Fluorescent Polyurethane Nanocapsules Prepared via Inverse Miniemulsion: Surface Functionalization for Use as Biocarriers

The functionalization of well‐defined PU nanocapsules with an aqueous core prepared by performing a polyaddition at the interface of inverse (water‐in‐oil) miniemulsion droplets is demonstrated. The miniemulsion technique involving the nanoreactor concept allows one to obtain an encapsulation efficiency as high as 90% within the nanocapsules. A pH independent fluorescent dye is used as a model system for the aqueous core. By varying the molar ratio of the diol to the diisocyanate at a fixed surfactant concentration, the shell thickness of the nanocapsules can be finely tuned. The carboxy‐ and amino‐functionalized surface of the nanocapsules can be tailored by an in‐situ carboxymethylation reaction and by physical adsorption of a cationic polyelectrolyte, i.e. PAEMA or PEI. The increased uptake of amino‐functionalized fluorescent nanocapsules by HeLa cells clearly demonstrates the potential of the functionalized nanocapsules to be successfully exploited as biocarriers.

     

Manganese(II) Complexes with Bridging Selenidoarsenate(III) Anions [AsSe2(Se2)]3− and [(AsSe2)2(μ‐Se2)]4−

Solvothermal reaction of [MnCl₂(terpy)] with elemental As and Se at a 1:1:2 molar ratio in H₂O/trien (10:1) at 150 °C affords the linear trimanganese(II) complex [{Mn(terpy)}₃(μ‐AsSe₄)₂] ( 1 ). The tridentate [AsSe₂(Se₂)]^3? anions of 1 chelate the terminal {Mn(terpy)}²⁺ fragments and bridge these through their remaining Se atom to the central {Mn(terpy)}²⁺ moiety. Weak interactions of Mn1···Se and Mn3···Se bonds with length 2.914(7) and 3.000(7) Å link the molecules of 1 into infinite chains. Treatment of [MnCl₂(cyclam)]Cl with As and Se at a 1:1:2 molar ratio in superheated H₂O/CH₃OH (1:1) at 150 °C yields the dinuclear complex [{Mn(cyclam)}₂ (μ‐As₂Se₆)] ( 2 ), whose novel [(AsSe₂)₂(μ‐Se₂)]^4? ligands bridge the Mn^II atoms in a μ‐1κ²Se¹, Se²: 2κ²Se⁵,Se⁶ manner.     

Inter-hydrogen bond dynamical coupling effects in polarized IR spectra of N-methylacetamide single crystals

This article presents the investigation results of polarized IR spectra of the hydrogen bond in N-methylacetamide (NMA) crystals measured in the frequency range of the proton and deuteron stretching vibration bands, ν_N–H and ν_N–D. A similar study was also performed for crystals of the deuterium isotopomers of the compound, D₇-NMA (CD₃CONDCD₃) and D₆-NMA (CD₃CONHCD₃). On the basis of the analysis of the linear dichroic and temperature effects, the two-branch structure of the ν_N–H bands in the spectra was ascribed to centrosymmetric hydrogen bond pairs in the lattice. Each hydrogen bond in such a dimeric system belonged to another chain of the associated molecules. The exciton interactions involving the dimer hydrogen bonds were considered to be responsible for the band shape generation. For the deuterium-bonded crystals the exciton interactions were found to be weaker since the ν_N–D bands were less split. Within an individual hydrogen or deuterium bond chain the in-chain exciton couplings involving hydrogen bonds were estimated as considerably weaker than the inter-chain ones. The exciton dilution retains the two-branch fine structure pattern of the “residual” ν_N–H and ν_N–D bands. This means that the inter-chain couplings involving hydrogen bonds do not change, when the in-chain couplings vanish. These results are the evidence of the influence of non-conventional co-operative interactions occurring in the hydrogen bond systems on the spectra. These co-operative interactions are responsible for the non-random distribution of the hydrogen isotope atoms in the hydrogen bridge lattices, namely for the grouping of identical hydrogen isotope atoms in the dimers. The proposed interpretation of the IR spectra of the hydrogen bond in N-methylacetamide (NMA) crystals casts light on the spectra generation mechanisms and gives a new meaning to the traditional nomenclature applied for describing the ν_N–H band structure pattern in IR spectra of amides.     

