Murraya Koenigii leaf-assisted rapid green synthesis of silver and gold nanoparticles

A facile bottom-up 'green' and rapid synthetic route using Murraya Koenigii leaf extract as reducing and stabilizing agent produced silver nanoparticles at ambient conditions and gold nanoparticles at 373 K. The nanoparticles were characterized using UV-vis, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR analysis. This method allows the synthesis of well-dispersed silver and gold nanoparticles having size ～10 nm and ～20 nm, respectively. Silver nanoparticles with size ～10 nm having symmetric SPR band centered at 411 nm is obtained within 5 min of addition of the extract to the solution of AgNO3 at room temperature. Nearly spherical gold nanoparticles having size ～20 nm with SPR at 532 nm is obtained on adding the leaf extract to the boiling solution of HAuCl4. Crystallinity of the nanoparticles is confirmed from the high-resolution TEM images, selected area electron diffraction (SAED) and XRD patterns. From the FTIR spectra it is found that the biomolecules responsible for capping are different in gold and silver nanoparticles. A comparison of the present work with the author's earlier reports on biosynthesis is also included.     

Large Zeolite H‐ZSM‐5 Crystals as Models for the Methanol‐to‐Hydrocarbons Process: Bridging the Gap between Single‐Particle Examination and Bulk Catalyst Analysis

The catalytic, deactivation, and regeneration characteristics of large coffin‐shaped H‐ZSM‐5 crystals were investigated during the methanol‐to‐hydrocarbons (MTH) reaction at 350 and 500 °C. Online gas‐phase effluent analysis and examination of retained material thereof were used to explore the bulk properties of large coffin‐shaped zeolite H‐ZSM‐5 crystals in a fixed‐bed reactor to introduce them as model catalysts for the MTH reaction. These findings were related to observations made at the individual particle level by using polarization‐dependent UV‐visible microspectroscopy and mass spectrometric techniques after reaction in an in situ microspectroscopy reaction cell. Excellent agreement between the spectroscopic measurements and the analysis of hydrocarbon deposits by means of retained hydrocarbon analysis and time‐of‐flight secondary‐ion mass spectrometry of spent catalyst materials was observed. The obtained data reveal a shift towards more condensed coke deposits on the outer zeolite surface at higher reaction temperatures. Zeolites in the fixed‐bed reactor setup underwent more coke deposition than those reacted in the in situ microspectroscopy reaction cell. Regeneration studies of the large zeolite crystals were performed by oxidation in O₂/inert gas mixtures at 550 °C. UV‐visible microspectroscopic measurements using the oligomerization of styrene derivatives as probe reaction indicated that the fraction of strong acid sites decreased during regeneration. This change was accompanied by a slight decrease in the initial conversion obtained after regeneration. H‐ZSM‐5 deactivated more rapidly at higher reaction temperature.     

Conversion of methanol over 10-ring zeolites with differing volumes at channel intersections: comparison of TNU-9, IM-5, ZSM-11 and ZSM-5

Four 3D 10-ring zeolites, IM-5, TNU-9, ZSM-11 and ZSM-5, with Si/Al = 14-24 and crystal sizes below 2 microns, were tested as catalysts for the methanol to hydrocarbons reaction (MTH) at atmospheric pressure, 350 °C and WHSV = 9 h(-1). All catalysts gave initially full methanol conversion, and showed strikingly similar effluent product selectivities. However, their life-time duration differed significantly, and decreased in the order: ZSM-11 > ZSM-5 ? TNU-9 > IM-5. A main difference between the two groups of stability behaviour was the size of cavities formed by channel intersections; larger cavities in TNU-9 and IM-5 leading to polyaromatics formation and a more rapid deactivation compared to ZSM-5 and ZSM-11. Effluent yield-conversion plots suggested that polymethylated benzene intermediates were more important in IM-5 and TNU-9 than in ZSM-5 and ZSM-11, where alkene methylation and cracking reactions seemed to dominate product formation. However, this difference had only minor influence on effluent selectivity.     

