Low‐Cost‐Membranen für die Vanadium‐Redox‐Flow‐Batterie

Vanadium redox‐flow batteries are a technology that can be used to store fluctuating energies from solar and wind power. In order to reduce the manufacturing costs of the batteries, e.g., cheaper raw materials can be used. By using polystyrene‐based polymers for membrane production, conductivities comparable to perfluorosulfonic acid membranes can be achieved. A way to produce these heterogeneous membranes consisting of disperse and continuous phase is shown.     

N‐Alkyl‐, 1‐C‐Alkyl‐, and 5‐C‐Alkyl‐1,5‐dideoxy‐1,5‐imino‐(l)‐ribitols as Galactosidase Inhibitors

A series of 1,5‐dideoxy‐1,5‐imino‐(l )‐ribitol (DIR) derivatives carrying alkyl or functionalized alkyl groups were prepared and investigated as glycosidase inhibitors. These compounds were designed as simplified 4‐epi‐isofagomine (4‐epi‐IFG) mimics and were expected to behave as selective inhibitors of β‐galactosidases. All compounds were indeed found to be highly selective for β‐galactosidases versus α‐glycosidases, as they generally did not inhibit coffee bean α‐galactosidase or other α‐glycosidases. Some compounds were also found to be inhibitors of almond β‐glucosidase. The N‐alkyl DIR derivatives were only modest inhibitors of bovine β‐galactosidase, with IC₅₀ values in the 30–700 μm range. Likewise, imino‐l ‐ribitol substituted at the C1 position was found to be a weak inhibitor of this enzyme. In contrast, alkyl substitution at C5 resulted in enhanced β‐galactosidase inhibitory activity by a factor of up to 1000, with at least six carbon atoms in the alkyl substituent. Remarkably, the ‘pseudo‐anomeric’ configuration in this series does not appear to play a role. Human lysosomal β‐galactosidase from leukocyte lysate was, however, poorly inhibited by all iminoribitol derivatives tested (IC₅₀ values in the 100 μm range), while 4‐epi‐IFG was a good inhibitor of this enzyme. Two compounds were evaluated as pharmacological chaperones for a GM1‐gangliosidosis cell line (R301Q mutation) and were found to enhance the mutant enzyme activity by factors up to 2.7‐fold.     

Characterization of 4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine

4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine (DANT) was prepared with a 35 % yield from cyanuric chloride in a three step process. DANT was characterized by IR and NMR spectroscopy (¹H, ¹³C, ¹⁵N), single‐crystal X‐ray diffraction, and DTA. The crystal density of DANT is 1.849 g cm⁻³. The cyclization of one azido group and one nitrogen atom of the triazine group giving tetrazole was observed for DANT in a dimethyl sulfoxide solution using NMR spectroscopy. An equilibrium exists between the original DANT molecule and its cyclic form at a ratio of 7 : 3. The sensitivity of DANT to impact is between that for PETN and RDX, sensitivity to friction is between that for lead azide and PETN, and sensitivity to electric discharge is about the same as for PETN. DANT′s heat of combustion is 2060 kJ mol⁻¹.     

Synthesis and Characterization of 1‐Azido‐2‐Nitro‐2‐Azapropane and 1‐Nitrotetrazolato‐2‐Nitro‐2‐Azapropane

1‐Azido‐2‐nitro‐2‐azapropane ( 1 ) was synthesized in high yield from 1‐chloro‐2‐nitro‐2‐azapropane and sodium azide. 1‐Nitrotetrazolato‐2‐nitro‐2‐azapropane ( 2 ) was synthesized in high yield from 1‐chloro‐2‐nitro‐2‐azapropane and silver nitrotetrazolate. The highly energetic new compounds ( 1 and 2 ) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁴N), elemental analysis and low‐temperature single crystal X‐ray diffraction. 1‐Azido‐2‐nitro‐2‐azapropane ( 1 ) represents a covalently bound liquid energetic material which contains both a nitramine unit and an azide group in the molecule. 1‐Nitrotetrazolato‐2‐nitro‐2‐azapropane ( 2 ) is a covalently bound room‐temperature stable solid which contains a nitramine group and a nitrotetrazolate ring unit in the molecule. Compounds 1 and 2 are hydrolytically stable at ambient conditions. The impact sensitivity of compound 1 is very high (<1 J) whereas compound 2 is less sensitive (<6 J).     

