Direct observation of nanoparticle embedding into the surface of a polymer melt

Direct embedding of metal nanoparticles (NPs) into the surface of a polymer melt is observed by TEM and a new embedding mechanism proposed. Upon annealing above the glass transition temperature of polystyrene (PS), NPs (20 nm gold) are rapidly covered by a thin PS wetting layer, h* approximately 1.3-1.8 nm (i.e., about two or three monomers). Because it creates capillary pressure on a NP, this "universal" wetting layer is proposed to be responsible for NP embedding. The value of h* is independent of the molecular weight of PS and constant during the embedding process. The value of h* is found to be similar to the equilibrium wetting layer thickness of a polymer melt spreading on a metal substrate. Using a model that includes the spreading coefficient, long-range van der Waals interactions, and a chain-stretching penalty, h* is shown to be independent of the molecular weight of the polymer. Using this model and the measured value of h*, the interfacial energy between Au NP and PS is estimated to be 8.7 J/m2.     

Determination of δ‐[L‐α‐aminoadipyl]‐L‐cysteinyl‐D‐valine in cell extracts of Penicillium chrysogenum using ion pair‐RP‐UPLC‐MS/MS

δ‐[L ‐α‐Aminoadipyl]‐L ‐cysteinyl‐D ‐valine (ACV) is a key intermediate in the biosynthesis pathway of penicillins and cephalosporins. Therefore, the accurate quantification of ACV is relevant, e.g. for kinetic studies on the production of these β‐lactam antibiotics. However, accurate quantification of ACV is a challenge, because it is an active thiol compound which, upon exposure to air, can easily react with other thiol compounds to form oxidized disulfides. We have found that, during exposure to air, the oxidation of ACV occurs both in aqueous standard solutions as well as in biological samples. Qualitative and quantitative determinations of ACV and the oxidized dimer bis‐δ‐[L ‐α‐aminoadipyl]‐L ‐cysteinyl‐D ‐valine have been carried out using ion pair reversed‐phase ultra high‐performance liquid chromatography, hyphenated with tandem mass spectrometry (IP‐RP‐UPLC‐MS/MS) as the analytical platform. We show that by application of tris(2‐carboxy‐ethyl)phosphine hydrochloride (TCEP) as the reducing reagent, the total amount of ACV can be determined, while using maleimide as derivatizing reagent enables to quantify the free reduced form only.     

Stability of a charged drop near a conductor wall

The effect of conductor boundaries on the deformation and stability of a charged drop is presented. The motivation for such a study is the occurrence of a charged conductor drop near a conductor wall in experiments (Millikan-like set-up in studies on Rayleigh break-up) and applications (such as electrospraying, ink-jet printing and ion mass spectroscopy). In the present work, analytical (linear stability analysis (LSA)) and numerical methods (boundary element method (BEM)) are used to understand the instability. Two kinds of boundaries are studied: a spherical, conducting, grounded enclosure (similar to a spherical capacitor) and a planar conducting wall. The LSA of a charged drop placed at the center of a spherical cavity shows that the Rayleigh critical charge (corresponding to the most unstable l = 2 Legendre mode) is reduced as the non-dimensional distance ?d = (b - a)/a decreases, where a and b are the radii of the drop and spherical cavity, respectively. The critical charge is independent of the assumptions of constant charge or constant potential conditions. The trans-critical bifurcation diagram, constructed using BEM, shows that the prolate shapes are subcritically unstable over a much wider range of charge as [Formula: see text] decreases. The study is then extended to the stability of a charged conductor drop near a flat conductor wall. Analytical theory for this case is difficult and the stability as well as the bifurcation diagram are constructed using BEM. Moreover, the induced charges in the conductor wall lead to attraction of the drop to the wall, thereby making it difficult to conduct a systematic analysis. The drop is therefore assumed to be held at its position by an external force such as the electric field. The case when the applied field is much smaller than the field due to inherent charge on the drop ((a(3)ρg)/(3ε(0)Ψ(2)) ? 1 is considered. The wall breaks the fore-aft symmetry in the problem, and equilibrium, predominantly prolate shapes corresponding to the legendre mode, l = 2 , are observed. The deformation increases with increasing charge on the drop. The breakup of the prolate equilibrium shapes is independent of the legendre modes of the initial perturbations. The prolate perturbations are subcritically unstable. Since the equilibrium prolate shapes cannot continuously exchange instability with equilibrium oblate shapes, an imperfect transcritical bifurcation is observed. A variety of highly deformed equilibrium oblate shapes are predicted by the BEM calculations.     

