows enhanced photocatalytic activity for the degradation of methylene blue (MB) under visible light illumination. In addition to improved photocatalytic performance, this prepared nanocomposite shows increased photostability and is magnetically separable from the aqueous media. The degradation rate constant (k_app) of the optimized photocatalyst, i.e. CdS–NiFe₂O₄ (0.05)/rGO 25 wt% nanocomposite, was higher than the corresponding CdS and NiFe₂O₄ nanoparticles by factors of 11.1 and 8.9, respectively. The synergistic interactions between CdS, NiFe₂O₄ and rGO lead to enhanced surface area, reduced aggregation of the nanoparticles, decreased the recombination of photogenerated electron–hole pairs, and increased the charge separation efficiency and effective electron–hole generation transfer. According to the obtained results, a proposed mechanism of the photodegradation of MB under visible light irradiation is finally mentioned.     

Synthesis and characterization of new (N‐diphenylphosphino)‐isopropylanilines and their complexes: crystal structure of (Ph2P S)NH?C6H4?4?CH(CH3)2 and catalytic activity of palladium(II) complexes in the Heck and Suzuki cross‐coupling reactions

Three new (N‐diphenylphosphino)‐isopropylanilines, having isopropyl substituent at the carbon 2‐ (1) 4‐ (2) or 2,6‐ (3) were prepared from the aminolysis of chlorodiphenylphosphine with 2‐isopropylaniline, 4‐isopropylaniline or 2,6‐diisopropylaniline, respectively, under anaerobic conditions. Oxidation of 1,2 and 3 with aqueous hydrogen peroxide, elemental sulfur or gray selenium gave the corresponding oxides, sulfides and selenides (Ph₂P?E)NH? C₆H₄? 2‐CH(CH₃)₂, (Ph₂P?E)NH? C₆H₄? 4‐CH(CH₃)₂ and (Ph₂P?E)NH? C₆H₄? 2,6‐{CH(CH₃)₂}₂, where E = O, S, or Se, respectively. The reaction of [M(cod)Cl₂] (M = Pd, Pt; cod = 1,5‐cyclooctadiene) with two equivalents of 1,2 or 3 yields the corresponding monodendate complexes [M((Ph₂P)NH? C₆H₄? 2‐CH(CH₃)₂)₂Cl₂], M = Pd 1d, M = Pt 1e, [M((Ph₂P)NH? C₆H₄? 4‐CH(CH₃)₂)₂Cl₂], M = Pd 2d, M = Pt 2e and [M((Ph₂P)NH? C₆H₄? 2,6‐(CH(CH₃)₂)₂)₂Cl₂], M = Pd 3d, M = Pt 3e, respectively. All the compounds were isolated as analytically pure substances and characterized by NMR, IR spectroscopy and elemental analysis. Furthermore, representative solid‐state structure of [(Ph₂P?S)NH? C₆H₄? 4‐CH(CH₃)₂] (2b) was determined using single crystal X‐ray diffraction technique. The complexes 1d–3d were tested and found to be highly active catalysts in the Suzuki coupling and Heck reaction, affording biphenyls and stilbenes, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

PICOSECOND FLUORESCENCE DECAY TIME MEASUREMENTS OF NUCLEIC ACIDS AT ROOM TEMPERATURE IN AQUEOUS SOLUTION

Abstract— We report the room-temperature fluorescence decay times of calf thymus DNA when native and when 16% of its guanine residues are methylated at theN–7 position. The samples were excited with single, 25 ps, 266 nm laser pulses from a frequency-quadrupled Nd: YAG laser. Fluorescence was detected with a streak camera-optical multichannel analyzer system that has a time jitter of about 2 ps. For DNA and methylated DNA we detected a major component that has a decay time of about 10 and 20 ps, respectively. A second component has a corresponding decay time of about 65 and 80 ps and makes a contribution of0–10% and20–40% depending on the transmission characteristics of the emission filter employed. In contrast, the decay time of 7-methyl GMP, which contains the same fluorophore as methylated DNA, is approximately single exponential and has a decay time of180–210 ps depending on the emission filter. The absence of a pronounced time delay between the fluorescence decay profiles of the nucleic acids and the exciting light pulse points against the formation of excited-state complexes (excimers).     

Synthesis and Spectroscopic Characterization of Group 6 Pentacarbonyl(4-substituted pyridine)metal(0) Complexes

Carbonyl-metal (M:Cr, Mo, W) derivatives of 4-substituted pyridines [4-methylpyridine (4-mp), 4-tert-butylpyridine (4-tbp) and 4-dimethylaminopyridine (4-dmap)] where the metal center is bonded to the nitrogen atom of the substituted pyridine ring are described. The organometallic complexes, M(CO)₅L, were synthesized by either the direct reaction of the metal hexacarbonyls or by the thermal substitution of M(CO)₅(THF) with the pyridine ligands; 4-methylpyridine (1), 4-tert-butylpyridine (2), 4-dimethylaminopyridine (3). The reported complexes were purified by column chromatography and recrystallization. The complexes were all characterized in solution by elemental analysis, MS, ir , ¹H-nmr and ¹³C-nmr spectroscopies.