The synthesis of (4S,5S)-(−)-isocytoxazone

(4S,5S)-(?)-Isocytoxazone, which is needed for a configurational study, was synthesized from the commercially available (1S,2S)-(+)-2-amino-1-(4-nitrophenyl)-1,3-propanediol in which the p-nitro substituent was replaced by a p-methoxyl group; the thus prepared p-methoxyphenyl amino diol was cyclized via an N-Boc derivative.     

Active media based on SiO2 matrices with incorporated molecules of rhodamine dyes

SiO₂ matrices with incorporated molecules of Rhodamine 6G and Rhodamine 800 laser dyes were synthesized by the sol?Cgel method. The spectral properties of the matrices were studied. It was found that the incorporation of Rhodamine 6G molecules into the xerogel network decreased their association. The influence of the molar ratio of water and formamide on the transparency of the samples was studied. Laser emission of SiO₂ matrices activated with Rhodamine 800 was obtained in the near infrared spectral range. The values of laser spectrum halfwidth of SiO₂ matrices with Rhodamine 6G and Rhodamine 800 are 2?C6?nm. A well-defined structure of the laser emission spectra of the matrices at microsecond pumping duration testifies to their relatively high optical quality.     

Investigation of Pd content in C–Pd films for hydrogen sensor applications

Nanocomposite carbonaceous-palladium (Nc-C-Pd) films were synthesized by physical vapor deposition method (PVD). Scanning electron microscopy studies showed that they were composed of carbonaceous matrix containing Pd nanograins. Nc-C-Pd films were also characterized by thermogravimetric analysis, X-ray powder diffraction, and Fourier transform infrared (FTIR) spectral analysis. The content of Pd in films synthesized at different PVD conditions was determined based on TG measurements. Technological parameters of PVD process affected C/Pd ratio. FTIR spectra exhibited characteristic absorption bands for the precursors of carbonaceous-palladium samples (fullerene C₆₀ and palladium acetate). The influence of hydrogen on electrical properties of the films was tested by measuring their resistance in the presence of hydrogen (1% H₂/N₂).     

A multi-reference coupled-cluster study on the potential energy surface of N2 including ground and excited states: spin projections and wavefunction overlaps

This article reports on the calulation of 12 low lying states of the nitrogen molecule along its dissociation using the multi-reference exponential wavefunction ansatz (Hanrath in J Chem Phys 123:84102, 2005), the single-reference formalism multi-reference coupled cluster (Oliphant and Adamowicz in J Chem Phys 94:1229, 1991), and MRCI methods. Spin projection errors and state overlap errors are calculated and allow an analysis of the wavefunction with respect to properties different from correlation energies. Both criteria are very sensitive to errors in the wavefunction. Due to its lack of Fermi vacuum invariance the errors are more significant for the single-reference formalism based approach.     

Application of microbioreactors in fermentation process development: a review

Biotechnology process development involves strain testing and improvement steps aimed at increasing yields and productivity. This necessitates the high-throughput screening of many potential strain candidates, a task currently mainly performed in shake flasks or microtiter plates. However, these methods have some drawbacks, such as the low data density (usually only end-point measurements) and the lack of control over cultivation conditions in standard shake flasks. Microbioreactors can offer the flexibility and controllability of bench-scale reactors and thus deliver results that are more comparable to large-scale fermentations, but with the additional advantages of small size, availability of online cultivation data and the potential for automation. Current microbioreactor technology is analyzed in this review paper, focusing on its industrial applicability, and directions for future research are presented.     

Generation and stereoselective transformations of 3-phenylcyclopropene

A convenient and inexpensive approach to the generation of 3-phenylcyclopropenes is described. Reaction of these compounds with a range of dienophiles and dipolarophiles led to the stereoselective formation of [4+2]- and [3+2]-cycloadducts, which were exclusively exo-3-phenyl-cis-1,2-disubstituted cyclopropanes. Efficient trapping of 1-lithio-3-phenylcyclopropene with different electrophiles is also discussed. Ab initio calculations suggest that the lowest energy conformation of 3-phenylcyclopropene has the plane of the benzene ring perpendicular to the cyclopropene π-bond but with a low rotation barrier.