Showing papers in "Journal of Chemical Sciences in 2014"

Electrocatalytic activity of Cu2O nanocubes based electrode for glucose oxidation

Abstract: A direct electrocatalytic activity of glucose oxidation on cuprous oxide modified glassy carbon electrode is reported. Cu2O nanocubes were synthesized by a simple wet chemical route in the absence of surfactants. Purity, shape and morphology of Cu2O are characterized by XRD, SEM, XPS and DRS-UV. The Cu2O nanocubes-modified glassy carbon electrode (GCE) exhibited high electrocatalytic activity towards glucose oxidation compared with bare GCE electrode. At an applied potential of +0.60 V, the Cu2O electrode presented a high sensitivity of 121.7 μA/mM. A linear response was obtained from 0 to 500 μM, a response time less than 5 s and a detection limit of 38 μM (signal/noise=3). The Cu2O nanocubes modified electrode was stable towards interfering molecules like uric acid (UA), ascorbic acid (AA) and dopamine (DA). In short, a facile chemical preparation process of cuprous oxide nanocubes, and the fabricated modified electrode allow highly sensitive, selective, and fast amperometric sensing of glucose, which is promising for the future development of non-enzymatic glucose sensors.

Synthesis and visible light photocatalytic activity of nanocrystalline PrFeO 3 perovskite for hydrogen generation in ethanol–water system

Abstract: Nanocrystalline PrFeO3 perovskite type orthoferrite was synthesized at 700°C by using three different synthesis methods, namely sol–gel, template and combustion method. The synthesized materials were characterized by XRD, BET-SA, SEM, HRTEM, XPS, FTIR and UV-DRS techniques to understand their physico-chemical properties. Characterization data reveal the formation of nanocrystalline PrFeO3 perovskite composition with improved physical properties, possibly due to lower synthesis temperature used. PrFeO3 synthesized by sol–gel method consists of crystallite size of about 20 nm with absorption maxima at 595 nm wavelength in visible light range. This photocatalyst shows hydrogen generation of about 2847 μmol.g−1.h−1, under visible light irradiation in ethanol–water system. The photocatalyst was further investigated for various operational parameters such as photocatalyst dose variation, illumination intensity, time, etc. in a view to optimize the hydrogen generation as well as to understand mechanistic aspects. This material appears to follow a semiconductor type mechanism for ethanol-assisted visible light photocatalyic water-splitting and can also be an interesting candidate to develop hetero-junction type photocatalysts.

Nano-titania-supported Preyssler-type heteropolyacid: An efficient and reusable catalyst in ultrasound-promoted synthesis of 4H-chromenes and 4H-pyrano[2,3-c]pyrazoles

Abstract: An efficient and convenient procedure has been described for one-pot multi-component synthesis of tetrahydrobenzo[b]pyrans known as 4H-chromenes and 1,4-dihydropyrano[2,3-c]pyrazole derivatives in the presence of nano-titania-supported Preyssler-type heteropolyacid, n-TiO2/H14[NaP5W30O110], as a heterogeneous catalyst. The reactions proceeded smoothly under ultrasound irradiation condition to afford the corresponding products in quantitative yields. The catalyst can be easily recovered and reused for several successive fresh runs with no significant loss of catalytic activity.

Interaction of cyclodextrins with human and bovine serum albumins: A combined spectroscopic and computational investigation

Abstract: Interaction of cyclodextrins (CDs) with the two most abundant proteins, namely human serum albumin (HSA) and bovine serum albumin (BSA), has been investigated using steady-state and time-resolved fluorometric techniques, circular dichroism measurements and molecular docking simulation. The study reveals that the three CDs interact differently on the fluorescence and fluorescence lifetimes of the serum albumins. However, fluorescence anisotropy and circular dichroism are not affected. Depending on their size, different CDs bind to the serum albumins in different positions, resulting in changes in the spectral behaviour of the proteins. Docking study suggests the probable binding sites of the three CDs with the proteins. Combined experimental and computational studies imply that sufficiently high concentration of CDs causes loosening of the rigid structures of these transport proteins, although their secondary structures remain intact. Thus, CDs are found to be safe for the serum proteins from the structural point of view.