Effect of molecular association and reactivity on substitution in chromium(III)–salprn complexes

A new chromium(III)–Schiff base complex, [Cr(5-chlorosalprn)(H₂O)₂]ClO₄, where salprn = N,N-propylenebis(salicylideneimine) has been prepared and characterized by electrospray ionization mass spectrometric (ESIMS) analysis and other spectroscopic techniques. Single crystal X-ray data reveal that the complex assumes a trans-diaquo structure, [Cr(C₁₇H₁₈Cl₂N₂O₄)]ClO₄ · H₂O. The effect of phenyl ring substituents on the rate of formation of [O=Cr^V Schiff base]⁺ has been investigated. The bimolecular rate constant for the formation of O=Cr^V species by the [Cr(Schiff base)(H₂O)₂]ClO₄, where the Schiff base = salprn, (1) and 5-chlorosalprn, (2) with PhOI was compared. In the case of (2) the rate was found to be faster by an order of magnitude at pH = 4 compared to (1). The introduction of a chloro-substituent on the phenyl ring not only influences the rate of redox reactivity but also the pKa values of aquo ligands of the complexes, indicating the difference in the electronic environment around the metal ion in both (1) and (2).     

Formation and Functioning of Bimetallic Nanocatalysts: The Power of X‐ray Probes

Bimetallic nanocatalysts are key enablers of current chemical technologies, including car exhaust converters and fuel cells, and play a crucial role in industry to promote a wide range of chemical reactions. However, owing to significant characterization challenges, insights in the dynamic phenomena that shape and change the working state of the catalyst await further refinement. Herein, we discuss the atomic‐scale processes leading to mono‐ and bimetallic nanoparticle formation and highlight the dynamics and kinetics of lifetime changes in bimetallic catalysts with showcase examples for Pt‐based systems. We discuss how in situ and operando X‐ray spectroscopy, scattering, and diffraction can be used as a complementary toolbox to interrogate the working principles of today's and tomorrow's bimetallic nanocatalysts.     

Axially chiral biaryl diols catalyze highly enantioselective hetero-Diels-Alder reactions through hydrogen bonding

Axially chiral 1,1'-biaryl-2,2'-dimethanol (3, BAMOL) family of diols are highly effective catalysts for enantioselective hetero-Diels-Alder reactions between aminosiloxydiene 1 and a wide variety of unactivated aldehydes. The reactions proceed in useful yields and excellent enantioselectivities. The diols function in the same capacity as Lewis acids, by activating the aldehyde carbonyl group through hydrogen bonding.     

Characterization and biological activities of two copper(II) complexes with diethylenetriamine and 2,2'-bipyridine or 1,10-phenanthroline as ligands

Two new mixed ligand copper(II) complexes with diethylenetriamine, 2,2'-bipyridine and 1,10-phenanthroline have been synthesized. The crystal and molecular structures of [Cu(dien)(phen)](ClO(4))(2) and [Cu(dien)(bipy)](BF(4))(2) (dien=diethylenetriamine, phen=1,10-phenanthroline, bipy=2,2'-bipyridine) were determined by X-ray crystallography from single crystal data. These two complexes have similar structures. The EPR spectral data also suggest that these complexes have distorted square pyramidal geometry about copper(II). Anti-microbial and superoxide dismutase activities of these complexes have also been measured. They show the higher SOD activity than the corresponding simple Cu(II)-dien/Cu(II)-PMDT (PMDT=N,N,N',N',N'-pentamethyldiethylenetriamine) complexes because of a strong axial bond of one of the nitrogen atoms of the alpha-diimine. Both the complexes have been found to cleave plasmid DNA in the presence of co-reductants such as ascorbic acid and glutathione.     

Synthesis of cadmium sulphide in pure and mixed Langmuir-Blodgett films of n -octadecylsuccinic acid

Cadmium sulphide (CdS) nanoparticles were grown by the reaction of sodium sulphide (Na₂S) with Langmuir-Blodgett (LB) films of cadmium salts ofn-octadecylsuccinic acid (ODSU) and with LB films of ODSU in mixtures of octadecylamine and octadecyl alcohol. The results indicate that heterogeneous nucleation and aggregation in the pure ODSU LB films due to processes like Ostwald ripening are destabilized by the presence of the long-chain amine and alcohol in mixed systems. CdS nanoparticles in the LB films were monitored by UV-visible absorption spectra, which allow an estimation of the size of the particles. The morphology, size and nature of the nanocrystallites formed depend on whether the sulphidation was done on the pure film or in the mixed films. It is seen that particles of size around 1.6 nm were formed in ODSU/octadecylalcohol and ODSU/ octadecylamine mixed LB films while in pure ODSU films the size was about 2.7 nm. These films showed typical needle-shaped structures, as observed by the optical microscopic technique. Mean size and morphology were confirmed by transmission and scanning electron microscopy, while selective area electron diffraction patterns showed six-fold symmetry and indicated that the CdS crystals grow epitaxially with respect to the monolayer. Further, the crystallisation enhanced in the mixed LB films showed a characteristic zinc oxide (Wurtzite) structure compared with the pure ODSU matrix.