Synthesis,Crystal Structure and Vibrational Spectra of Barium Cyclotetraphosphate Hydrate Ba2(P4O12)∙3.5H2O

Barium tetrametaphosphate hydrate Ba₂(P₄O₁₂)∙3.5H₂O was synthesized as a single‐phase crystalline powder starting from an aqueous solution of barium hydroxide and phosphorus pentoxide at 300 K. Ba₂(P₄O₁₂)∙3.5H₂O crystallizes in a new structure type in which the Ba²⁺ ions form a distorted hexagonal diamond‐like arrangement with the (P₄O₁₂)^4– anions in the trigonal prismatic voids (Ba₂(P₄O₁₂)∙3.5H₂O, C2/c, Z = 4, a = 777.3(2), b = 1297.6(2), c = 1346.1(3) pm, b = 95.38(2)°, wR₂ = 0.071, R₁ = 0.018, 1180 reflections, 118 parameters). The vibrational spectra of Ba₂(P₄O₁₂)∙3.5H₂O and its thermal behavior up to 720 K are also reported.     

Effective Approximation for the Semiclassical Schrödinger Equation

The computation of the semiclassical Schrödinger equation presents major challenges because of the presence of a small parameter. Assuming periodic boundary conditions, the standard approach consists of semi-discretisation with a spectral method, followed by an exponential splitting. In this paper we sketch an alternative strategy. Our analysis commences with the investigation of the free Lie algebra generated by differentiation and by multiplication with the interaction potential: it turns out that this algebra possesses a structure which renders it amenable to a very effective form of asymptotic splitting: exponential splitting where consecutive terms are scaled by increasing powers of the small parameter. This leads to methods which attain high spatial and temporal accuracy and whose cost scales as \({\mathcal {O}}\!\left( M\log M\right) \) , where \(M\) is the number of degrees of freedom in the discretisation.     

Topotecan dynamics,tautomerism and reactivity—1H/13C NMR and ESI MS study

Topotecan (TPT) is in clinical use as an antitumor agent, hycamtin^?. Because of this, it requires both biologically and chemically useful information to be available. TPT acts by binding to the covalent complex formed by nicked DNA and topoisomerase I. This has a poisonous effect since inserted into the single‐strand nick and TPT inhibits its religation. We used NMR to trace TPT dynamics, tautomerism and solvolysis products in various solvents and conditions. Chemical stability was assessed in methanol and DMSO as compared to water, and the regioselectivity of the N‐ and O‐methylation was studied using various alkylating agents. The reaction products of quaternization of the nitrogen atom and methylation of the oxygen atom were characterized by means of ESI MS, ¹H/¹³C‐HMBC and ‐HSQCAD NMR. We have focused on the NMR characterization of TPT with an anticipation that its aggregation, tumbling properties and the intramolecular dipolar interactions will be a common feature for other compounds described in this article. These features can also be useful in tracing the interactions of this class of topoisomerase I (TopoI) poisons with DNA. Moreover, the results explained shed light on the recently disclosed problem of lack of stability of TPT in the heart tissue homogenate samples using the analytical assays developed for this class of compounds carried out in the presence of methanol. Copyright © 2010 John Wiley & Sons, Ltd.     

α‐Peptide–Oligourea Chimeras: Stabilization of Short α‐Helices by Non‐Peptide Helical Foldamers

Short α‐peptides with less than 10 residues generally display a low propensity to nucleate stable helical conformations. While various strategies to stabilize peptide helices have been previously reported, the ability of non‐peptide helical foldamers to stabilize α‐helices when fused to short α‐peptide segments has not been investigated. Towards this end, structural investigations into a series of chimeric oligomers obtained by joining aliphatic oligoureas to the C‐ or N‐termini of α‐peptides are described. All chimeras were found to be fully helical, with as few as 2 (or 3) urea units sufficient to propagate an α‐helical conformation in the fused peptide segment. The remarkable compatibility of α‐peptides with oligoureas described here, along with the simplicity of the approach, highlights the potential of interfacing natural and non‐peptide backbones as a means to further control the behavior of α‐peptides.     