Novel catalysts for valorization of biomass to value-added chemicals and fuels

Abstract: Key furan compounds such as 5-hydroxymethylfurfural (HMF), 2,5-furandicarboxylic acid (FDCA) and 2,5-dimethylfuran (DMF) were synthesized from renewable feedstocks. Dehydration of fructose was carried out in biphasic conditions employing several solid acid catalysts by targeting selective formation of HMF. Its selectivity is linearly dependent on total acidity clearly revealing that lower acidity favours selective formation of HMF. Oxidation and hydrogenolysis of HMF has been explored using 2 wt% Ru-K-OMS-2. The catalysts used for each transformation were subjected to detailed characterization using XRD, BET surface area, temperature-programmed desorption and transmission electron microscopy. The effect of various reaction parameters was also investigated for obtaining high yields of desired chemical intermediates. High FDCA yields of 93.4 mol% and 66 mol% were achieved in alkaline and base-free conditions, respectively. The 2 wt% Ru-K-OMS-2 is a versatile catalyst as it also catalyses HMF hydrogenolysis giving 33 mol% of DMF. Thus, utility of various novel materials as catalysts has been demonstrated in the multistep transformations of hexoses to furan-based fuels and chemicals.

Cobalt(II) supported on ethylenediamine-functionalized nanocellulose as an efficient catalyst for room temperature aerobic oxidation of alcohols

Abstract: Ethylenediamine-functionalized nanocellulose complexed with cobalt(II) was found to be a highly efficient heterogeneous catalyst for the room temperature aerobic oxidation of various types of primary and secondary benzylic alcohols into their corresponding aldehydes and ketones, respectively. The catalyst showed no significant loss of efficiency after five reaction cycles.

Colorimetric detection of Cu2+ and Pb2+ ions using calix[4]arene functionalized gold nanoparticles

Abstract: Calixarene functionalized gold nanoparticles (CFAuNPs) have been prepared and characterized by spectroscopic and microscopic (TEM) techniques. To use this material as potential colorimetric sensor, the binding property of this new material has been investigated with a large number of metal ions. It exhibited sharp colour change from dark brown to green and blue, detectable by naked-eye, in the presence of Cu2+ and Pb2+ ions, respectively. It has also triggered substantial change in surface plasmon resonance (SPR) band of the functionalized gold nanoparticles, which in case of Pb(II) is due to the inter particle plasmon coupling arising from the metal-induced aggregation of the nanoparticles and for Cu(II), it is because of the formation of AuCu alloy due to anti-galvanic exchange. The size and aggregation of the nanoparticles are confirmed from HRTEM images, elemental analysis and the line profiling for both the metal ions have been done by STEM-EDX analysis.

How strongly are the magnetic anisotropy and coordination numbers correlated in lanthanide based molecular magnets

Abstract: Ab initio CASSCF + RASSI-SO investigations on a series of lanthanide complexes [LnIII = Dy(1), Tb(2), Ce(3), Nd(4), Pr(5) and Sm(6)] have been undertaken and in selected cases (for 1, 2, 3 and 4) coordination number (C.N.) around the LnIII ion has been gradually varied to ascertain the effect of C.N. on the magnetic anisotropy. Our calculations reveal that complex 3 possesses the highest barrier height for reorientation of magnetisation (Ueff) and predict that 3 is likely to exhibit Single Molecule Magnet (SMM) behaviour. Complex 5 on the other hand is predicted to preclude any SMM behaviour as there is no intrinsic barrier for reorientation of magnetization. Ground state anisotropy of all the complexes show mixed behaviour ranging from pure Ising type to fully rhombic behaviour. Coordination number around the lanthanide ion is found to alter the magnetic behaviour of all the lanthanide complexes studied and this is contrary to the general belief that the lanthanide ions are inert and exert small ligand field interaction. High symmetric low-coordinate LnIII complexes are found to yield large Ueff values and thus should be the natural targets for achieving very large blocking temperatures.

