Versatile Aerogel Fabrication by Freezing and Subsequent Freeze‐Drying of Colloidal Nanoparticle Solutions

A versatile method to fabricate self‐supported aerogels of nanoparticle (NP) building blocks is presented. This approach is based on freezing colloidal NPs and subsequent freeze drying. This means that the colloidal NPs are directly transferred into dry aerogel‐like monolithic superstructures without previous lyogelation as would be the case for conventional aerogel and cryogel fabrication methods. The assembly process, based on a physical concept, is highly versatile: cryogelation is applicable for noble metal, metal oxide, and semiconductor NPs, and no impact of the surface chemistry or NP shape on the resulting morphology is observed. Under optimized conditions the shape and volume of the liquid equal those of the resulting aerogels. Also, we show that thin and homogeneous films of the material can be obtained. Furthermore, the physical properties of the aerogels are discussed.     

Synthesis,characterization and cytotoxicity of polyethylene glycol coupled zinc oxide–chemically converted graphene nanocomposite on human OAW42 ovarian cancer cells

Present work reports for the first time on successful synthesis of polyethylene glycol (PEG) coupled ZnO–chemically converted graphene (CCG) nanocomposites (ZGP) as well as pristine nano ZnO (ZO), ZnO–CCG (ZG) and ZnO–PEG (ZP) by adopting facile solvothermal method using zinc acetate dihydrate, graphene oxide and PEG as precursor materials. X‐ray diffraction measurement of samples showed nanocrystalline hexagonal ZnO. Agglomeration of ZnO nanoparticles formed microspheres in ZG, and the agglomeration was found to be decreased in ZGP as revealed from field emission scanning and transmission electron microscopes. Raman and FTIR spectral studies evidenced the presence of chemically interacted CCG and polyethylene glycol in the nanocomposites. Content of the organics in ZGP was determined by thermogravimetric analysis. A mechanism was proposed on the formation of ZGP nanocomposite. From the measurement of in vitro cytotoxicity, quantitative cell viability (CV) of human ovarian cancer cell line, OAW42, was obtained from control to a maximum of 200 µg/ml of sample concentrations. An excellent CV of the cancer cells was observed (nearly ~80% of viable cells at 50 µg/ml dose with respect to the control) for ZGP compared to ZO, ZG and ZP samples. The effective role of CCG and PEG in ZGP nanocomposite for enhancing the cell viability was explained. This simple strategy could be beneficial for synthesis of other metal oxide towards biomedical applications. Copyright © 2015 John Wiley & Sons, Ltd.     

A review on adsorption mediated phosphate removal and recovery by biomatrices

Low cost biosorbents have gained considerable importance in the past decade for their removal efficiency of contaminants from wastewaters. Both removal and recycle of the phosphate anion through benign methods are relevant to sustain a steady balance. An attempt has been made to give a comprehensive insight into several physico-chemical factors leading to the adsorption process by various natural biosorbents. Few important facts regarding phosphate biosorption have emerged out as key points viz., pH < pHpzc, high uptake capacity; correlation with Langmuir isotherm model and pseudo second order kinetics; decrease of uptake capacity with longer contact time; enhancement of adsorption process in presence of counter ions, etc. Also, it was noted that the adsorbate: adsorbent ratio is crucial for the removal efficiency of the phosphate ions. A few biosorbents exhibit removal efficiency to a large extent (>95%) although even higher adsorption capacity can be obtained by the modification of the adsorbents. Commercial biomatrices like biochars have shown wide applications for removal of phosphates. Magnetic biochars have shown special performance owing to the presence of iron and a porous nature of their structure. Desorption studies revealed that almost complete recovery of the phosphate ion is possible through simple ion exchange mechanism.     