Crystallization behavior of 1,3‐dipalmitoyl‐2‐oleoyl‐glycerol and 1‐palmitoyl‐2,3‐dioleoyl‐glycerol

A model margarine was stored under a temperature fluctuation cycle of 5—20 °C until granular crystals were observed. Using information obtained from the granular crystals, the crystallization behaviors of major triacylglycerols of palm oil, 1,3‐dipalmitoyl‐2‐oleoyl‐glycerol (POP), 1‐palmitoyl‐2,3‐dioleoyl‐glycerol (POO), and their mixtures were then investigated. It was shown that in the model margarine, the POP content in the granular crystals was higher than in their surrounding materials, and the X‐ray diffraction pattern of the granular crystals revealed that they were the most stable polymorph, β. 99% pure POP, POO, and their mixtures were then stored under the above‐mentioned temperature cycle. POP was found to form the unstable polymorph, α, when cooled rapidly from the melt. Within 24 hours transformation into the γ polymorph and then into the β polymorph was observed. POO was shown to transform into the β' polymorph from α. When POP and POO were mixed, the β polymorph did not emerge, instead it was shown that POP and POO were both agglomerated in the mixtures, giving rise to the formation of granular crystals.     

Metal‐ion‐retention properties of the poly(2‐acrylamido‐2‐methyl‐1‐propanosulfonic acid‐co‐4‐vinyl pyridine) resin

The water‐insoluble resin poly(2‐acrylamido‐2‐methyl‐1‐propanosulfonic acid‐co‐4‐vinyl pyridine), through a radical polymerization solution, was synthesized with ammonium persulfate as an initiator and N,N‐methylene bisacrylamide as a crosslinking reagent. The metal‐ion‐retention properties were studied by batch and column equilibrium procedures for the following metal ions: Hg(II), Cu(II), Cd(II), Zn(II), Pb(II), and Cr(III). These properties were investigated under competitive and noncompetitive conditions. The effects of the pH, maximum retention capacity, and regeneration capacity were studied. The resin showed a high retention ability for Hg(II) ions at pH 2.0. The retention of Hg(II) ions from a mixture of ions was greater than 90%. The resin showed a high selectivity for Hg(II) with respect to other metal ions. The Hg(II)‐loaded resin was able to be recovered with 4M HClO₄. The retention capacity was kept after four cycles of adsorption and desorption. The retention properties for Hg(II) were very similar with the batch and column methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3556–3562, 2003     

Lewis Acid‐Mediated Transformations of trans‐2‐Aroyl‐3‐aryl‐ cyclopropane‐1,1‐dicarboxylates into 2‐Pyrones and 1‐Indanones

trans‐2‐Aroyl‐3‐arylcyclopropane‐1,1‐dicarboxylates upon treatment with aluminium(III) chloride (AlCl₃) underwent ring‐opening, fragmentation, recombination and lactonization to give highly substituted 2‐pyrones. Alternatively, when treated with titanium(IV) chloride (TiCl₄), the cyclopropane diesters underwent a Nazarov cyclization to afford 1‐indanones with high diastereoselectivity.

     

Lecithin‐enhanced biotransformation of cholesterol to androsta‐1,4‐diene‐3,17‐dione and androsta‐4‐ene‐3,17‐dione

A biotransformation process using Mycobacterium sp was studied for androsta‐1, 4‐diene‐3,17‐dione (ADD) and androsta‐4‐ene‐3,17‐dione (AD) production from cholesterol. Cholesterol has a poor solubility in water (～1.8 mg dm^?3 at 25 °C), which makes it difficult to use as the substrate for biotransformation. Lecithin is a mixture of phospholipids of phosphatidylcholine (PC) and phosphatidylethanolamine (PE), which behave like surfactants and can form planar bi‐layer structures in an aqueous medium. Therefore, a small amount of lecithin (<1 g dm^?3) can be used to form stable colloids with cholesterol at a relatively high concentration (20 g dm^?3) in water. In this work, an energy density of 1000 J cm^?3 from sonication was provided to overcome the self‐association of cholesterol and to generate a stable lecithin–cholesterol suspension that could be used for enhanced biotransformation. The lecithin–cholesterol suspension was stable and could withstand typical autoclaving conditions (121 °C, 15 psig, 20 min). In contrast to conventional surfactants, such as Tween 80, that are commonly used to help solubilize cholesterol, lecithin did not change the surface tension of the aqueous solution nor cause any significant foaming problem. Lecithin was also biocompatible and showed no adverse effect on cell growth. Compared with the medium with Tween 80 as the cholesterol‐solubilizing agent, lecithin greatly improved the biotransformation process in regard to its final product yield (～59% w/w), productivity (0.127–0.346 g dm^?3 day^?1), ADD/AD ratio (6.7–8), as well as the long‐term process stability. Cells can be reused in repeated batch fermentations for up to seven consecutive batches, but then lose their bioactivity due to aging problems, possibly caused by product inhibition and nutrient depletion. © 2002 Society of Chemical Industry     

Studies on ethylene‐propylene‐diene rubber modification by N‐chlorothio‐N‐butyl‐benzenesulfonamide