Chitosan-based Schiff base-metal complexes (Mn, Cu, Co) as heterogeneous, new catalysts for the β-isophorone oxidation

Abstract: A new chitosan-based Schiff base was prepared and complexed with manganese, cobalt and copper. These Schiff base metal complexes were used as heterogeneous catalysts for the air oxidation of β-isophorone to ketoisophorone. The obtained complexes were characterized by means of FT-IR,1HNMR spectroscopy, elemental analysis, powder X-ray diffraction, field emission gun scanning electron microscopy, electron spin resonance spectroscopy, ICP-AES and solubility tests. Thermal properties were also investigated using thermal gravimetric analysis. Data obtained by thermal analysis revealed that these complexes showed good thermal stability. The conversion and selectivity of β-isophorone to ketoisophorone for each prepared catalyst was studied using a batch reactor and gas chromatography for product identification and quantification. The results were compared against the homogeneous bis-salicylaldehyde ethylenedi-imine-Mn catalyst. The use of methanol, acetone, methyl isobutyl ketone and n-hexane as solvent and its effect on conversion and selectivity was also investigated. Acetone was found to be a promising solvent for the β-isophorone oxidation. The role of triethyl amine and acetyl acetone in the oxidation reaction has also been investigated.

Could glutaric acid (GA) replace glutaraldehyde in the preparation of biocompatible biopolymers with high mechanical and thermal properties

Abstract: In the field of natural and/or synthetic polymer preparation and stabilization, glutaraldehyde is the most commonly used cross-linker. Glutaraldehyde is focused by several scientists due its ease of cross-linking ability through the formation of Schiff base type of compound. Though glutaraldehyde cross-linked product has several advantages, the main drawback lies with the toxicity and poor mechanical stability. The poor mechanical strength of glutaraldehyde cross-linked product is due to the bonding pattern (–C=N–) between glutaraldehyde and amine group containing compound, where, there is a large energy barrier to rotation associated with groups joined by double bond. This is the time to search for an alternative cross-linker which will provide a non-toxic and mechanically stable biopolymer material. In order to achieve the requisite property, in the present study, we have chosen glutaric acid (oxidized form of glutaraldehyde) and studied its interaction with chitosan and type- I collagen. The chemistry behind the interaction and the characteristics of the biopolymer material obtained upon cross-linking suggests that non-covalent interactions play a major role in deciding the property of the said materials and its suitability for biomedical applications.

Click synthesis of 1,4-disubstituted-1,2,3-triazoles catalysed by CuO–CeO2 nanocomposite in the presence of amberlite-supported azide

Abstract: A CuO–CeO2 nanocomposite in the presence of amberlite-supported azide has been used for the click synthesis of 1,4-disubstituted-1,2,3-triazoles in good yields. This catalyst can be reused several times without any significant decrease in the catalytic activity.

Understanding the structure and electronic properties of N-doped graphene nanoribbons upon hydrogen saturation

Abstract: Structures and electronic properties of zigzag graphene nanoribbon (ZGNR) with pyridine (3NV-ZGNR) functionalized by Scandium (Sc) at the edge were studied through quantum chemical calculations in the formalism of density-functional theory (DFT). Pyridine-like nitrogen defects is very crucial for enhancing the Sc atom binding to the defects and is thermodynamically favoured. During Sc decoration of ZGNR there is a shift from 0.35 eV small gap semiconductor regime to that of a metal which can be used for band gap tuning by controlled saturation of Sc. ZGNR decorated with Sc can attract H2. Upon saturation of multiple H2 in quasi-molecular fashion, the metallic character is converted to semiconductors of small gap of 0.10 eV, which are predicted to be interesting materials not only for hydrogen storage but also for their band gap engineered properties.

Determination of conduction and valence band electronic structure of anatase and rutile TiO 2

Abstract: Electronic structures of rutile and anatase polymorph of TiO2 were determined by resonant inelastic X-ray scattering measurements and FEFF9.0 calculations. Difference between crystalline structures led to shifts in the rutile Ti d-band to lower energy with respect to anatase, i.e., decrease in band gap. Anatase possesses localized states located in the band gap where electrons can be trapped, which are almost absent in the rutile structure. This could well explain the reported longer lifetimes in anatase. It was revealed that HR-XAS is insufficient to study in-depth unoccupied states of investigated materials because it overlooks the shallow traps.