Synthesis of N‐lactosylated thiourea and benzothiazolyl thiourea

Several N‐lactosylated aryl thioureas and benzothiazolyl thioureas have been prepared by the condensation of hepta‐O‐acetyl‐β‐D ‐lactosyl isothiocyanate with aryl amines and 2‐aminobenzothiazole/substituted benzothiazoles. Hepta‐O‐acetyl‐β‐D ‐lactosyl isothiocyanate was prepared by the interaction of hepta‐O‐acetyl‐α‐D ‐lactosyl bromide and lead thiocyanate. The structures of these new N‐lactosides have been established on the basis of IR, NMR, and mass spectral studies. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:306–309, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20207     

Syntheses and antimicrobial activities of 4‐aryl‐5‐phenylimino‐3‐S‐(hepta‐O‐acetyl lactosyl)‐1,2,4‐thiadiazolines

A series of 4‐aryl‐5‐phenylimino‐3‐S‐(hepta‐O‐acetyl lactosyl)‐1,2,4‐thiadiazolines have been synthesized by the interaction of S‐(hepta‐O‐acetyl lactosyl)‐1‐arylisothiocarbamides and S‐chloro‐N‐phenyl isothiocarbamoyl chloride. The title compounds were characterized on the basis of elemental analysis and IR, NMR, mass spectral studies. The title compounds exhibited comparable antimicrobial activities against pathogens such as E. coli, S. aureus, P. vulgaris, S. typhi, A. niger, and Candida guilliermondii. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:390–392, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20310     

Spherical submanifolds in a Euclidean space

In this paper, we are interested in extending the study of spherical curves in R ³ to the submanifolds in the Euclidean space R ^n+p . More precisely, we are interested in obtaining conditions under which an n-dimensional compact submanifold M of a Euclidean space R ^n+p lies on the hypersphere S ^n+p−1(c) (standardly imbedded sphere in R ^n+p of constant curvature c). As a by-product we also get an estimate on the first nonzero eigenvalue of the Laplacian operator Δ of the submanifold (cf. Theorem 3.5) as well as a characterization for an n-dimensional sphere S ⁿ (c) (cf. Theorem 4.1).     

On the possibility of using organic phosphors in thermoluminescence dosimetry

Organic materials in general and polymers in particular have traditionally been considered as to be phosphors and have been ruled out as materials which could be useful in dosimetry of ionizing radiations by thermoluminescence. Some results reported during the past decade suggested possibilities of organic phosphors with good thermoluminescence characteristics. Experiments were undertaken to exploit the various possibilities. The results show that “crystalline polymers” can have adequate thermoluminescence properties to be useful in dosimetry. It is suggested that further studies on thermoluminesence in crystalline polymers and highly drawn fibers of high polymers will prove fruitful.     

Arthrichitin. A New Cell Wall Active Metabolite from Arthrinium phaeospermum

Arthrichitin (1), C(33)H(46)N(4)O(9), is a new cell wall active depsipeptide isolated from the fermentation broth of Arthrinium phaeospermum (HIL Y-903022). Its structure was elucidated on the basis of spectroscopic and chemical degradation studies. Arthrichitin consists of serine, beta-keto tryptophan, glutamic acid, and 2,4-dimethyl-3-hydroxydodecanoic acid units.