Solid state white light emitting systems based on CeF3: RE3+ nanoparticles and their composites with polymers

A series of doped CeF(3): RE(3+) (RE(3+): Tb(3+), Eu(3+) and Dy(3+)) nanoparticles were synthesized, with the aim of obtaining a white light emitting composition, by a simple polyol route at 160°C and characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FT-IR) and photoluminescence. Uniformly distributed and highly water-dispersible rectangular nanoparticles (length ~15-20 nm, breadth ~5-10 nm) were obtained. The steady state and time resolved luminescence studies confirmed efficient energy transfer from the host to activator ions. Lifetime studies revealed that optimum luminescence is observed for 2.5 mol% Dy(3+) and 7.5 mol% Tb(3+). The energy transfer efficiencies (Ce(3+) to activators) were found to be 89% for CeF(3): Tb(3+) (7.5 mol%) nanoparticles and 60% for CeF(3): Dy(3+) (2.5 mol%) nanoparticles. Different concentrations of Tb(3+), Eu(3+) and Dy(3+) were doped to achieve a white light emitting phosphor for UV-based LEDs (light emitting diodes). Finally CeF(3), triply doped with 2.0 mol%Tb(3+), 4.5 mol% Eu(3+) and 3.5 mol% Dy(3+), was found to have impressive chromaticity co-ordinates, close to broad day light. The colloidal solutions of doped CeF(3) nanoparticles emitted bright green (Tb(3+)), blue (Dy(3+)) and white (triply doped) luminescence upon host excitation. Composites of poly methyl methacrylate (PMMA) and poly vinyl alcohol (PVA) were made with CeF(3): 5.0 mol%Tb(3+), CeF(3): 5.0 mol% Dy(3+) and triply doped white light emitting composition. The CeF(3)/PMMA (PVA) nanocomposite films, so obtained, are highly transparent (in the visible spectral range) and exhibit strong photoluminescence upon UV excitation.     

Synthesis of 5‐aryl and 5‐amidocamptothecins

A variety of 5‐aryl‐(20S)‐camptothecin derivatives were synthesized by the reaction of 5‐hydroxy‐(20S)‐camptothecin with aromatic hydrocarbons under Friedel‐Craft reaction conditions in moderate to good yield as diastereomeric pairs. The methodology was then extended for the synthesis of 5‐amido‐(20S)‐camptothecin derivatives by reacting 5‐hydroxy‐(20S)‐camptothecin with alkyl and aryl nitriles under Ritter type reaction conditions. The reaction is presumed to proceed through an iminium ion intermediate under Friedel Craft and Ritter type reaction condition, which is further trapped by nucleophile present in the reaction medium. J. Heterocyclic Chem., 00 , 00 (2011).     

Triazoles as complexing agents: Synthesis and structural studies of some bivalent metal ion complexes with Bi- and tridentate ligands

Summary Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of 4-amino-5-mercapto-3-trifluoromethyl-s-triazole (AMTT) and 5-mercapto-4-salicylideneamino-3-trifluoromethyl-s-triazole (MSTT) have been synthesized and characterized on the basis of elemental analyses, magnetic measurements, infrared and electronic spectral data. The ligandsAMTT andMSTT were characterized by elemental analyses, infrared and¹H NMR spectral studies.AMTT, involving N and S as donor atoms, andMSTT, involving N, O and S as donor atoms, act as bi- and tridentate ligands, respectively. The geometry of the complexes has been assigned on the basis of magnetic and electronic spectral data. EPR parameters for copper (II) complexes have been calculated. Thermal stabilities of the complexes are also reported. Due to insolubility in water and common organic solvents and infusibility at higher temperatures, all the complexes are thought to be polymeric in nature.