Square planar Ni(II) thiosemicarbazone complexes as functional models for carbon monoxide dehydrogenase

Two Ni(II) complexes, [Ni(dmoTSCH)Cl] (1) and [Ni(dmoPhTSCH)Cl] (2) of the tridentate thiosemicarbazone ligands diacetylmonooxime thiosemicarbazone (dmoTSCH₂) and diacetylmonooxime (4-phenyl)thiosemicarbazone (dmoPhTSCH₂) have been synthesized. X-ray crystal structure of [Ni(dmoTSCPhTSCH)Cl] (2) indicates that the Ni(II) assumes a square planar geometry in the complexes, with the ligand coordinated in a monoanionic N,N,S donor mode and the fourth coordination position of Ni(II) is occupied by a chloride ion. Cyclic and differential pulse voltammetric experiments suggest that the Ni(II) complexes can undergo a two electron reduction at about ?1.0V. It is shown that the Ni(II) complexes in DMF or DMSO solutions can mimic CO-dehydrogenase activity by oxidizing CO to CO₂ in presence of a base like NaOAc and a sacrificial electron acceptor like methyl viologen and the colour of the resultant MV^.+ can be used to monitor the reaction.     

Synthesis and Crystal Structure of a Complex of Palladium(II) with 2-Hydroxyimino-3-(2-hydrazonopyridyl)-butane

Abstract  

Schiff-base condensation of an equimolar proportion of diacetyl-monoxime and 2-hydrazino pyridine in methanol gives rise to 2-hydroxyimino-3-(2-hydrazonopyridyl)-butane (HL). The ligand has been characterised by FT-IR, ¹H NMR and UV–Vis spectra. Reaction of 1:1 stoichiometric proportion of HL with Na₂[PdCl₄] in methanol affords a mononuclear palladium(II) compound, [PdLCl]·H₂O (1). The compound is characterised by C, H and N analyses, FT-IR, conductivity measurement, UV–Vis spectra, thermal analysis and magnetic susceptibility measurement. The X-ray crystal structure of the title compound (1) has been determined. The compound crystalises in the triclinic space group P[`1] P\overline{1} with a = 7.3033(3), b = 9.4139(4), c = 9.4445(5) ?, α = 79.789(3), β = 68.285(2), γ = 77.978(3)o, V = 586.42(5) ?³ and Z = 2. Pd(II) is in ‘N₃Cl’ coordination chromophore. The geometry around Pd(II) is square-planar. The compound is essentially diamagnetic.     

Simultaneous pseudo-time stepping for aerodynamic shape optimization

In this paper we discuss about numerical methods for aerodynamic shape optimization problems. These problems require efficient CFD techniques to solve the state (as well as costate) equations and fast algorithms for solving the optimization problems. Both of these are independent active areas of research since long time. Wide range of applications in science and engineering involve solution of optimization problems where the governing PDEs appear as constraints. Therefore, merging the two for the purpose of practical applicability is relatively new. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

One-shot multigrid method for aerodynamic shape optimization

This paper presents a numerical method for aerodynamic shape optimization problems. It is based on simultaneous pseudotime-stepping in which the optimality is reached simultaneously with the state and costate feasibility. An optimization-based multigrid strategy results in efficient convergence of the method. The total effort of optimization is less than two forward simulation runs. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Über Poterinchemie. 82. Mitteilung. Bildung von Formimidoyl-Derivaten aus Aminen und Benzylisocyanid; Eine neue Umpolungsmöglichkeit für bestimmte C-Atome

Formation of Formimidoyl Derivatives from Amines and Benzylisocyanide; A New Possibility of Umpolung for Certain C-Atoms Cu(I)Cl can give a colorless and well-crystallized complex with 4 molecules of benzylisocyanide. This complex is able to transfer the benzylisocyanide ligands to primary and secondary amines and to form N-benzylformimidoyl derivatives. Catalyic hydrogenolysis removes the benzyl group, and free formimidoyl compounds are obtained in good yield. The method which succeeds with aliphatic amines, could not be applied to the secondary amino group of tetrahydropterines.     

Crystal engineering with aroyl hydrazones of diacetyl monooxime – Molecular and supramolecular structures of two Ni(II) and two Zn(II) complexes

Four new Schiff bases of aroyl hydrazides with diacetyl monooxime have been prepared, and Ni(II) and Zn(II) complexes of these ligands have been synthesized. Two Ni(II) and two Zn(II) complexes have been characterized by X-ray crystallography. The aroyl hydrazone ligands were designed in such a way that there is a systematic variation in the H-bond forming abilities of their aroyl moiety, e.g. both H-bond acceptor and donor (salicyloyl), only H-bond donor (anthraniloyl), only H-bond acceptor (isonicotinoyl). It is shown in this work that such a variation in the H-bond donor acceptor properties of the ligands leads to considerable diversity in their supramolecular architecture.