Mixed-ligand binuclear copper(II) complex of 5-methylsalicylaldehyde and 2,2 -bipyridyl: Synthesis, crystal structure, DNA binding and nuclease activity

Abstract: A new mixed-ligand binuclear copper(II) complex [Cu(MS)(bpy)]2.(ClO4)2, built of 5-methylsalicylaldehyde and 2,2′-bipyridyl has been synthesized and characterized by using elemental analysis, IR and UV-Vis spectroscopy. Crystal structure of the complex shows that copper(II) ion lies in a square pyramidal coordination environment. The structure consists of two symmetrical half units in which the copper(II) ion of one half unit connected with the phenolate oxygen atom of other half unit along with one perchlorate anion in the crystal lattice as free molecule. Presence of uncoordinated perchlorate anion was also confirmed by IR spectroscopy. Absorption spectroscopy exhibits d-d transition at 628 nm, which further supports the square pyramidal geometry around the copper(II) ions. EPR spectrum of the copper(II) complex at room temperature shows a broad signal without any splitting pattern at g || = 2.26,g ⊥ = 2.03 and the magnetic moment (μ eff= 1.31 BM) obtained at room temperature indicate an antiferromagnetic interaction between the two copper(II) ions through phenoxide-bridge. Binding studies reveal that the complex possesses good binding propensity (K b = 5.2 ± 1.7 × 104 M−1) and bind to nitrogenous bases of DNA through intercalation. Nuclease activity of the complex with pBR322 DNA shows that the effect of hydrolytic cleavage is dose-dependent and the oxidative cleavage indicates the involvement of hydroxyl radical and singlet-oxygen as reactive oxygen species.

Molecular dynamics simulations and free energy profile of Paracetamol in DPPC and DMPC lipid bilayers

Abstract: Molecular dynamics (MD) simulations and biased MD simulation were carried out for the neutral form of Paracetamol inserted in fully hydrated dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) lipid bilayers. For comparison, fully hydrated DMPC and DPPC lipid bilayers were also simulated separately without Paracetamol. The simulation time for each system was 50 ns. At two concentrations of Paracetamol, various properties of the lipid bilayer such as area per lipid, order parameter, diffusion coefficient, radial distribution function, electrostatic potential, mass density and hydrogen bonds have been calculated. Also, the convergence in time of the free energy profile of the Paracetamol along a DPPC bilayer normal was calculated by umbrella sampling method. From the obtained results, it can be concluded that neutral form of Paracetamol shows a generally similar behaviour in DPPC and DMPC lipid bilayers. It was shown that the addition of Paracetamol causes a decrease in tail order parameter of both DPPC and DMPC lipid bilayers and the tail of Paracetamol adopts an inward orientation in the lipid bilayers. Also from the free energy profile, the high penetration barrier in the bilayer centre was determined.

Syntheses, characterization, and anti-cancer activities of pyridine-amide based compounds containing appended phenol or catechol groups

Abstract: Several pyridine-amide compounds appended with phenol/catechol groups are synthesized. These compounds consist of protected or deprotected phenol/catechol groups and offer pyridine, amide, and phenol/catechol functional groups. All compounds have been well-characterized by various spectroscopic methods, elemental analysis, thermal studies, and crystallography. The biological activities of all compounds were investigated while a few compounds significantly decreased the metabolic viability, growth and clonogenicity of T98G cells in dose dependent manner. Accumulation of ROS was observed in T98G cells, which displayed a compromised redox status as evident from increased cellular Caspase 3/7 activity and formation of micronuclei. The in silico pharmacokinetic studies suggest that all compounds have good bioavailability, water solubility and other drug-like parameters. A few compounds were identified as the lead molecules for future investigation due to their: (a) high activity against T98G brain, H-460 lung, and SNU-80 thyroid cancer cells; (b) low cytotoxicity in non-malignant HEK and MRC-5 cells; (c) low toxic risks based on in silico evaluation; (d) good theoretical oral bioavailability according to Lipinski ‘rule of five′ pharmacokinetic parameters; and (e) better drug-likeness and drug-score values.

Silica-acac-Supported Palladium Nanoparticles as an Efficient and Reusable Heterogeneous Catalyst in the Suzuki-Miyaura Cross-Coupling Reaction in Water.