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Triazole als Komplexierungs-Agentien: Synthese und Strukturuntersuchungen an einigen bivalenten Metallionenkomplexen mit zwei- und dreizähnigen Liganden

Zusammenfassung Es wurden Co(II)-, Ni(II)-, Cu(II)-, Zn(II)- und Cd(II)-Komplexe von 4-Amino-5-mercapto-3-trifluormethyl-s-triazol (AMTT) und 5-Mercapto-4-salizylidenamino-3-trifluormethyl-s-triazol (MSTT) hergestellt und mittels Elementaranalyse, magnetischen Messungen, Infrarot- und Elektronenspektroskopie charakterisiert. Die LigandenAMTT undMSTT wurden elementaranalytisch und spektroskopisch (IR und¹H-NMR) charakterisiert.AMT wirkt über die N-und S-Donoratome als zweizähniger Ligand,MSTT über N, O und S als dreizähniger Ligand. Die Geometrie der Komplexe wurde auf der Basis von magnetischen und elektronenspektroskopischen Daten zugeordnet. Für die Cu(II)-Komplexe wurden die EPR-Parameter berechnet. Die thermischen Stabilitäten der Komplexe wurde ebenfalls untersucht. Wegen ihrer Unlöslichkeit in Wasser und gängigen organischen Lösungsmitteln und der Unschmelzbarkeit bei höheren Temperaturen wird eine polymere Natur der Komplexe angenommen.

     

Activation and stabilization of enzymes entrapped into reversed micelles

Observations of the activity of two hydrolyzing enzymes—protease and α-amylase—entrapped inside the reversed micelles formed by surfactants in hexane, benzene, and cyclohexane are reported. The surfactants chosen for this study are: Tween 80, a nonionic surfactant, Cetyl pyridinium chloride, a cationic surfactant, and two anionic surfactants, sodium lauryl sulfate and Aerosol OT. Tween 80 enhances the activity of both protease and α-amylase. Sodium lauryl sulfate and Aerosol OT, which are ionic surfactants, enhance the activity of protease, but inhibit the activity of α-amylase. Cetyl pyridinium chloride, however, enhances the activity of α-amylase, but inhibits the activity of protease. Enhanced activity is generally severalfold greater in comparison to the activity observed in the usual aqueous system in the absence of reversed micelles. It has also been observed that the enhanced activity of the enzymes entrapped inside the reversed micelles remains preserved for a much longer period of time in comparison to the activity in the usual aqueous systems. These observations, which support the view that with proper choice of surfactant and the organic solvent, reversed micelles act like a microreactor that provides a favorable aqueous microenvironment for enzyme activity, have biotechnological overtones.     

Synthesis of α‐Benzylthiobenzimidazoleacetonitriles and Their Chemoselective Reduction of the Double Bond with NaBH4

Condensation of 2‐((1H‐benzimidazol‐2‐yl)thio)acetonitre 1 with aromatic aldehydes in methanol containing piperidine gave the corresponding 2‐((1H‐benzimidazol‐2‐yl)thio)‐3‐arylacrylonitrile 2 , which on treatment with NaBH₄ in ethanol unexpectedly and chemoselectively gave 2‐((1H‐benzimidazol‐2‐yl)thio)‐3‐arylpropanenitrile 3 by the reduction of the double bond of 2 . 3 on methylation with dimethyl sulfate containing K₂CO₃ as a base and tetrabutylammonium bromide as PTC gave 2‐((1‐methylbenzimidazol‐2‐yl)thio)‐3‐arylpropanenitrile 6 . The latter could also be prepared in an alternative way by reaction of 1 with dimethyl sulfate giving the intermediary 2‐((1‐methylbenzimidazol‐2‐yl)thio)acetonitrile 4 , followed by condensation with aromatic aldehydes yielding 5 and subsequent reduction of 5 with NaBH₄ in methanol. 6 could be directly synthesized by treatment of 4 with benzyl chloride in DMF and triethylamine as a base at 60°C for 5 h.     

