Quantification of clenbuterol in equine plasma,urine and tissue by liquid chromatography coupled on-line with quadrupole time-of-flight mass spectrometry

Clenbuterol (CBL) is a potent beta(2)-adrenoceptor agonist used for the management of respiratory disorders in the horse. The detection and quantification of CBL can pose a problem due to its potency, the relatively low dose administered to the horse, its slow clearance and low plasma concentrations. Thus, a sensitive method for the quantification and confirmation of CBL in racehorses is required to study its distribution and elimination. A sensitive and fast method was developed for quantification and confirmation of the presence of CBL in equine plasma, urine and tissue samples. The method involved liquid-liquid extraction (LLE), separation by liquid chromatography (LC) on a short cyano column, and pseudo multiple reaction monitoring (pseudo-MRM) by electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS). At very low concentrations (picograms of CBL/mL), LLE produced better extraction efficiency and calibration curves than solid-phase extraction (SPE). The operating parameters for electrospray QTOF and yield of the product ion in MRM were optimized to enhance sensitivity for the detection and quantification of CBL. The quantification range of the method was 0.013-10 ng of CBL/mL plasma, 0.05-20 ng/0.1 mL of urine, and 0.025-10 ng/g tissue. The detection limit of the method was 13 pg/mL of plasma, 50 pg/0.1 mL of urine, and 25 pg/g of tissue. The method was successfully applied to the analysis of CBL in plasma, urine and various tissue samples, and in pharmacokinetic (PK) studies of CBL in the horse. CBL was quantified for 96 h in plasma and 288 h in urine post-administration of CLB (1.6 micro g/kg, 2 x daily x 7 days). This method is useful for the detection and quantification of very low concentrations of CBL in urine, plasma and tissue samples.     

A facile one‐pot synthesis of novel substituted 1,2,3,4‐tetrahydropyrimidine,part 2: Synthesis of 1‐(aralkyl/aryl)‐3‐(alkyl/aralkyl/aryl)‐5‐aroyl‐1,2,3,4‐tetrahydropyrimidines

1‐(Aralkyl/aryl)‐3‐(alkyyaralkyl)‐5‐aroyl‐1,2,3,4‐tetrahydropyrimidines ( 2a‐c ) have been synthesized by dethiomethylation of 5‐aroyl‐6‐methylthio‐1,2,3,4‐tetrahydropyrimidines ( 1a‐c ). An alternative one‐pot synthetic strategy has been developed for the title compounds 2a‐t by the reaction of enaminones 3 with pri mary amine and formaldehyde in refluxing methanol in good yields.     

One-pot thioetherification of aryl halides with thiourea and benzyl bromide in water catalyzed by Cu-grafted furfural imine-functionalized mesoporous SBA-15

Surface functionalization of SBA-15 followed by its reaction with Cu(OAc)(2) has been carried out to develop a new Cu-grafted functionalized mesoporous material, which catalyzes one-pot three component coupling of different aryl halides with thiourea and benzyl bromide in aqueous medium to produce aryl thioethers in very good yields (80-88%).     

Zeolite-mediated photochemical charge separation using a surface-entrapped ruthenium-polypyridyl complex

Employing the strategy of quaternization of the 2,2' N atoms of the conjugated bipyridine ligand 1,4-bis[2-(4'-methyl-2,2'-bipyrid-4-yl)ethenyl]benzene (L), a polypyridyl complex of ruthenium(II) was tethered on the surface of zeolite Y. Electrochemical and spectroscopic properties of the complex suggest that, upon visible photoexcitation of the MLCT band, the electron is localized on the conjugated ligand rather than the bipyridines. Electron transfer from the surface complex to bipyridinium ions (methyl viologen) within the zeolite was observed. Visible light photolysis of the ruthenium-zeolite solid ion-exchanged with diquat and suspended in a propyl viologen sulfonate solution led to permanent formation of the blue propyl viologen sulfonate radical ion in solution. The model that is proposed involves intrazeolitic charge transfer to ion-exchanged diquat followed by interfacial (zeolite to solution) electron transfer to propyl viologen sulfonate in solution. Because of the slow intramolecular back-electron-transfer reaction and the forward electron propagation via the ion-exchanged diquat, Ru(III) is formed. This Ru(III) complex formed on the zeolite is proposed to react rapidly with water in the presence of light, followed by reaction with the propyl viologen sulfonate, to form pyridones and regeneration of Ru(II), which then continues the photochemical process.     

