Littrow-type discretely tunable, Q-switched Nd:YAG laser around 1.3 μm

An all-solid-state, side diode array pulse pumped Nd:YAG laser tunable for six wavelengths ranging from 1318.8 nm to 1356.0 nm is developed. The tunability is obtained by using a grating in Littrow mode that also serves as an output coupler. The configuration ensures a line width as low as 0.04 nm. Thermal effects limit the maximum average power to 250 mW for an average absorbed pump power of 8.0 W in the free-running condition. An acousto-optic Q-switching of the laser provides pulses of width 251 ns with peak power of 733 W for an average pump power of 11.5 W. The laser may find application in microsurgery and dermatology. PACS 42.55.Xi; 42.60.-v; 42.60.Fc; 42.60.Gd; 42.62.Be     

Direct analysis of anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption-dielectric barrier discharge ionization mass spectrometry

Rapid detection of trace level anabolic steroids in urine is highly desirable to monitor the consumption of performance enhancing anabolic steroids by athletes. The present article describes a novel strategy for identifying the trace anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption (LPTD) coupled to dielectric barrier discharge (DBD) ionization mass spectrometry. Using this method the steroid molecules are enriched within a liquid droplet during the thermal desorption process and desorbed all-together at the last moment of droplet evaporation in a short time domain. The desorbed molecules were ionized using a dielectric barrier discharge ion-source in front of the mass spectrometer inlet at open atmosphere. This process facilitates the sensitivity enhancement with several orders of magnitude compared to the thermal desorption at a lower temperature. The limits of detection (LODs) of various steroid molecules were found to be in the range of 0.05–0.1 ng mL⁻¹ for standard solutions and around two orders of magnitude higher for synthetic urine samples. The detection limits of urinary anabolic steroids could be lowered by using a simple and rapid dichloromethane extraction technique. The analytical figures of merit of this technique were evaluated at open atmosphere using suitable internal standards. The technique is simple and rapid for high sensitivity and high throughput screening of anabolic steroids in urine.     

Confirmation of far infrared laser assignments from CH3-deformation and CH3-rocking states of optically pumped methanol

High-resolution Fourier transform spectroscopy has been applied to confirm previously proposed assignments for nine far infrared (FIR) laser lines from the CH₃-deformation state of CH₃OH and one line from the CH₃-rocking state. Accurate frequencies are deduced for the observed and other predicted FIR laser transitions. FIR torsional branch frequencies in the ground state which were used in the confirmation are presented. Comments are also made on the OH-bending mode of CH₃OH.     

Extraction of uranium(VI) by tri iso-amyl phosphate (TiAP) in ionic liquids

Batch extraction of uranium(VI) from uranyl nitrate solutions using TiAP in ionic liquids ([BMIM]PF₆ and [HMIM]PF₆) is studied. Effects of acidity, TiAP concentration in ionic liquid and temperature on distribution coefficient are studied. Results show that distribution coefficient increases with an increase in acidity and reduces with an increase in the alkyl chain length of the cation of the ionic liquid. Extraction of uranium(VI) by TiAP-[HMIM]PF₆ system is found to involve two molecules of the extractant per metal ion and extraction is found to change from being exothermic to endothermic as the percentage of the extractant is increased.     

Flexible enzymatic and chemo-enzymatic approaches to a broad range of uridine-diphospho-sugars

Enzymatic and chemo-enzymatic approaches provide straightforward access to uridine diphospho sugars irrespective of the relative and absolute configuration of the sugar, its ring size and substitution pattern.     

Kinetics and mechanism of the displacement of aqua ligands from cis-diaqua-bis(biguanide)chromium(III) by pyridine-2-aldoxime in EtOH-H2O mixtures

Kinetic and mechanistic studies of the displacement of aqua ligands from cis-[Cr(BigH)₂(H₂O)₂]³⁺ (BigH = H₂NC(NH)CHC(NH)NH₂) by pyridine-2-aldoxime (LH) in EtOH-H₂O mixtures, in the 30–45° C range, obey the following rate law over the 3.5–6.0 pH range,

Copper(II) complexes of thioarylazo-pentanedione: Structures,magnetism, redox properties and correlation with DFT calculations

Copper(II) complexes of 3-((2-(alkylthio)phenylazo)-2,4-pentanedione, tridentate O, N, S donor ligands, are described in this work. Chloride bridged copper(II) polymers (1) and thiocyanato bridged copper(II) dimmers (2) are characterized by a single crystal X-ray diffraction study. The complexes show antiferromagnetic interactions, with J = −0.5 ± 0.1 cm⁻¹ (1a) and −25.8 ± 0.5 cm⁻¹ (2b), which implies stronger coupling in the –SCN-bridging compound. The spectra, redox and magnetism are explained by DFT studies.     

Mass spectrometry of rhenium complexes: a comparative study by using LDI‐MS,MALDI‐MS,PESI‐MS and ESI‐MS

A group of rhenium (I) complexes including in their structure ligands such as CF₃SO₃‐, CH₃CO₂‐, CO, 2,2′‐bipyridine, dipyridil[3,2‐a:2′3′‐c]phenazine, naphthalene‐2‐carboxylate, anthracene‐9‐carboxylate, pyrene‐1‐carboxylate and 1,10‐phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF‐ESI‐CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M]^+. and to produce their reduction yielding the gas species [M]^–.. It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV–visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix‐assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor‐harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M]^–. species. Results obtained with 2‐[(2E)‐3‐(4‐tert‐buthylphenyl)‐2‐methylprop‐2‐enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of pyridine on the kinetics of polymerization of methyl methacrylate initiated by benzoyl peroxide and azobisisobutyronitrile at 60°C

Solution polymerization of MMA, with pyridine as the solvent and BZ₂O₂ and AIBN as thermal initiators, was studied kinetically at 60°C. The monomer exponent varied from 0.45 to 0.91 as [BZ₂O₂] was increased from 1 × 10^?2 to 30 × 10^?2 mole/liter in a concentration range of 8.3-4.6 mole/liter for MMA. For AIBN-initiated polymerization the monomer exponent remained constant at 0.69 as [AIBN] varied from 0.4 × 10^?2 to 1.0 × 10^?2 mole/liter in the same concentration range for MMA. The k²_p/k_t Value increased in both cases with an increase in pyridine concentration in the system. This was explained in terms of an increase in the k_p value, which was due presumably to the increased reactivity of the chain radicals by donor-acceptor interaction between the molecules of solvent pyridine and propagating PMMA radicals and in terms of lowering the k_t value for the diffusion-controlled termination reaction due to an increase in the medium viscosity and pyridine content.