Synthesis of a highly soluble superstructured phenanthroline strapped porphyrin

A highly soluble phenanthroline strapped porphyrin is prepared on multigram scale by appropriate functionalization with C₁₂ chains after the cyclization of the tetrapyrrolic macrocycle.     

The application of highly soluble amine-terminated aromatic polyimides with pendent tert-butyl groups as a tougher for epoxy resin

Polyimides(PIs) with various molecular weights synthesized via the reaction of aromatic diamine monomer containing tert-butyl groups with aromatic dianhydride were highly soluble in common organic solvents and some epoxy resins at room temperature. These PIs can be incorporated in the absence of organic solvent into epoxy resin E51 with the loading below 2 wt% forming EP-PI composites. No phase separation is observed by SEM on cryogenically fractured surfaces of EP-PI composites. The PI can improve mechanical properties, especially impact strength. Adding 2 wt% PI-1.5W, the impact strength reaches to 55 k J/m2 with the increase in tensile and flexural strengths by 14% and 3%, respectively. SEM analyses for the fracture surface suggest that PI reduces the crosslink density, improves the plasticity of epoxy resin and changes the mode of fracture from fragile to ductile. Moreover, the glass transition temperature of EP-PI composites was found to increase to a significant extent.     

Electrochemical preparation of a soluble conducting aniline-thiophene copolymer

A new of soluble sulfonated conductive copolymer has been synthesized by electrochemical oxidation in the presence of anhydrous FSO₃H. The sulphur-to-nitrogen ratios indicated that copolymers were formed in addition to the incorporation of groups into polymeric backbone. The sulfonated copolymer films have better solubility in DMSO and KOH. The conductivity of the copolymer films increases with the increase in the number of thiophene rings in the polymeric backbone. Copolymer films synthesized were investigated by cyclic voltammetry, UV-visible, FT-IR and ¹H-NMR spectroscopy, dry conductivity and intrinsic viscosity measurements, elemental analysis and SEM pictures.     

Hydrophobic mechanochemical treatment of metallic surfaces wettability measurements as a means of assessing homogeneity

Hydrophobicity, lubrication and anticorrosion properties of steel substrates have been obtained by a deposition of thin film (i.e. by mechanochemical treatment) at room conditions. Stearic acid and paraffin were chosen as reactive molecules. Different abrasive powders were selected to generate active sites on the treated surfaces for adsorption of the reactive molecules and then, the results were compared. The surfaces were analyzed by reflection-absorption infrared spectroscopy (RAIRS). The results emphasize that, a thick layer of mixed stearic acid/paraffin was deposited onto the metallic surface after the treatment. After hexane rinsing we could only detect a very thin layer of oriented stearic acid molecules chemically adsorbed onto the metallic surface and which engages strong interactions with it. Whereas, RAIRS only provides molecular analysis, the XPS technique was complementary for discriminating the different surfaces. It was possible to show differences in thickness as well as in coverage according to the size and shape of abrasive particles. Furthermore, we could conclude that deposit layer is not uniform. Defects were always present and were dependent on abrasive powders used. Then wettability was assessed as a way to test the homogeneity of thin films generated by the mechanochemical treatment. In agreement with theoretical data, receding contact angle was very dependent on the defects in the deposited film. If holes or aggregates were increased in the deposit layer, the receding contact angle was decreased while advancing contact angles and equilibrium contact angles remained constant. A very important point for technological applications was that the homogeneity of the deposited film was governed by abrasive powder involved in mechanochemical treatment and contact angle values were a direct measurement of the homogeneity of surfaces generated by mechanochemical treatment.     