Structurally Stabilized Organosilane‐Templated Thermostable Mesoporous Titania

Structurally thermostable mesoporous anatase TiO₂ (m‐TiO₂) nanoparticles, uniquely decorated with atomically dispersed SiO₂, is reported for the first time. The inorganic Si portion of the novel organosilane template, used as a mesopores‐directing agent, is found to be incorporated in the pore walls of the titania aggregates, mainly as isolated sites. This is evident by transmission electron microscopy and high‐angle annular dark field scanning transmission electron microscopy, combined with electron dispersive X‐ray spectroscopy. This type of unique structure provides exceptional stability to this new material against thermal collapse of the mesoporous structure, which is reflected in its high surface area (the highest known for anatase titania), even after high‐temperature (550 °C) calcination. Control of crystallite size, pore diameter, and surface area is achieved by varying the molar ratios of the titanium precursor and the template during synthesis. These mesoporous materials retain their porosity and high surface area after template removal and further NaOH/HCl treatment to remove silica. We investigate their performance for dye‐sensitized solar cells (DSSCs) with bilayer TiO₂ electrodes, which are prepared by applying a coating of m‐TiO₂ onto a commercial titania (P25) film. The high surface area of the upper mesoporous layer in the P25–m‐TiO₂ DSSC significantly increases the dye loading ability of the photoanode. The photocurrent and fill factor for the DSSC with the bilayer TiO₂ electrode are greatly improved. The large increase in photocurrent current (ca. 56 %) in the P25–m‐TiO₂ DSSC is believed to play a significant role in achieving a remarkable increase in the photovoltaic efficiency (60 %) of the device, compared to DSSCs with a monolayer of P25 as the electrode.     

Self‐Assembly of DNA–Oligo(p‐phenylene‐ethynylene) Hybrid Amphiphiles into Surface‐Engineered Vesicles with Enhanced Emission

Surface‐addressable nanostructures of linearly π‐conjugated molecules play a crucial role in the emerging field of nanoelectronics. Herein, by using DNA as the hydrophilic segment, we demonstrate a solid‐phase “click” chemistry approach for the synthesis of a series of DNA–chromophore hybrid amphiphiles and report their reversible self‐assembly into surface‐engineered vesicles with enhanced emission. DNA‐directed surface addressability of the vesicles was demonstrated through the integration of gold nanoparticles onto the surface of the vesicles by sequence‐specific DNA hybridization. This system could be converted to a supramolecular light‐harvesting antenna by integrating suitable FRET acceptors onto the surface of the nanostructures. The general nature of the synthesis, surface addressability, and biocompatibility of the resulting nanostructures offer great promises for nanoelectronics, energy, and biomedical applications.     

Ion beam irradiation of ZnS dispersed in PMMA and its photocatalytic application

ZnS nanoparticles implanted with 45 keV O⁵⁺ ion beam exhibited 83.6 % degradation of methyl blue in 2 h. This idea was utilized to fabricate nanocomposite system of ZnS and PMMA where ZnS nanoparticles were immobilized in PMMA film and irradiated with 45 keV O⁵⁺ ion beam at particle fluence of 2.5 × 10¹⁵, 1 × 10¹⁶ and 4 × 10¹⁶ particles/cm². These irradiated batches of ZnS nanoparticle immobilized in PMMA batches revealed formation of porous structure characterized by scanning electron microscopy and these batches exhibited 54 % photocatalytic degradation of methyl blue in 80 min which was higher as compared to the pristine ZnS nanoparticles.     

Self-propagating assembly of a molecular-based multilayer

Accelerated growth of a molecular-based material that is an active participant in its continuing self-propagated assembly has been demonstrated. This nonlinear growth process involves diffusion of palladium into a network consisting of metal-based chromophores linked via palladium.     

Computation-led design of pollutant gas sensors with bare and carbon nanotube supported rhodium alloys

Quantum chemical study has been performed on finite-sized bi-metallic Rh3M alloys, M = Ag, Ir, Pd, Pt, Au, derived from magic cluster, Rh4. Bond length of C–O and N–O are noticed to be elongated in the presence of rhodium alloy clusters. CO2 and NO2 gases are found to be highly adsorbed on Rh3M clusters, which is confirmed by stretching frequency of C–O and N–O. DFT evaluated dipole moment and electronic charge redistribution suggests the sensing capability of CO2 and NO2 gases by Rh3M clusters which is further confirmed by the calculated HOMO–LUMO gap. Mixed rhodium alloy clusters supported on single-wall carbon nanotube (SWCNT) exhibits much higher ability to sense CO2 and NO2. On the other hand, SWCNT@Rh3M shows higher catalytic activity for the activation of CO2 and NO2 in comparison to bare Rh3M because of the higher electronic charge redistribution in the case of SWCNT@Rh3M. In case of SWCNT-supported gas adsorbed clusters, p electrons play a major role in bonding.