Fully Biodegradable Poly(lactic acid)/Poly(propylene carbonate) Shape Memory Materials with Low Recovery Temperature Based on in situ Compatibilization by Dicumyl Peroxide

Fully biodegradable blends with low shape memory recovery temperature were obtained based on poly(lactic acid)(PLA) and poly(propylene carbonate)(PPC). By virtue of their similar chemical structures, in situ cross-linking reaction initiated by dicumyl peroxide(DCP) between PLA and PPC chains was realized in PLA/PPC blends. Therefore, the compatibility between PLA and PPC was increased, which obviously changed the phase structures and increased the elongation at break of the blends. The compatibilized blends had a recovery performance at 45 °C. Combining the changes of phase structures, the mechanism of the shape memory was discussed. It was demonstrated that in situ compatibilization by dicumyl peroxide was effective to obtain eco-friendly PLA/PPC blends with good mechanical and shape memory properties.     

Towards the optimization of carbon nanotube properties via <Emphasis Type="Italic">in situ</Emphasis> and <Emphasis Type="Italic">ex situ</Emphasis> studies of the growth mechanism

The synthesis conditions of multi-walled carbon nanotubes (MWCNTs) indirectly determine their application potential through the decisive role in the characteristics of individual tubes: diameter distribution, structure and defectiveness of graphene walls, the amount of metal impurities and amorphous carbon. In the present work, we have studied the influence of the catalyst composition and synthesis conditions on the diameter distribution and the structure of nanotube walls. We have observed the influence of the particle size for MWCNT synthesis (i.e. size effect) on catalytic activity by ex situ and in situ techniques: in situ X-ray diffraction on synchrotron radiation (SRXRD), gas chromatography, and ex situ transmission electron microscopy. The data obtained by in situ SRXRD are in agreement with the results collected using laboratory tubular fix-bed catalytic reactor allowing thereby extending the applicability of the approach. For the first time we have shown the increase of the fraction of graphene walls in the total MWCNT diameter with time.     

<Emphasis Type="Italic">In situ</Emphasis> synthesis and modification of calcium carbonate nanoparticles via a bobbling method

Modified calcium carbonate (CaCO₃) nanoparticles with cubic- and spindle-like configuration were synthesized in situ by the typical bobbling (gas-liquid-solid) method. The modifiers, such as sodium stearate, octadecyl dihydrogen phosphate (ODP) and oleic acid (OA), were used to obtain hydrophobic nanoparticles. The different modification effects of the modifiers were investigated by measuring the active ratio, whiteness and the contact angle. Moreover, transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetry analysis (TGA analysis) were employed to characterize the obtained products. A preliminary reaction mechanism was discussed. According to the results, the active ratio of CaCO₃ modified by ODP was ca. 99.9% and the value of whiteness was 97.3% when the dosage of modifiers reached 2%. The contact angle was 122.25° for the CaCO₃ modified in the presence of sodium stearate, ODP and OA. When modified CaCO₃ was filled into PVC, the mechanical properties of products were improved greatly such as rupture intensity, pull intensity and fuse temperature. The compatibility and affinity between the modified CaCO₃ nanoparticles and the organic matrixes were greatly improved. Supported by the National Natural Science Foundation of China (Grant No. 50372025)     

<Emphasis Type="Italic">Z</Emphasis>-and <Emphasis Type="Italic">E</Emphasis>-conformers of <Emphasis Type="Italic">N</Emphasis>-chloroacetylcytisine

N-Chloroacetylcytisine was synthesized by acylation of (–)-cytisine. Stable Z- and E-conformers with respect to rotational isomerism around the N-12–CO bond were found in PMR spectra at room temperature. The point at which PMR resonances of the Z- and E-conformers coalesced upon heating was measured. The transition barrier between the conformers was estimated.     

Curing reaction of <Emphasis Type="Italic">o</Emphasis>-cresol-formaldehyde epoxy/LC epoxy(<Emphasis Type="Italic">p</Emphasis>-PEPB)/anhydride(MeTHPA)

The curing kinetics of a bi-component system about o-cresol-formaldehyde epoxy resin (o-CFER) modified by liquid crystalline p-phenylene di[4-(2,3-epoxypropyl) benzoate] (p-PEPB), with 3-methyl-tetrahydrophthalic anhydride (MeTHPA) as a curing agent, were studied by non-isothermal differential scanning calorimetry (DSC) method. The relationship between apparent activation energy E _a and the conversion α was obtained by the isoconversional method of Ozawa. The reaction molecular mechanism was proposed. The results show that the values of E _a in the initial stage are higher than other time, and E _a tend to decrease slightly with the reaction processing. There is a phase separation in the cure process with LC phase formation. These curing reactions can be described by the Šesták–Berggren (S–B) equation, the kinetic equation of cure reaction as follows: \frac\textda\textdt = Aexp( - \fracE_\texta RT )a^m ( 1 - a )ⁿ {\frac{{{\text{d}}\alpha }}{{{\text{d}}t}}} = A\exp \left( { - {\frac{{E_{\text{a}} }}{RT}}} \right)\alpha^{m} \left( {1 - a} \right)^{n} .     