Abstract: Supported Pd nanoparticles on acetyl acetone modified silica gel was prepared and its catalytic application in the Suzuki–Miyaura reaction of various aryl halides with phenylboronic acid was investigated. The reaction was carried out in water as solvent under green conditions in the presence of NaHCO3as the base. The catalyst was characterized by a combination of powder XRD, XPS, TEM and SEM. The catalyst is not sensitive to air and moisture, so reactions were carried out without using inert atmosphere. The catalyst can be reused up to six times without significant loss of catalyst activity. The cumulative turnover number (TON) over six runs is 13525.

Metal organic framework MIL-101(Cr) for dehydration reactions

Abstract: Porous chromium terephthalate MIL-101 (Cr-MIL-101) has been prepared by direct method under hydrothermal conditions and characterized using X-ray diffraction, N2 sorption, TGA and FT-IR. The nitrogen adsorption–desorption isotherm shows that the Cr-MIL-101 possesses BET specific surface area of 2563 m2/g. Catalytic performance of Cr-MIL-101 in the dehydration of 1,4-butanediol and 1-phenyl ethanol is assessed under vapour phase conditions in the temperature range of 513–533 K and time on stream (TOS) at 513 K. Cr-MIL-101 demonstrates superior catalytic activity with conversion of 95% of 1-phenyl ethanol. Moreover, high surface area and nanocages with coordinated unsaturated sites of Cr-MIL-101 have allowed us to attain higher dehydrated products selectivity than Cr-supported activated carbon (Cr/AC), amberlyst-15 and HZSM-5 catalysts.

Cytotoxic, DNA binding, DNA cleavage and antibacterial studies of ruthenium–fluoroquinolone complexes

Abstract: Six new Ru(II) and Ru(III) complexes have been synthesized and characterized by elemental analysis, LC-MS, electronic spectra, IR spectra and magnetic moment measurements. DNA-binding properties of Ru complexes have been studied by means of absorption spectrophotometry and viscosity measurements as well as their HS DNA cleavage properties by means of agarose gel electrophoresis. The experimental results show that all the complexes can bind to DNA via partial intercalative mode. The K b values of complexes were found in the range 2.14 × 10 4 to 2.70 × 10 5 M−1. All the complexes show excellent efficiency of cleaving DNA than respective fluoroquinolones. Brine shrimp lethality bioassay has been performed to check the cytotoxic activity. The IC 50 values of the complexes are in the range of 6.27 to 16.05 μg mL−1.

Nano copper and cobalt ferrites as heterogeneous catalysts for the one-pot synthesis of 2,4,5-tri substituted imidazoles

Abstract: A simple one-pot synthesis has been developed for the synthesis of 2,4,5-trisubstituted imidazoles using magnetic recyclable spinel nano copper and cobalt ferrites by the condensation of benzil, aromatic aldehyde and ammonium acetate in ethanol as solvent. The reaction, with these catalysts was carried out under mild reaction conditions with very good yields of substituted imidazoles. These catalysts can be recycled very easily and reused, which makes this methodology environmentally benign.

Facile synthesis of catalytically active CeO 2 –Gd 2 O 3 solid solutions for soot oxidation

Abstract: CeO2–Gd2O3 oxides were synthesized by a modified coprecipitation method and subjected to thermal treatments at different temperatures to understand their thermal behaviour. The obtained samples were characterized by XRD, BET, TEM, Raman and TPR techniques. Catalytic efficiencies for oxygen storage/release capacity (OSC) and soot oxidation were evaluated by a thermogravimetric (TG) method. XRD and Raman results indicated the formation of Ce0.8Gd0.2O2−δ (CG) solid solutions at lower calcination temperatures, and TEM studies confirmed nanosized nature of the particles. Raman studies further confirmed the presence of oxygen vacancies and lattice defects in the CG sample. TPR measurements indicated a facile reduction of ceria after Gd3+ addition. Activity studies revealed that incorporation of Gd3+ into the ceria matrix favoured the creation of more structural defects, which accelerates the oxidation rate of soot compared to pure ceria.