Facile synthesis and properties of a new generation of soluble and thermally stable polyimides

A new diamine, 1,4-phenylene bis((E)-1-(4-chloro-3-aminobenzylidene) thiourea) (PCABT), containing phenylthiourea and azomethine groups was prepared from the reduction of dinitro compound, 1,4-phenylene bis((E)-1-(4-chloro-3-nitrobenzylidene)thiourea), PCNBT. The structures of resulting monomers were characterized by elemental analysis, FTIR, ¹H and ¹³C NMR techniques. Afterwards, this diamine was reacted with various aromatic dianhydrides (ODPA, BTDA and 6FDA) in glacial acetic acid to afford poly(phenylthiourea azomethine imide)s (PPTAIs) with η_inh of 1.59-1.66 dL/g, depending on the dianhydride used. The ensuing PPTAIs exhibited ample solubility in organic solvents (DMAc, DMF, DMSO and NMP) and were obtained in quantitative yields. Also, all polyimides were amorphous according to wide-angle X-ray determination. GPC measurements of polymers revealed M_w around 69,000-72,000. Moreover, thermogravimetric analyses indicated that PPTAIs were fairly stable up to 550 °C, and 10% weight loss temperatures were recorded in the range of 563-578 °C (N₂ atmosphere). Ultimately, these polyimides own high glass transition temperatures about 281-285 °C.     

Changes in texture of ultramicroporous Zr/silica gels as a result of hydrothermal treatment

A study has been made of the hydrothermal modification of Zr/silica gels containing up to 4.3% ZrO₂ by weight, with pore sizes smaller than 0.69 nm. It has been established that silica gels become more resistant to hydrothermal treatment as the content of zirconium ions is increased.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 4, pp. 259–263, July–August, 1995.     

Conversion of SB 203580-insensitive MAP kinase family members to drug-sensitive forms by a single amino-acid substitution

Background: Specific inhibitors of protein kinases have great therapeutic potential, but the molecular basis underlying their specificity is only poorly understood. We have investigated the drug SB 203580 which belongs to a class of pyridinyl imidazoles that inhibits the stress-activated protein (SAP) kinases SAPK2a/p38 and SAPK2b/p38β2 but not other mitogen-activated protein kinase family members. Like inhibitors of other protein kinases, SB 203580 binds in the ATP-binding pocket of SAPK2a/p38. Results: The SAP kinases SAPK1γ/JNK1, SAPK3 and SAPK4 are not inhibited by SB 203580, because they have methionine in the position equivalent to Thr106 in the ATP-binding region of SAPK2a/p38 and SAPK2b/p38β2. Using site-directed mutagenesis of five SAP kinases and the type I and type II TGFβ receptors, we have established that for a protein kinase to be inhibited by SB 203580, the sidechain of this residue must be no larger than that of threonine. Sensitivity to inhibition by SB 203580 is greatly enhanced when the sidechain is even smaller, as in serine, alanine or glycine. Thus, the type I TGFβ receptor, which has serine at the position equivalent to Thr106 of SAPK2a/p38 and SAPK2b/p38β2, is inhibited by SIB 203580. Conclusions: These findings explain how drugs that target the ATP-binding site can inhibit protein kinases specifically, and show that the presence of threonine or a smaller amino acid at the position equivalent to Thr106 of SAPK2a/p38 and SAPK2b/p38β2 is diagnostic of whether a protein kinase is sensitive to the pyridinyl imidazole class of inhibitor.     

Mechanochemical Synthesis of Aryl Fluorides by Using Ball Milling and a Piezoelectric Material as the Redox Catalyst

Aryl fluorides are important structural motifs in many pharmaceuticals. Although the Balz–Schiemann reaction provides an entry to aryl fluorides from aryldiazonium tetrafluoroborates, it suffers from drawbacks such as long reaction time, high temperature, toxic solvent, toxic gas release, and low functional group tolerance. Here, we describe a general method for the synthesis of aryl fluorides from aryldiazonium tetrafluoroborates using a piezoelectric material as redox catalyst under ball milling conditions in the presence of Selectfluor. This approach effectively addresses the aforementioned limitations. Furthermore, the piezoelectric material can be recycled multiple times. Mechanistic investigations indicate that this fluorination reaction may proceed via a radical pathway, and Selectfluor plays a dual role as both a source of fluorine and a terminal reductant.     