N‐Chlorothiosulfonamides have been used to modify ethylene‐propylene‐diene rubber (EPDM) to enhance the compatibility of EPDM in, e.g., natural rubber (NR)/butadiene rubber (BR)/EPDM blends for ozone resistance. N‐Chlorothio‐N‐butyl‐benzenesulfonamide (CTBBS) was selected as a representative for N‐chlorothiosulfonamides. In this study, we found that CTBBS behaves differently with various types of EPDM. Three types of EPDM were selected: ethylidene norbornene (ENB)‐EPDM, hexadiene (HD)‐EPDM, and dicyclopentadiene (DCPD)‐EPDM. HD‐EPDM showed the greatest effectiveness toward CTBBS‐modification. However, this EPDM is not commercially available anymore. On the opposite side, DCPD‐EPDM showed the lowest reactivity so that almost no modification could be realized. The result with ENB‐EPDM was, that upon application of CTBBS to ENB‐EPDM, gelation occurred and, therefore, a low amount of modification was achieved. With the limited modification efficiency for ENB‐EPDM, there is no significant improvement when applying the modified ENB‐EPDM into NR/BR/EPDM blends. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of 5‐vinyl‐m‐ phenylene‐m′‐phenylene‐32‐ crown‐10 and its radical polymerization behavior

Synthesis of a vinyl monomer, containing a 32‐membered crown ether unit (VCE) as a pendant group, was achieved by using tetra(ethylene glycol) dichloride, resorcinol, and 3,5‐dihydroxyacetophenone as starting materials. The product was identified by means of FTIR and ¹H‐NMR. It was found that this monomer readily polymerizes by the conventional radical initiator 2,2′‐ azobisisobutyronitrile (AIBN) to afford a polymer whose number‐average molecular weight is 36 kg/mol; however, the final conversion of the polymer was < 80%. The results of the copolymerization of VCE with styrene (ST) or acrylonitrile (AN) are also discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2372–2379, 2002     

An Ab Initio Theoretical Study of 2,4,6‐Trinitro‐1,3,5‐Triazine, 3,6‐Dinitro‐1,2,4,5‐Tetrazine,and 2,5,8‐Trinitro‐Tri‐s‐Triazine

In order to evaluate 2,4,6‐trinitro‐1,3,5‐triazine (TNTAz), 3,6‐dinitro‐1,2,4,5‐tetrazine (DNTAz), and 2,5,8‐trinitro‐tri‐s‐triazine (TNTsTAz), the geometries of these compounds have been fully optimized employing the B3LYP density functional method and the AUG‐cc‐pVDZ basis set. The accurate gas phase enthalpies of formation have been obtained by using the atomization procedure and designing isodesmic reactions in which the parent rings are not destroyed. Based on B3LYP/AUG‐cc‐pVDZ calculated geometries and natural charges, the crystal structures have been predicted using the Karfunkel–Gdanitz method. Computed results show that there exists extended conjugation over the parent rings of these compounds. More energy content is reserved in DNTAz than in both TNTAz and TNTsTAz. The title compounds are much more sensitive than 1,3,5‐trinitrobenzene. The calculated detonation velocity of DNTAz reaches 9.73–9.88 km s⁻¹, being larger than those of CL‐20 and TNTAz. TNTsTAz has no advantage over the widely used energetic compounds such as RDX and HMX.     

Singlet oxygen generation and adhesive loss in stimuli‐responsive,fullerene‐polymer blends,containing polystyrene‐block‐polybutadiene‐block‐polystyrene and polystyrene‐block‐polyisoprene‐block‐polystyrene rubber‐based adhesives

The adhesive properties, as measured by bulk tack and peel strength analysis, were found to decrease in polystyrene‐block‐polybutadiene‐block‐polystyrene (SBS) and polystyrene‐block‐polyisoprene‐block‐polystyrene (SIS) PSA films containing common singlet oxygen generators, acridine, rose bengal, and C₆₀ fullerene, when irradiated with a tungsten halogen light in air. The addition of the singlet oxygen quencher, β‐carotene, to the C₆₀ fullerene samples was found to significantly deter the rate of adhesive loss in the fullerene‐SBS and ‐SIS PSA nanocomposites. The presence of oxygen was essential to the mechanism of adhesive loss and, in combination with the effects of singlet oxygen generators and a singlet oxygen scavenger, strongly supports a singlet‐oxygen mediated process. FTIR investigations of fullerene‐SBS and ‐SIS systems suggest the initial formation of peroxides which, upon further irradiation, lead to the generation of carbonyl‐containing compounds of a ketonic type after crosslinking. Rates of SBS and SIS C‐H abstraction were comparable and found to decrease when the high‐pressure, mercury xenon irradiation source was filtered to allow only light of λ > 390 nm. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermo‐electric‐visco‐elastic material

