Role of superheated water in the dissolution and perturbation of hydrogen bonding in the crystalline lattice of polyamide 4,6

Here, we demonstrate that water, in the superheated state, is a solvent for polyamide 4,6 (PA4,6) and that the water molecules can strongly influence hydrogen bonding. In the presence of superheated water, the melting temperature of PA4,6 can be suppressed by nearly 100 degrees C. The depression in the melting temperature follows the Flory-Huggins principle. The instantaneous dissolution of the polymer hardly influences the molar mass of the polymer. However, if the polymer is retained in solution above the dissolution temperature for more than 10 min, hydrolysis occurs. These findings suggest that the dissolution of the aliphatic polymer in superheated water is mainly a physical process as opposed to a chemical process. Time resolved X-ray studies show that the dissolution occurs prior to the Brill transition temperature, as reported earlier. Crystals grown from the water solution show a lath-like morphology with interchain and intersheet distances that are similar to the distances obtained for crystals grown from other known solvents. Electron diffraction further confirmed that the crystals grown from superheated water are single crystals, where the chains are perpendicular to the ab-plane. SAXS performed on dried sedimented water grown single crystals showed a lamellar thickness of 6 nm. The lamellar thickness is in accordance with other reported studies on PA4,6, confirming that the single crystals incorporate four repeat units between re-entrant folds with an amide group incorporated in the tight fold. Solid state NMR studies performed on mats of these single crystals showed two different mobilities of the proton associated with the amide groups: a higher mobility linked to the amide protons in the fold and a reduced mobility of the hydrogen bonded amide protons within the crystal. Additionally, the solid state NMR studies on the dried water crystallized single crystals show the presence of water molecule(s) in the vicinity of the amide groups. This was confirmed by infrared studies that conclusively demonstrated the appearance of two new bands arising due to the binding of a water molecule in the vicinity of the amide group (i.e., NH3(+) and COO(-) bands that disappear upon heating at approximately 200 degrees C). Additionally, DSC traces of the water crystallized PA4,6 show an exothermic event in the same temperature region (i.e., in the vicinity of the Brill transition temperature, where the bound water exits from the lattice). Furthermore, this event was corroborated by TGA data.     

Colon targeted delivery systems of metronidazole based on osmotic technology: development and evaluation

Colon targeted delivery systems of metronidazole (MTZ) based on osmotic technology were developed. The developed systems consisted of osmotic core (drug, osmotic agent and wicking agent), coated with semipermeable membrane (SPM) containing guar gum as pore former, coated core were then further coated with enteric coating to protect the system from acidic environment of stomach. The effect of various formulation variables namely the level of wicking agent (sodium lauryl sulphate), osmotic agent in the osmotic core, the level of pore former (guar gum) in SPM, and the thickness of SPM, were studied on physical parameters and drug release characteristics of developed formulations. MTZ release was inversely proportional to SPM thickness, but directly related to the level of pore former, wicking agent and osmotic agent. On the other hand burst strength of the exhausted shells was decreased with the increase in level of pore former in the membrane but increased with the increase in the thickness of SPM. The drug release from the developed formulations was independent of pH, and agitation intensity, but dependent on the osmotic pressure of the release media. The thickness of enteric coating could prevent formation of delivery pores before contact with simulated colonic fluid, but had no effect on drug release. Result of SEM studies showed the formation of in-situ delivery pores in the membrane from where the drug release occurred, and the number of pores formed were directly related to the initial level of pore former (guar gum) in SPM. The manufacturing procedure was found to be reproducible and formulations were found to be stable during 3 months of accelerated stability studies.     

Betterment in EDXRF analytical results for compositional characterization of mixed uranium thorium oxide samples with bead specimens compared with pressed pellet specimens

A comparative study on the energy dispersive X‐ray fluorescence analytical results of uranium determinations, in uranium and uranium–thorium mixed oxides, using specimens in the form of fused beads and pressed pellets, has been made. It was observed that in case of fusion bead specimens, the intensity of the analyte lines was approximately 1.6 times of that observed in pellet specimens under identical instrumental conditions. In case of uranium oxide samples, the analytical results with bead specimens were slightly better compared with the pellet specimens. However, in case of the uranium–thorium oxide mixtures, the average precision obtained with bead specimen was significantly better (1%, 1 s) in comparison with that achieved using pellet specimens (7%, 1 s). This difference may be due to the hardness of thorium oxide compared with uranium oxide, which affects the homogeneity of the pellet specimens prepared. In fusion bead method of sample preparation, even highly refractory material like ThO₂ forms uniform glass beads. Addition of internal standard further improves the analytical results, with reduction in the percent deviation of energy dispersive X‐ray fluorescence results from the expected values to 3% from 7% compared with that obtained using without internal standard. The fusion bead method of sample preparation will be very useful for characterization of sintered (U,Th)O₂ pellets, which are highly refractory and difficult to dissolve. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis,Crystal Structure,and Electrochemical Properties of a Simple Magnesium Electrolyte for Magnesium/Sulfur Batteries

Most simple magnesium salts tend to passivate the Mg metal surface too quickly to function as electrolytes for Mg batteries. In the present work, an electroactive salt [Mg(THF)₆][AlCl₄]₂ was synthesized and structurally characterized. The Mg electrolyte based on this simple mononuclear salt showed a high Mg cycling efficiency, good anodic stability (2.5 V vs. Mg), and high ionic conductivity (8.5 mS cm^?1). Magnesium/sulfur cells employing the as‐prepared electrolyte exhibited good cycling performance over 20 cycles in the range of 0.3–2.6 V, thus indicating an electrochemically reversible conversion of S to MgS without severe passivation of the Mg metal electrode surface.     