Synthesis and characterization of soluble polyimides derived from a novel unsymmetrical diamine monomer: 1,4-(2′,4″-diaminodiphenoxy)benzene

A new aromatic unsymmetrical diamine monomer, 1,4-(2′,4″-diaminodiphenoxy)benzene (OAPB), was successfully synthesized in three steps using hydroquinone as starting material and polymerized with various aromatic tetracarboxylic acid dianhydrides, including 4,4′-oxydiphthalic anhydride (ODPA), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 2,2′-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride (6FDA) and pyromellitic dianhydride (PMDA) via the conventional two-step thermal or chemical imidization method to produce a series of the unsymmetrical aromatic polyimides. The polyimides were characterized by solubility tests, viscosity measurements, IR, ¹H NMR, and ¹³C NMR spectroscopy, X-ray diffraction studies, and thermogravimetric analysis. The polyimides obtained had inherent viscosities ranged of 0.38-0.58 dL/g, and were easily dissolved in common organic solvents. The resulting strong and flexible PI films exhibited excellent thermal stability with the decomposition temperature (at 5% weight loss) of above 505 °C and the glass transition temperature in the range of 230-299 °C. Moreover, the polymer films showed outstanding mechanical properties with the tensile strengths of 41.4-108.5 MPa, elongation at breaks of 5-9% and initial moduli of 1.15-1.68 GPa.     

Prolonged durability of electroporation microarrays as a result of addition of saccharides to nucleic acids

The electroporation microarray is a useful tool for high-throughput analysis of gene functions. However, transfection efficiency is greatly impaired by storage of the microarrays, due to water evaporation from arrayed nucleotides. In this study, we aimed at evaluating the effect of saccharides and sugar alcohols, added to the solution of the plasmid DNA or small interfering RNA (siRNA). Microarrays loaded with plasmids and siRNAs were prepared with various polyols including sugars and sugar alcohols. After storage of these microarrays at different temperatures for various time periods, transfection efficiency was evaluated using human embryonic kidney cells. In the case of plasmid-loaded microarrays, addition of monosaccharides (glucose, fructose), disaccharides (trehalose, sucrose), and trisaccharide (raffinose) served to retain transfection efficiency at a reasonably high level after storage at −20 °C. The observed effects may be because moisture retention serves to maintain the solubility of DNA. In contrast, polysaccharide (dextran) and sugar alcohol (glycerol) had insignificant effects on retention of transfection efficiency. On the other hand, addition of saccharides and sugar alcohols had insignificant effects on the transfection of siRNA after storage of a microarray at 25 °C for 7 days, presumably due to the intrinsically-high solubility of siRNA which consists of short nucleotides. Figure (PPTX 3.80 MB)

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Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Degradation as a result of UV radiation of bloodmeal-based thermoplastics

Polymers are known for their susceptibility to degradation as a result of ultra-violet (UV) radiation. In this study, the UV stability of bloodmeal-based thermoplastics (BMT) was evaluated over a period of 12 weeks. Formulations with and without plasticiser were tested and moisture was excluded during accelerated weathering to isolate the effect of UV because of the material’s known sensitivity to moisture. It was found that embrittlement due to loss of water overshadowed the effect of UV degradation. Embrittlement caused the material’s toughness to be reduced by an order of magnitude after only two weeks of exposure, for either plasticised or unplasticised samples. An initial increase in tensile strength was observed after two weeks followed by a steady decline in strength. The elastic modulus reached a plateau after about two weeks of exposure. FTIR did not confirm any chemical changes after 12 weeks exposure and TGA suggested that low molecular mass species were quickly lost during the course of the test. The absence of chemical changes does not suggest resistance to environmental degradation, although the dark pigmentation of bloodmeal may have contributed to the lack of UV degradation. Embrittlement remains a greater concern and requires further attention.     

The solubility of the noble gases He,Ne, Ar,Kr, and Xe in water up to the critical point

The solubility of the noble gases Ar, He, Ne, Kr, and Xe in pure water was measured from 298 to 561°K. These data in turn were extrapolated to the critical point of water, thus providing a complete set of Henry's law constants from 274 to 647°K when combined with the existing literature data. Equations describing the behavior of the Henry's law constants over this temperature range are also given. The data do not confirm extrapolations of empirical correlations based on low-temperature solubility data.     

Inverse gas chromatography as a source of physiochemical data

Inverse gas chromatography (IGC) is presented as a useful method for the examination of physicochemical properties of various materials. The advantages of IGC are presented. However, the uncertainties and sources of possible errors are also indicated and discussed.     