In this work, we introduce the Seebeck effect in Ohm's law and Thomson heating effect in generalized Fourier's law, to the equations of the linear theory of electro‐magneto‐thermoviscoelasticity, allowing the second sound effects. A normal mode analysis is used. The resulting formulation is applied to a problem of a rotating thick plate subject to heat on parts of the upper and lower surfaces of the plate that varies exponentially with time. The exact formulas of temperature, displacement, stresses, electric field, magnetic field, and current density are obtained. The considered variables are presented graphically and discussions are made. Seebeck and Peltier effects on thermoelectric viscoelastic material are studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ultrafiltration of metal ions by water‐soluble chelating poly(N‐acryloyl‐N‐methylpiperazine‐co‐N‐acetyl‐α‐aminoacrylic acid)

Water‐soluble copolymers of N‐acryloyl‐N‐methylpiperazine and N‐acetyl‐α‐aminoacrylic acid were synthesized by radical polymerization. The copolymerization yield ranged between 60 and 97%. The FTIR and NMR spectra demonstrated that the copolymerization occurred. The copolymer composition was determined from ¹H‐NMR spectra by comparison of methyl groups from both moieties. The copolymers were richest in AAA units. The metal ion retention properties were investigated by the liquid‐phase polymer‐based retention (LPR) technique at different pH and filtration factors. The affinity for the metal ions depended on the copolymer composition, pH, and filtration factor. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2556–2561, 2002     

A Highly Regioselective Preparation of 4‐Chloromethyl‐5‐methyl‐2‐aryl‐1,3‐oxazoles

A facile highly regioselective process is described for the formation of 4‐chloromethyl‐1,3‐oxazoles from 1,3‐oxazole N‐oxide/HCl salts. An explanation is presented for the high regioselectivity in deoxygenation‐chlorination using POCl₃ with HCl salts compared to the corresponding free N‐oxides. The method is quite general and the products are isolated by direct precipitation in all cases studied.     

One‐pot Synthesis of N‐Formyl‐O‐acyl‐ threo‐ and erythro‐DL‐β‐phenylserine Ethyl Esters and their Antiviral Properties

A series of N‐formyl‐O‐acyl‐β‐phenylserine derivatives 1b ‐ 7b were prepared by the interaction of N‐acyl‐b‐phenylserine ethyl esters 1a ‐ 7a with formic acid in presence of 1.5% HF. One‐pot acyl group N → O migration followed N‐formylation under elaborated reaction conditions. The kinetics of the reaction was investigated. The carboxylic acid moiety in the structure of β‐phenylserine had a strong influence on the reproduction of the used test‐viruses. The toxicity and antiviral activity is dependent on the diastereomeric forms of evaluated compounds.     

Synthesis and Characterization of 1‐Nitroguanyl‐3‐nitro‐5‐amino‐1,2,4‐triazole

The synthesis of 1‐nitroguanyl‐3‐nitro‐5‐amino‐1,2,4‐triazole (ANTA‐NQ) ( 1 ) with good yield and high purity is described. DSC analysis showed that the material displays good thermal stability. An X‐ray crystallographic analysis confirms the structure of this material, as well as displays intramolecular hydrogen bonding. A gas pycnometry density for this material was measured to be 1.79 g cm⁻³. The heat of formation of this material was also measured. These data, along with the molecular formula were used as inputs to calculate the detonation velocity and detonation pressure using the Cheetah thermochemical code. The sensitivity of this material towards impact, spark and friction was also measured, as well as its vacuum thermal stability. The 3‐azido derivative 2 was also prepared and its properties are described as well. The above data show that (ANTA‐NQ) may be a high performing material with low sensitivity and good thermal stability.     

Recycled‐disposable‐chopstick‐fiber‐reinforced polypropylene green composites

The utilization of disposable chopsticks is very popular in Taiwan, China, and Japan and is one of the major sources of waste in these countries. In this study, recycled disposable chopstick fiber was chemically modified. Subsequently, this modified fiber and polypropylene‐graft‐maleic anhydride were added to polypropylene (PP) to form novel fiber‐reinforced green composites. A heat‐deflection temperature (HDT) test showed an increase of approximately 81% for PP with the addition of 60‐phr fibers, and the HDT of the composite could reach up to 144.8°C. In addition, the tensile strength, Young's modulus, and impact strength were 66, 160.3, and 97.1%, respectively, when the composite material was 40‐phr fibers. Furthermore, this type of reinforced PP would be more environmentally friendly than an artificial‐additive‐reinforced one. It could also effectively reduce and reuse the waste of disposable chopsticks and lower the costs of the materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012