Characterization and reactivity of 11-molybdo-1-vanadophosphoric acid catalyst supported on zirconia for dehydration of glycerol to acrolein

Abstract: A series of vanadium-substituted phosphomolybdic acid (HPA) catalysts supported on zirconia were prepared by impregnation method with varying the HPA active phase content from 10 to 50 wt% on the support. The calcined catalysts were characterized by X-ray diffraction, Raman spectroscopy, temperature-programmed desorption of NH3, FT-IR spectra of pyridine adsorption and surface area measurements. XRD results suggest that the active phase of heteropolyacid is present in a highly dispersed state at lower loadings and as a crystalline phase at higher HPA loadings and these findings are well-supported by the results of FT-IR and Raman spectra. Calcination of the samples did not affect the Keggin ion structure of HPA. The ammonia TPD results suggest that acidity of the catalysts was found to increase with increase of HPA loading up to 40 wt% and decreases at higher loadings. FT-IR spectra of pyridine adsorption show that the Bronsted acidic sites increase with increase of HPA loadings up to 40 wt% catalyst. However, Lewis acid sites decrease with increase of HPA loading. Catalytic properties were evaluated during vapour phase dehydration of glycerol to acrolein. The catalyst with 40 wt% HPA has exhibited excellent selectivity towards acrolein formation with complete conversion of glycerol at 225°C under atmospheric pressure. Catalytic performances during dehydration of glycerol are well-correlated with acidity of the catalysts.

Selective hydrogenation of maleic anhydride over Pd/Al2O3 catalysts prepared via colloid deposition

Abstract: Pd/Al2O3 catalysts were prepared via colloid deposition and the performance of the catalysts was examined in the selective hydrogenation of maleic anhydride to succinic anhydride. When the reaction was carried on in a batch system with 1,4-dioxane as the solvent (353 K and 1.0 MPa), high conversion of maleic anhydride (>98%) and high selectivity (>99%) for succinic anhydride were observed after 5 h. The as-prepared Pd/Al2O3 catalyst also showed excellent performance in solvent-free system and fixed-bed systems. The maleic anhydride (MA) conversion was greater than 98%, and high selectivity (>99%) for succinic anhydride was obtained after 1600 h in a fixed bed reacter. The results showed that the activity of the Pd/Al2O3 catalysts was excellent due to its high active surface area.

Chiral and achiral helical coordination polymers of zinc and cadmium from achiral 2,6-bis(imidazol-1-yl)pyridine: Solvent effect and spontaneous resolution

Abstract: Four 2D helical coordination polymers (CPs) (1–4) were synthesized using achiral 2,6-bis (imidazol-1-yl)pyridine (pyim2) ligand with metal nitrates (metal = zinc and cadmium), which showed that variation in the solvent condition leads to difference in geometry around the central metal ion and results in chiral/achiral behaviour of these CPs. By using (pyim2), [trans-Zn(pyim2)2(NO3)2]n (1) was obtained by unary solvent (MeOH), while [trans- Cd(pyim2)2(NO3)2] n (2) was formed under binary solvent mixtures (DMF/MeOH). On the other hand, in ternary solvent mixture (DMF/MeOH/H2O) it resulted into an achiral {[trans-Zn(pyim2)2(H2O)2] ·(NO3)2}n (3) and homochiral {[cis-Cd(pyim2)2(H2O)2] ·(NO3)2}n (4) coordination polymer, respectively. The homochiral behaviour of the coordination polymer (4) was further studied by solid state CD spectra and also its optical behaviour was analyzed by polarimetry.

Synthesis of new biphenyl-substituted quinoline derivatives, preliminary screening and docking studies

Abstract: New quinoline derivatives containing biphenyl ring were synthesized and characterized by IR, 1H NMR and mass spectral studies. The synthesized compounds were screened for antimicrobial, anthelmintic activities as well as free radical scavenging property against the DPPH radical. The minimum inhibition concentration values showed promising inhibiting activity and are potent biological agents. The compounds showed minimum binding energy towards β-tubulin. The compounds 11a, 11c, 13c and 13d have good affinity towards the active pocket and may be considered as a good inhibitor of β-tubulin.

