Polymerized ionic liquids with guanidinium cations as host for gel polymer electrolytes in lithium metal batteries

Polymerized ionic liquids (PILs) having guanidinium cations with different counter‐anions, such as PF₆^? and N(CF₃SO₂)₂^? (TFSI^?), were synthesized by copolymerization of a guanidinium ionic liquid monomer with methyl acrylate followed by an anion exchange reaction. Furthermore, incorporating a guanidinium ionic liquid, LiTFSI salt and nano‐size SiO₂, a quaternary gel polymer electrolyte based on one of the PILs as the polymer host was prepared. The quaternary gel polymer electrolyte was chemically stable even at a higher temperature of 80 °C in contact with the lithium anode. In particular, the electrolyte exhibited high lithium ion conductivity, wide electrochemical stability window and good lithium stripping/plating performance. Li/LiFePO₄ batteries with the quaternary gel polymer electrolyte at 80 °C had capacities of 140 and 130 mA h g^?1 respectively at 0.1 and 0.2 C current rates. Copyright © 2011 Society of Chemical Industry     

Impact of compression,physical aging,and freezing rate on the crystallization characteristics of an amorphous sugar matrix

Amorphous matrices made up of sugar molecules, are frequently used in food and pharmaceutical industries. A drawback to their use is that they are susceptible to collapse, as a result of water uptake and an increase in temperature and subsequently crystallize. Herein, the crystallization characteristics of amorphous sugar (sucrose and α-lactose) preparations were analyzed, with the purpose of obtaining knowledge that could lead to the prediction of how long the amorphous state is retained under various conditions. The impact of compression, physical aging and freezing rate on the induction period (t_ind) for crystallization were examined. Freeze-dried sugar samples were compressed at 74 or 443 MPa (5 min) and then rehumidified at specified RHs. Some freeze-dried sucrose samples were physically aged, and alternatively freeze-drying was conducted under different conditions. The isothermal crystallization of the prepared samples at different temperatures (T), the glass transition and the crystallization temperature (T_cry) were measured, using differential scanning calorimetry. The compression markedly decreased the t_ind, while significantly lowered the hygroscopicity. Physical aging and slower-freezing also shortened the t_ind. The t_ind was found to be correlated exclusively with (T_cry–T), regardless of rehumidification, compression, sugar type, physical aging and freezing rate in the freeze-drying process.     

Feasible method,utilizing density changes,for estimating in situ dynamic strength and deformation properties of sand samples

Laboratory tests and design reliability are directly controlled by sample quality. The frozen sampling (FS) method is useful for dynamic strength and deformation tests of undisturbed clean sand. However, it is very expensive and requires considerable equipment. The sample quality of Toyoura sands obtained from 48 mm and 75 mm samplers are scrutinized based on void ratio, dynamic strength and deformation properties through model and cyclic undrained triaxial tests. A conventional method for estimating in-situ dynamic strength and deformation properties of sand samples utilizing density changes is examined and the applicability of the proposed method is discussed for the samples obtained from Niigata sand deposits.The main conclusions obtained from this study are summarized as follows:(1) A conventional method for estimating in-situ void ratio (e₀), D_r, stress ratio (R_L20) in a 20 cyclic time frame and the initial modulus of rigidity (G₀) of sand samples utilizing density changes is proposed.(2) The in-situ R_L20 and G₀ estimated from the proposed method for sand samples from tube samplers were similar to those of frozen sampling and the in-situ modulus of initial rigidity was calculated from the secondary wave velocity for Niigata sand deposits.Therefore, dynamic strength and deformation properties changes, caused by sampling, can be modified appropriately to an in-situ condition by this proposed method.     

The Role of a Nonribosomal Peptide Synthetase in l‐Lysine Lactamization During Capuramycin Biosynthesis

Capuramycins are one of several known classes of natural products that contain an l ‐Lys‐derived l ‐α‐amino‐?‐caprolactam (l ‐ACL) unit. The α‐amino group of l ‐ACL in a capuramycin is linked to an unsaturated hexuronic acid component through an amide bond that was previously shown to originate by an ATP‐independent enzymatic route. With the aid of a combined in vivo and in vitro approach, a predicted tridomain nonribosomal peptide synthetase CapU is functionally characterized here as the ATP‐dependent amide‐bond‐forming catalyst responsible for the biosynthesis of the remaining amide bond present in l ‐ACL. The results are consistent with the adenylation domain of CapU as the essential catalytic component for l ‐Lys activation and thioesterification of the adjacent thiolation domain. However, in contrast to expectations, lactamization does not require any additional domains or proteins and is likely a nonenzymatic event. The results set the stage for examining whether a similar NRPS‐mediated mechanism is employed in the biosynthesis of other l ‐ACL‐containing natural products and, just as intriguingly, how spontaneous lactamization is avoided in the numerous NRPS‐derived peptides that contain an unmodified l ‐Lys residue.     