Influence of the soft segment length on the properties of water‐cured poly(carbonate‐urethane‐urea)s

Poly(carbonate‐urethane‐urea)s (PCUU) based on oligocarbonate diols (M_n ≈ 2000) with different length of the hydrocarbon chain as soft segments were synthesized and investigated. Carbonate oligomerols were obtained in a two‐step method from dimethyl carbonate (DMC) and linear α,ω‐diols (1,4‐butanediol, 1,5‐pentanediol, 1,6‐hexanediol, 1,9‐nonanediol, 1,10‐dekanediol and 1,12‐dodecanediol). Oligo(trimethylene carbonate) diol was synthesized using ring‐opening polymerization of trimethylence carbonate. PCUUs were obtained by prepolymer method using isophorone diisocyanate (IPDI) and water as a chain extender. Changes in polymers properties with increase of methylene group number between carbonate linkages were investigated by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), tensile strength and hardness measurements. The thermal stability was also analyzed by means of thermogravimetric analysis (TGA). Based on FTIR analysis influence of methylene groups number between carbonate linkages on phase separation and concentration of allophanate and biuret groups in the samples were investigated. The obtained poly(carbonate‐urethane‐urea)s exhibited very good mechanical properties. Tensile strength and elongation at break were 40 MPa and 400–600%, respectively, depending on the oligocarbonate used. Copyright © 2014 John Wiley & Sons, Ltd.     

Development of zinc alkyl/air systems as radical initiators for organic reactions

This paper reports a series of comparative experiments on the activity of carbon- and oxygen-centred radical species in a model reaction of the radical addition of THF to imines mediated by a series of zinc alkyl/air reaction systems. The study strongly contradicts the notion that generally R˙ radicals are the initiating species in organic reactions mediated by R_nM/air systems, and simultaneously demonstrates that oxygen-centred radical species are the key intermediates responsible for the initiation process. In addition, a new efficient RZn(L)/air initiating system for radical organic reactions exampled by a model reaction of radical addition of THF to imines is developed. Moreover, the isolation and structural characterization of the first zinc alkylperoxide supported by a carboxylate ligand, [Zn₄(μ₃-OOtBu)₃(μ₄-O)(O₂CEt)₃]₂, as well as the novel octanuclear zinc oxo(alkoxide) aggregate with entrapped O–THF species, [Zn₄(μ₄-O)(μ₃-2-O–THF)(O₂CEt)₅]₂, provide clear mechanistic signatures for the mode of function of the RZn(O₂CR′)/air system.     

Iron‐Catalyzed C(sp2)H and C(sp3)H Methylations of Amides and Anilides

The so‐called magic methyl effect significantly boosts the bioactivities and physical properties of pharmacologically active drugs. Direct introduction of the methyl group by C?H activation was accomplished with a versatile iron catalyst, which enabled the C?H methylation of (hetero)benzamides, anilides, alkenes, and even alkanes by triazole assistance in a chemo‐, site‐ and diastereo‐selective fashion.     

Effect of composition and drying method on glass transition temperature,water sorption characteristics and surface morphology of newly designed β-lactoglobulin/retinyl palmitate/disaccharides systems

Epoxy-based nanocomposites containing different concentrations (0–3%) of surface-modified graphene nanosheets (GNS) with 3-aminopropyltriethoxysilane were prepared and their thermal and mechanical properties including dynamic mechanical analysis, tensile strength, hardness, and abrasion tests were evaluated in order to have a database for thermo-mechanical properties of epoxy nanocomposites. The main aim of this study was to understand the optimum percentage of GNS which would perform the best reinforcing influence on mechanical and physical performance of an epoxy nanocomposite. The results explain how applying the analysis of variance (ANOVA) method as a useful tool in optimization of GNS concentration in preparation of high-performance epoxy-based nanocomposites.     

Organic-coated silver nanoparticles in biological and environmental conditions: Fate,stability and toxicity

This review paper presents the overview of processes involved in transformation of organic-coated silver nanoparticles (AgNPs) in biological systems and in the aquatic environment. The coating on AgNPs greatly influences the fate, stability, and toxicity of AgNPs in aqueous solutions, biological systems, and the environment. Several organic-coated AgNP systems are discussed to understand their stability and toxicity in biological media and natural water. Examples are presented to demonstrate how a transformation of organic-coated AgNPs in an aqueous solution is affected by the type of coating, pH, kind of electrolyte (mono- or divalent), ionic strength, organic ligands (inorganic and organic), organic matter (fulvic and humic acids), redox conditions (oxic and anoxic), and light. Results of cytotoxicity, genotoxicity, and ecotoxicity of coated AgNPs to food chain members (plants, bacteria, and aquatic and terrestrial organisms) are reviewed. Key factors contributing to toxicity are the size, shape, surface coating, surface charge, and conditions of silver ion release. AgNPs may directly damage the cell membranes, disrupt ATP production and DNA replication, alternate gene expressions, release toxic Ag⁺ ion, and produce reactive oxygen species to oxidize biological components of the cell. A progress made on understanding the mechanism of organic-coated AgNP toxicity using different analytical techniques is presented.