Conductive polymer nanocomposites containing <Emphasis Type="Italic">in situ</Emphasis> ultra-fine metal particles

A conductive polymeric composite containing in situ ultra-fine metal particles is prepared by melt blending. Incorporation of elastomeric nano-particles and carbon nanotubes hinders the coalescing of metal particles and causes a shift to the breakup direction in the breakup/coalescence equilibrium of metal particles. The prime metal particles (about 26 μm) are in situ converted into the ultra-fine metal particles (UFMP, about 932 nm). The network of carbon nanotubes has been improved due to in situ ultra-fine metal particles and the percolation threshold of the composite with 1.96 vol% UFMP is only 0.25 vol% carbon nanotubes.     

Molecular structure of <Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">o</Emphasis>-and <Emphasis Type="Italic">p</Emphasis>-hydroxybenzyl)cytisine

The molecular structures of N-(o-and p-hydroxybenzyl)cytisine were investigated by NMR spectroscopy, x-ray structure analysis, and molecular modeling. It was found that NMR resonances of the OH and aromatic protons in N-(o-hydroxybenzyl)cytisine were doubled because of the presence of two conformers in solution. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 165–168, March–April, 2008.     

Synthesis of <Emphasis Type="Italic">ortho</Emphasis>-carboranyl derivatives of (<Emphasis Type="Italic">S</Emphasis>)-asparagine and (<Emphasis Type="Italic">S</Emphasis>)-glutamine

(S)-Asparagine and (S)-glutamine ortho-carboranyl derivatives with free amino and carboxy groups in the α-position were synthesized. By an example of N ^γ-(1,2-dicarba-closo-dodecarboran-3-yl)-(S)-glutamine it was demonstrated that the developed synthetic approach carboranyl derivatives of amino acids allowed the preparation of optically pure isomers.     

Synthesis of <Emphasis Type="Italic">N,N</Emphasis>-disubstituted (<Emphasis Type="Italic">Z</Emphasis>)-<Emphasis Type="Italic">O</Emphasis>-methylnicotinamide oximes

A number of (Z)-N,N-dialkyl- and (Z)-N-acyl-N-alkyl-O-methylnicotinamide oximes was synthesized. Their configuration was confirmed by the NOESY experiment. Evaluation of fungicidal activity of compounds obtained was performed.     

Synthesis of (<Emphasis Type="Italic">E</Emphasis>)-<Emphasis Type="Italic">N</Emphasis>-(3-alkoxy-4-acyloxyphenylmethylene)-<Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">e</Emphasis>-cyclohexyl)amines

Previously unknown E isomers of azomethines (Schiff bases) were synthesized from vanillal and vanillin esters by their reaction with cyclohexylamine.     

Conformations and properties of <Emphasis Type="Italic">O</Emphasis>-Alkyl-<Emphasis Type="Italic">S</Emphasis>-(2-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dialkylamino)-ethylmethylthiophosphonates

Conformers of the biologically active compounds CH₃P(O)(OR)(SCH₂CH₂NR ₂ ^′ ), where (I) R = i-C₄H₉, R′ = C₂H₅ and (II) R = C₂H₅, R′ = i-C₃H₇, are calculated within the AM1 level of theory. The elongated and twisted forms with maximum and minimum distances between a nitrogen atom and those of a phosphorus tetrahedron, respectively, and bearing a syn and anti oriented alkoxy group relative to a phosphoryl oxygen, are studied. It is found that the differences between the energy, electronic, and geometric parameters of these forms are apparent in differences between their properties, e.g., the ability to participate in complexation and protonation, reactions that to some extent simulate the interaction between a substance and a biological object.     

Molecular properties of the copolymers of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diallyl-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylammonium chloride and maleic acid

The hydrodynamic and conformational properties of molecules of poly(N,N-diallyl-N,N-dimethylammonium chloride) and N,N-diallyl-N,N-dimethylammonium chloride-maleic acid copolymers of different compositions in solutions with various ionic-strength and pH values, as well as of the polyelectrolyte complex based on the copolymer with dodecyl sulfate anions in chloroform, are studied. For poly(N,N-diallyl-N,N-dimethylammonium chloride) molecules in a 1 M NaCl solution, the Kuhn segment length and the hydrodynamic diameter of the chain are estimated as A = 3.9 nm and d = 0.48 nm, respectively. In acidic solutions with pH 3.5, the copolymers demonstrate behavior typical for polyelectrolytes. In an alkaline solution with pH 13, when 1 M NaCl is added to the solution of the copolymer containing 29 mol % maleic acid units, there is an antipolyelectrolyte effect that manifests itself as an increase in the intrinsic viscosity of the copolymer and in the hydrodynamic radius of its molecules. It is found that an increase in the fraction of maleic acid units in the copolymer from 12 to 42 mol % brings about a reduction in the equilibrium rigidity of its macromolecules from 4.1 to 2.2 nm. The equilibrium rigidity of polyelectrolyte-complex molecules is higher than that of initial copolymer molecules owing to steric interactions arising between the aliphatic chains of dodecyl sulfate anions. In an electric field, the molecules of the complex are oriented owing to the induced dipole moment resulting from the displacement of dodecyl sulfate anions along the chain contour.     