Synthesis of thiophene-linked pyrimidopyrimidines as pharmaceutical leads

Abstract: Thiophene-substituted chalcones were cyclised with guanidine in the presence of potassium hydroxide to get 4-substituted-6-thiophenopyrimidines 2a–e which were then refluxed with acetylacetone to obtain pyrimidopyrimidines 3a–e. Compounds 2a–e were also refluxed with ethylacetoacetate to afford pyirmidopyirimidines 4a–e which on refluxing with POCl3 in presence of DMF produced compounds 5a–e. Nucleophilic substitution reactions on 5a-e were carried out with aniline to obtain 6a-e. The structures of the newly synthesised compounds have been confirmed by elemental analysis and spectral studies. Some selected compounds have been screened for antibacterial and analgesic activities.

Value addition to lignocellulosics and biomass-derived sugars: An insight into solid acid-based catalytic methods

Abstract: For the synthesis of important platform chemicals such as sugars (xylose and arabinose) and furans (furfural and 5-hydroxymethylfurfural (HMF)) from carbohydrates (hemicellulose and fructose) solid acid catalysts are employed. Similarly, over solid acid catalysts, conversion of lignin into aromatic monomers is performed. It is observed that in the dehydration of fructose, because of higher hydrothermal stability, silicoaluminophosphate (SAPO) catalysts give better activity (78% HMF yield) compared with other solid acid catalysts (<63% HMF yield) at 175°C. Particularly, SAPO-44 catalyst can be reused at least 5 times with marginal decrease in the activity. Zeolite, HUSY (Si/Al = 15) is active in the conversion of isolated (pure) hemicellulose to produce 41% C5 sugars in water. The catalyst is also active in the selective conversion of hemicellulose from bagasse to yield 59% C5 sugars. It is possible to obtain high yields of furfural (54%) directly from bagasse if instead of water, water+toluene solvent system is used. Depolymerization of lignin using HUSY catalyst produced aromatic monomers with 60% yield at 250°C. A detailed catalyst characterization study is performed to understand the correlation between catalyst activity and morphology. To understand the effect of impurities present in the substrate over solid acid catalysts, metal-exchange study is carried out.

Copper catalysed synthesis of indolylquinazolinone alkaloid bouchardatine

Abstract: We describe the total synthesis of indolylquinazolinone alkaloid bouchardatine and some of the quinazolinone derivatives. The aerobic oxidation induced by copper(I) bromide, followed by Vilsmeier-Haack formylation gives the natural product bouchardatine alkaloid in good yield.

Synthesis, characterization and photoluminescence properties of graphene oxide functionalized with azo molecules

Abstract: Two different azo molecules functionalized graphene oxide (GO) through an ester linkage have been synthesized for the first time. Chemical structure of the azo-GO hybrids was confirmed by Fourier transform infrared spectroscopy and UV-visible spectroscopy. The GO functionalized with 5-((4-methoxyphenyl)azo)-salicylaldehyde was further characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The SEM studies demonstrated that the morphology of the azo-GO hybrid was found to be similar to the GO sheets but slightly more wrinkled. Further, TEM image of azo-GO indicates some dark spots on the GO sheets due to azo functionalization. AFM results also reveal that the azo functionalization increases the thickness of GO sheet to 4–5 nm from 1.2–1.8 nm. Both the azo-hybrids show absorption band around 379 nm due to the π–π* transition of the trans azo units. Photoluminescence spectra of azo-GO hybrids show a strong quenching compared with azo molecules due to the photoinduced electron or energy transfer from the azo chromophore to the GO sheets. It also reveals strong electronic interaction between azo and GO sheets.

G4MP2, DFT and CBS-Q calculation of proton and electron affinities, gas phase basicities and ionization energies of hydroxylamines and alkanolamines

Abstract: The proton affinities, gas phase basicities and adiabatic ionization energies and electron affinities of some important hydroxylamines and alkanolamines were calculated using B3LYP, CBS-Q and G4MP2 methods. Also, the B3LYP method was used to calculate vertical ionization energies and electron affinities of the molecules. The calculated ionization energies are in the range of 8-10.5 eV and they decrease as the number of carbon atoms increases. Computational results and ion mobility spectrometry study confirm that some alkanolamines lose a water molecule due to protonation at oxygen site and form cationic cyclic compounds. Effect of different substitutions on the cyclization of ethanolamine was studied theoretically.