New iron(III) complexes with thiosemicarbazones derived from 5-methyl-3-formylpyrazole

New iron(III) complexes of 5-methyl-3-formylpyrazole thiosemicarbazone (HMPzTS) and 5-methyl-3-formylpyrazole-4-phenylthiosemicarbazone (HMPzPTS), namely [Fe(MPzTS)₂]X and [Fe(MPzPTS)₂]X respectively, where X=Cl, NO₃, SCN and ClO₄, have been synthesised and physico-chemically characterised by magnetic measurements (polycrystalline state), electronic, i.r., e.s.r. and Mössbauer spectra. All are cationic complexes containing two monoprotonic tridentate ligands with NNS donor sites and an anionic counterpart; they behave as 1:1 electrolytes in MeOH/DMF. Coordination to central iron(III) via the pyrazolyl nitrogen (²N), the azomethine nitrogen and the thiolato sulphur atom is confirmed in the complexes from i.r. data. E.s.r. data (RT & LNT) reveal the presence of a spin-paired iron(III) cation with d² _xyd² _yzd¹ _xy configuration. The ⁵⁷Fe Mössbauer spectral data (RT) are commensurate with the presence of two iron(III) spin states, the percentage of each being dependent upon the counterion of the species.     

Review of Building Integrated Photovoltaics System for Electric Vehicle Charging

The transition to sustainable transportation has fueled the need for innovative electric vehicle (EV) charging solutions. Building Integrated Photovoltaics (BIPV) systems have emerged as a promising technology that combines renewable energy generation with the infra-structure of buildings. This paper comprehensively reviews the BIPV system for EV charging, focusing on its technology, application, and performance. The review identifies the gaps in the existing literature, emphasizing the need for a thorough examination of BIPV systems in the context of EV charging. A detailed review of BIPV technology and its application in EV charging is presented, covering aspects such as the generation of solar cell technology, BIPV system installation, design options and influencing factors. Furthermore, the review examines the performance of BIPV systems for EV charging, focusing on energy, economic, and environmental parameters and their comparison with previous studies. Additionally, the paper explores current trends in energy management for BIPV and EV charging, highlighting the need for effective integration and recommending strategies to optimize energy utilization. Combining BIPV with EV charging provides a promising approach to power EV chargers, enhances building energy efficiency, optimizes the building space, reduces energy losses, and decreases grid dependence. Utilizing BIPV-generated electricity for EV charging provides electricity and fuel savings, offers financial incentives, and increases the market value of the building infrastructure. It significantly lowers greenhouse gas emissions associated with grid and vehicle emissions. It creates a closed-loop circular economic system where energy is produced, consumed, and stored within the building. The paper underscores the importance of effective integration between Building Integrated Photovoltaics (BIPV) and Electric Vehicle (EV) charging, emphasizing the necessity of innovative grid technologies, energy storage solutions, and demand-response energy management strategies to overcome diverse challenges. Overall, the study contributes to the knowledge of BIPV systems for EV charging by presenting practical energy management, effectiveness and sustainability implications. It serves as a valuable resource for researchers, practitioners, and policymakers working towards sustainable transportation and energy systems.     

Modeling force-induced bio-polymer unfolding

We study the conformations of polymer chains in a poor solvent, with and without bending rigidity, by means of a simple statistical mechanics model. This model can be exactly solved for chains of length up to N = 55 using exact enumeration techniques. We analyze in detail the differences between the constant force and constant distance ensembles for large but finite N. At low temperatures, and in the constant force ensemble, the force–extension curve shows multiple plateaus (intermediate states), in contrast with the abrupt transition to an extended state prevailing in the N → ∞ limit. In the constant distance ensemble, the same curve provides a unified response to pulling and compressing forces, and agrees qualitatively with recent experimental results. We identify a cross-over length, proportional to N, below which the critical force of unfolding decreases with temperature, while above, it increases with temperature. Finally, the force–extension curve for stiff chains exhibits “saw-tooth” like behavior, as observed in protein unfolding experiments.     

An efficient, rapid, and regioselective bromination of anilines and phenols with 1-butyl-3-methylpyridinium tribromide as a new reagent/solvent under mild conditions

1-Butyl-3-methylpyridinium tribromide, [BMPy]Br₃ proves to be a highly efficient, regioselective reagent/solvent for nuclear bromination of various anilines and phenols. The synthesis and characterization of the room temperature ionic liquid [BMPy]Br₃ (2) is described. The bromination was carried out in the absence of organic solvents and in most cases the only extraction solvent needed was water. The spent 1-butyl-3-methylpyridinium bromide (1) was easily recycled.     

Tetrabutylammonium bromide (TBAB): a neutral and efficient catalyst for the synthesis of biscoumarin and 3,4-dihydropyrano[c]chromene derivatives in water and solvent-free conditions

A simple, efficient and ecofriendly procedure has been developed using tetrabutylammonium bromide as catalyst for the synthesis of biscoumarin and dihydropyrano[c]chromene derivatives in water and solvent-free neat conditions. The present methodology offers several advantages such as excellent yields, short reaction time and environmentally benign milder reaction conditions.