Synthesis of ethyl (2<Emphasis Type="Italic">E</Emphasis>,4<Emphasis Type="Italic">E</Emphasis>)- and (2<Emphasis Type="Italic">E</Emphasis>,4<Emphasis Type="Italic">Z</Emphasis>)-5-chloropenta-2,4-dienoates

An efficient synthetic approach to 2E,4E and 2E,4Z isomers of ethyl 5-chloropenta-2,4-dienoate has been developed on the basis of one-pot oxidation–olefination of readily accessible (E)- and (Z)-3-chloroprop-2-en-1-ols by the action of barium manganate and ethyl (triphenyl-λ⁵-phosphanylidene)acetate.     

<Emphasis Type="Italic">In situ</Emphasis> XPS study of InAs oxidation in glow-discharge plasma

This is the first in situ XPS study of the InAs oxidation kinetics in glow-discharge plasma in the atmosphere of O₂ and CO₂ gases and in a mixture of O₂ and NF₃ gases. Chemical composition of the oxide films produced by cathodic and anodic polarization of samples was examined. Main regularities and features of the oxide film formation on the InAs surface in the normal and dark glow discharge modes were revealed. Normal glow discharge in oxygen-containing plasma was shown to form bilayer oxide films on the InAs surface. The bottom layer with thickness of some nanometers, which consists of arsenic and indium oxides, forms at the initial oxidation steps, its thickness remaining virtually unchanged. The upper layer consists of Al₂O₃ produced by sputtering of cathode material; it serves as a barrier to oxygen diffusion, its thickness building up linearly with the treatment time in glow-discharge plasma. Chemical composition of the growing proper InAs oxide film and the stoichiometry of subsurface region of a semiconductor substrate strongly depend on the oxidation process parameters. The obtained regularities are discussed.     

Copolymer of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diallyl-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylammonium chloride with maleic acid as drug carrier

A copolymer of N,N-diallyl-N,N-dimethylammonium chloride with maleic acid of constant composition was prepared under the conditions of radical initiation. The possibility of the functionalization of the copolymer with drugs containing amino groups by polymer-analogous transformations was examined. Conditions were found for preparing conjugates of the copolymer with isoniazid. The structures and the quantitative compositions of the conjugates were determined by ¹³С NMR spectroscopy, and the possibility of preparing conjugates with controlled drug content was demonstrated.     

A universal blown film apparatus for <Emphasis Type="Italic">in situ</Emphasis> X-ray measurements

A setup of blown film machine combined with in situ synchrotron radiation X-ray diffraction measurements and infrared temperature testing is reported to study the structure evolution of polymers during film blowing. Two homemade auto-lifters are constructed and placed under the blown machine at each end of the beamline platform which move up and down with a speed of 0.05 mm/s bearing the 200 kg weight machine. Therefore, structure development and temperature changes as a function of position on the film bubble can be obtained. The blown film machine is customized to be conveniently installed with precise servo motors and can adjust the processing parameters in a wide range. Meanwhile, the air ring has been redesigned in order to track the structure information of the film bubble immediately after the melt being extruded out from the die exit. Polyethylene (PE) is selected as a model system to verify the feasibility of the apparatus and the in situ experimental techniques. Combining structure information provided by the WAXD and SAXS and the actual temperature obtained from the infrared probe, a full roadmap of structure development during film blowing is constructed and it is helpful to explore the molecular mechanism of structure evolution behind the film blowing processing, which is expected to lead to a better understanding of the physics in polymer processing.     

Sonogashira reaction catalyzed by palladium isocyanide complex modified <Emphasis Type="Italic">in situ</Emphasis>

Palladium isocyanide complex modified in situ by addition of benzohydrazide as nucleophile was shown to catalyze Sonogashira reactions of phenylacetylene with iodobenzenes in refluxing ethanol in the presence of potassium carbonate. The reactions were complete in 2 h, and neither preliminary degassing nor protection from atmospheric moisture and oxygen was necessary. The yields of the cross-coupling products, unsymmetrical diarylacetylenes were only slightly lower than those obtained with the preliminarily prepared catalyst. The proposed procedure was used to synthesize a series of diarylacetylenes containing both electrondonating and electron-withdrawing substituents in the benzene rings.     

Analysis of <Emphasis Type="Italic">Escherichia coli</Emphasis> nicotinate mononucleotide adenylyltransferase mutants <Emphasis Type="Italic">in vivo</Emphasis> and <Emphasis Type="Italic">in vitro</Emphasis>

Background  

Adenylation of nicotinate mononucleotide to nicotinate adenine dinucleotide is the penultimate step in NAD⁺ synthesis. In Escherichia coli, the enzyme nicotinate mononucleotide adenylyltransferase is encoded by the nadD gene. We have earlier made an initial characterization in vivo of two mutant enzymes, NadD72 and NadD74. Strains with either mutation have decreased intracellular levels of NAD⁺, especially for one of the alleles, nadD72.