Ion-exchange studies of <Superscript>110m</Superscript>Ag(I) using synthetic inorganic ion-exchanger

In the present investigation, the selective adsorption of silver on synthetic inorganic ion exchanger, zinc(II) ferrocyanide, has been established by batch method, under specific conditions, using ^110mAg as a tracer. The efficiency of adsorption has been determined by γ-ray spectrometry and was found to be greater than 96%. The Ag(I) uptake by the exchanger has also been evaluated. The selectivity of the method was checked by studying the adsorption of Ag(I) in the presence of a number of foreign ions using their corresponding tracers. The interfering ions were removed by washing the ion-exchanger with appropriate reagents, so that it could be applied for the determination of trace amount of Ag(I) in complex matrices, containing trace amount of other metal ions.     

In situ derivatization hollow fiber mediated liquid phase microextraction of alkylphosphonic acids from water

Alkylphosphonic acids (APAs), particularly the methyl-, ethyl-, isopropyl- and n-propyl-phosphonic acids are important markers of extremely toxic nerve agents. Hence, their detection and identification is of vital importance to verification of chemical weapons convention (CWC). Verification analysis of CWC requires development of fast, reliable, simple and reproducible sample preparation methods of water and soil samples. Present investigation is focused on the optimization of alkylation of APAs in water with subsequent extraction of alkylated acids by hollow fiber liquid phase microextraction (HF-LPME). This simple and sensitive sample preparation of APAs from water offered better recoveries in comparison to conventionally used extraction technique. Under optimized conditions, the APAs were detected at the concentration of 0.5-0.75 microg/mL with S/N ratio > or = 5, whereas the LODs for alkyl APAs (monobasic APAs) were achieved up to 0.1 microg/mL. The developed method was finally tested with water samples supplied in 19th official proficiency test conducted by the OPCW.     

An evaluation of the CYP2D6 and CYP3A4 inhibition potential of metoprolol metabolites and their contribution to drug–drug and drug–herb interaction by LC‐ESI/MS/MS

The aim of the present study was to evaluate the contribution of metabolites to drug–drug interaction and drug–herb interaction using the inhibition of CYP2D6 and CYP3A4 by metoprolol (MET) and its metabolites. The peak concentrations of unbound plasma concentration of MET, α‐hydroxy metoprolol (HM), O‐desmethyl metoprolol (ODM) and N‐desisopropyl metoprolol (DIM) were 90.37 ± 2.69, 33.32 ± 1.92, 16.93 ± 1.70 and 7.96 ± 0.94 ng/mL, respectively. The metabolites identified, HM and ODM, had a ratio of metabolic area under the concentration–time curve (AUC) to parent AUC of ≥0.25 when either total or unbound concentration of metabolite was considered. In vitro CYP2D6 and CYP3A4 inhibition by MET, HM and ODM study revealed that MET, HM and ODM were not inhibitors of CYP3A4‐catalyzed midazolam metabolism and CYP2D6‐catalyzed dextromethorphan metabolism. However, DIM only met the criteria of >10% of the total drug related material and <25% of the parent using unbound concentrations. If CYP inhibition testing is solely based on metabolite exposure, DIM metabolite would probably not be considered. However, the present study has demonstrated that DIM contributes significantly to in vitro drug–drug interaction. Copyright © 2016 John Wiley & Sons, Ltd.     

Asymmetric synthesis of (–)-leiocarpin A via (–)-(S)-goniothalamin employing Julia–Kocienski olefination

A concise and enantioselective syntheses of antileukemic natural products such as (–)-(S)-goniothalamin and (–)-leiocarpin A has been accomplished in excellent yields. By employing reported conditions on suitable substrates via Julia–Kocienski olefination, intramolecular lactonization, and subsequently dehydroxylative olefination, (–)-(S)-goniothalamin was synthesized. Then Sharpless asymmetric dihydroxylation–intramolecular Michael addition on (–)-(S)-goniothalamin provided (–)-leiocarpin A.