Preparation of poly(N-isopropylacrylamide)–SiO2 hybrid gels and their thermosensitive properties

The swelling and adsorption behavior of poly(N-isopropylacrylamide)–SiO₂ hybrid gels, derived from copolymerization of N-isopropylacrylamide and 3-methacryloxypropyltrimethoxysilane (MPTMOS) and following hydrolysis and condensation, were investigated. The hybrid gels exhibited temperature dependence of both the swelling ratio and adsorption of solutes, and their temperature dependence of both the swelling ratio and adsorption of solutes, and their temperature dependence was related to the MPTMOS content in the hybrid gels. In addition, the modification of thermosensitive properties of the hybrid gels could be achieved by treatment with other silane compounds. © 1996 John Wiley & Sons, Inc.     

Burning Rate Augmentation of BAMO Based Propellants

Thermal decomposition and the burning properties of BAMO based propellants with HMX or AN/HMX have been investigated. The heat generated by the azide binder decomposition initiated and accelerated the thermal decomposition of HMX and AN. Ammonium perchlorate (AP) and lead stearate with carbon black significantly altered the mechanisms of the thermal decomposition and the burning properties of the HMX based propellants. AP showed an increase in burning rate with a slight decrease in burning rate pressure exponent. The lead catalyst yielded high value of the burning rate with the lowest pressure exponent. The ammonium dichromate also influenced the mechanisms of the thermal decomposition and the burning properties of the AN/HMX samples. The combination of ammonium dichromate and copper chromite was the most effective on the burning rate augmentation of AN/HMX based propellants. AN sublimed and evaporated from the condensed phase and mainly reacted exothermically in the gas phase HMX and AN/HMX based propellants showed smokeless burning characteristics in the small rocket motor combustion tests.     

A molten metal jet impingement on a flat spreading surface

ABSTRACT

In the event of a severe accident, past experiences such as Three Mile Island and Fukushima Daichi have shown that the reactor core of a light-water nuclear reactor, if not properly safeguarded, could go through a meltdown. This will be followed by the formation of a corium, a mix of molten fuel elements, and liquid metals from the Reactor Pressure Vessel (RPV). In the worst-case scenario, a melt through from the RPV can occur and lead to the spreading of the corium, in the form of a molten element’s jet impinging on a flat concrete structure of the Primary Containment Vessel (PCV). To enhance the decommissioning and the safety procedure, scope of the present article is to deepen the understanding of the phenomena involved in the mentioned scenario, mainly jet-instability and molten material spreading. In the present study, experiments were carried out, by using corium simulant materials such as Copper and Tin, to investigate the link between the instability of the gravity-driven molten metal jet and the impinging followed by its spreading over a flat area.     

Determination of hyoscyamine and scopolamine in serum and urine of humans by liquid chromatography with tandem mass spectrometry

A simple method was developed for the analysis of hyoscyamine and scopolamine in human serum and urine using liquid chromatography with tandem mass spectrometry (LC/MS/MS). Hyoscyamine and scopolamine in serum and urine were cleaned up with an Oasis HLB cartridge and a PSA cartridge. The LC separation was carried out on an ODS column, using linear gradient elution with 5 mmol/L IPCC-MS3-methanol as the mobile phase. The mass spectral acquisition was done in the positive ion mode by applying selected reaction monitoring (SRM). The recoveries of hyoscyamine and scopolamine were 86.0-105% from human serum and urine fortified at 0.2 ng/mL and 10 ng/mL. The detection limits of hyoscyamine and scopolamine were 0.02 ng/mL. Four serum and three urine samples of humans poisoned by eating Datura innoxia Mill. were analyzed by this method. Hyoscyamine and scopolamine were detected at the levels of 0.45-3.5 ng/mL in all serum samples and 170-670 ng/mL in all urine samples.     

Occurrence of two genotypes of tetracycline (TC) resistance gene tet(M) in the TC-resistant bacteria in marine sediments of Japan

The tetracycline (TC) resistance gene tet(M) was monitored in bacteria isolated from Japanese coastal and off-shore marine sediments. The high rate of occurrence of TC resistant (TC(r)) bacteria (120 microg mL(-1) TC) was observed at frequency ranges between 0.0-0.08% in Tokyo Bay, 1.67-1.82% in Sagami Bay and 0.0-4.35% in the open Pacific Ocean. The tet(M) gene was PCR amplified from the TC(r) isolates, showing 127 of 209 isolates (60.8%) as positive. The rate of occurrence of tet(M) was between 32.0-96.0%, 21.1 -28.0% and 0.0-83.3% in the isolates from Tokyo Bay, Sagami Bay and the open Pacific Ocean, respectively. The tet(M) positive isolates belonged to 4 orders of bacteria. Bacillales was the most dominant order (121 strains) among tet(M) possessing bacteria, followed by Actinomycetales (three strains), Flavobacteriales (one strain) and Pseudomonadales (one strain). This indicates that tet(M) is present in various bacterial species and suggests that marine sediments are a natural reservoir of the tet(M) gene. Nucleotide sequence of the tet(M) revealed that two genotypes of tet(M) were found in the bacteria. The two genotypes were placed in genetically distant branches of the phylogenetic tree, suggesting that the two tet(M)s have different origins.