Titanium Dioxide as a Mild and Efficient Catalyst for Conversion of Epoxides to Thiiranes

Abstract

Titanium dioxide (TiO₂) efficiently catalyze the reaction of a variety of epoxides with ammonium thiocyanate in refluxing acetonitrile to afford the corresponding thiirane in high to excellent yields.     

Application of β-Glucosidase in a Biphasic System for the Efficient Conversion of Polydatin to Resveratrol

Resveratrol, an ingredient of traditional Chinese medicine, has beneficial effects on human health and huge potential for application in modern medicine. Polydatin is extracted from plants and then deglycosylated into resveratrol; enzymatic methods are preferred for this reaction. In this study, a β-D-glucosidase from Sphingomonas showed high efficiency in transforming polydatin into resveratrol and was tolerant toward organic solvents. Applying this enzyme in a biphasic transformation system resulted in 95.3% conversion of 20% concentration crude polydatin to resveratrol in 4 h. We thus report a new method for high-efficiency, clean production of resveratrol.     

Synthesis and characterization of soluble polyimides based on a new fluorinated diamine: 4-Phenyl-2,6-bis[3-(4′-amino-2′-trifluoromethyl-phenoxy) phenyl] pyridine

A new kind of pyridine-containing aromatic diamine monomer, 4-phenyl-2,6-bis[3-(4′-amino-2′-trifluoromethyl-phenoxy) phenyl] pyridine (m-PAFP), was successfully synthesized by a modified Chichibabin reaction of 3-(4′-nitro-2′-trifluoro-methyl-phenoxy)-acetophenone with benzaldehyde, followed by a catalytic reduction. A series of fluorinated pyridine-bridged aromatic poly(ether-imide)s were prepared from the resulting diamine monomer with various aromatic dianhydrides via a conventional two-step thermal or chemical imidization method. The inherent viscosities values of these polyimides were in the range of 0.56-1.02 dL/g, and they could be cast and thermally converted into transparent, flexible, and tough polyimide films. The polyimides displayed higher solubility in polar solvents such as NMP, DMSO and m-cresol. The polyimides had good thermal stability, with the glass transition temperatures (T_g) of 187-211 °C, the temperatures at 5% weight loss of 511-532 °C, and the residue at 800 °C in air was higher than 50%. These films also had dielectric constants of 2.64-2.74 at 10 MHz and low water uptake 0.53-0.66%. Wide-angle X-ray diffraction measurements revealed that these polyimides were predominantly amorphous. Moreover, the polymer films of these novel polyimides showed outstanding mechanical properties with the tensile strengths of 90.1-96.6 MPa, elongations at breakage of 8.9-10.7% and tensile modulus of 1.65-1.98 GPa.     

Transfer of electron density as a result of hydrogen bond formation

It has been found that the amount of charge transfer between donor and acceptor molecules in four sets of hydrogen‐bonded complexes may be adequately described as an exponential function of the equilibrium distance between the hydrogen atom and the nearest atom of the acceptor molecule. The exponential factors of the transfer are of the same order but somewhat larger than the factors found otherwise in the investigations of dynamic electron transfer. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

The compensation effect as a result of integration of theArrhenius equation

Summary It has been shown that joined segments of straight lines are observed upon plotting the logarithm of the rate constant against the reciprocal temperature, exhibiting sharp breaks at so-called critical temperatures indicating sudden changes in activation energy [3, 5–8]. If the integration of the differential form of theArrhenius equation from 0 toT K is taken into account, the compensation effect can easily be explained.

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Der Kompensationseffekt als Ergebnis der Integration derArrhenius-Gleichung

Zusammenfassung Wenn man den Logarithmus der Geschwindigkeitskonstante gegen die reziproke Temperatur aufträgt, erhält man aufeinanderfolgende Teilstücke von Geraden mit scharfen Knicks bei sogenannten kritischen Temperaturen, welche jeweils eine Änderung der Aktivierungsenergie anzeigen [3, 5–8]. Integration derArrhenius-Gleichung zwischen 0 undT K führt zu einer zwanglosen Erklärung des Kompensationseffekts.