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Isomerization is extensively utilized in the petroleum industry, and this study demonstrates an energy-efficient process utilizing an ionic liquid catalyst. 1-Ethyl-3-methylimidazolium triflate [Emim][TFO] as an ionic liquid was immobilized on solid support Fe/SBA-15. Variants of the catalyst were developed with the Fe constant at 5% and different ratios of ionic liquid. In the catalyst Fe/[Emim][TFO]/SBA-15, the metal Fe was loaded via the impregnation method, and subsequently, the ionic liquid variants Fe/[Emim][TFO](10)/SBA-15, Fe/[Emim][TFO](20)/SBA-15, and Fe/[Emim][TFO](30)/SBA-15 were synthesized. The physical properties of the synthesized catalyst were studied using standard characteristic techniques. The process performance was studied for variants of each parameter, which include temperature, hydrogen flow rate, pressure, and weight hourly space velocity. The iso-products of n -heptane and n -octane were obtained with an appreciable conversion of >90% and a selectivity of >95% with the catalyst Fe/[Emim][TFO](20)/SBA-15 among the other synthesized catalysts. The process yielded a high quantum of iso-products with negligible cracked products at a low temperature of 140 °C. The catalyst Fe/[Emim][TFO](20)/SBA-15 at 140 °C delivered the highest yield of iso-alkanes among the three catalysts. Iso-alkanes are instrumental tools for increasing the octane number of a fuel. This study delivers high iso-alkane content fuel, which can provide the best anti knock capability and enhance fuel efficiency for the life of modern high-powered engines. The results demonstrate a process that is energy-efficient, economic, and environmentally friendly.

This study aimed to investigate the efficacy of a rice straw biosorbent in batch adsorption for the removal of chromium (Cr(VI)) and lead (Pb(II)) heavy-metal ions from wastewater. The biosorbent was chemically synthesized and activated by using concentrated sulfuric acid. The produced biosorbent was then characterized by using Fourier transform infrared (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD) analyses, which provided insights into surface morphology and functional groups. The study examined the effects of pH, rice straw dose, ion concentration, and contact time on metal ion adsorption. Optimal conditions for efficient removal (95.57% for Cr(VI) and 85.68% for Pb(II)) were achieved at a pH of 2.0, a biosorbent dose of 2 g/L, an initial concentration of 20 mg/L, and a contact time of 50 min in synthetic solutions. The isotherms and kinetics model fitting results found that both metal ion adsorption processes were multilayer on the hetero surface of rice straw biosorbent via rate diffusion kinetics. Thermodynamic investigations were conducted, and the results strongly indicate that the adsorption process is endothermic and spontaneous. Notably, the results indicated that the highest desorption rate was achieved by adding 0.3 N HCl to the system., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Four model compounds, nifedipine, indomethacin, felodipine, and ketoconazole, all with nearly identical glass transition temperatures, were chosen to study the effects of thermodynamics and molecular mobility on their crystallization propensities. The time and temperature dependence of the crystallization induction time of each compound was determined by differential scanning calorimetry (DSC) and enabled the generation of their time-temperature-transformation (TTT) diagrams. The relaxation times (τ α ) were measured by dielectric spectroscopy, and the Gibbs free energy (Δ G ) and entropy (Δ S ) difference between the crystalline and amorphous states were obtained by DSC. The temperature dependence of the crystallization induction time (τ 0 ( T )) is a function of the thermodynamic activation barrier and the frequency of "attempted jumps" (1/τ α ( T )) to overcome the barrier. Even though the four model compounds exhibited very similar molecular mobility (relaxation time) over a wide range of temperatures, their crystallization propensities were very different. The observed difference in crystallization propensity was explained in terms of the difference in the thermodynamic barrier, and it is correlated to the empirical relation ( T Δ S 3 )/Δ G 2 .

High magnitudes of permittivity with the permeability of the materials help to absorb electromagnetic waves more efficiently. Snoek's limit directly puts a constraint on the enhancement of the permeability of the material. However, the incorporation of the lossy material may help to enhance the permittivity abruptly. In this study, we prepared a FeSi/SiC composite material with the mechanical ball milling method and investigated its enhancement of the dielectric behavior. The bianisotropic nature was observed along with the phase purity in the morphological studies. The Cole-Cole relaxation mechanisms were observed to validate a complex relaxation mechanism with 10 4 times higher dielectric loss in the composite material. The detection of the Warburg capacitance using the impedance technique sheds new light on the ion diffusion mechanism in the metallic composite materials., Competing Interests: The authors declare no competing financial interest.

Herein, we report the synthesis, self-assembly, and electroluminescence characteristics of a new green-emitting, pseudodiscoid chiral molecule, OXDC, containing an electron-donating stilbene core and an electron-accepting oxadiazole substituent. The helical organization and specific interaction of the chiral pseudodiscoid molecule resulted in the formation of self-assembled nanofibers with a columnar superstructure. Macroscopic chirality was observed in both the liquid-crystalline phases and the self-assembled nanofibers of OXDC, a feature which was absent in the analogous achiral oxadiazole derivative reported earlier [ Sivadas , A. P. ; Supergelation via Purely Aromatic π-π Driven Self-Assembly of Pseudodiscotic Oxadiazole Mesogens . J. Am. Chem. Soc. 2014 , 136 , 5416 - 5423 ]. A high-performance organic light-emitting device was demonstrated using OXDC as the emitting material, with a luminous intensity of 10 115 cd m -2 at 5 V and chromaticity coordinates of (0.32, 0.51).

A series of highly luminescent oxadiazole-based stilbene molecules (OXD4, OXD8, OXD10, and OXD12) exhibiting interesting enantiotropic liquid crystalline and gelation properties have been synthesized and characterized. The molecules possessing longer alkyl substituents, OXD10 and OXD12, possess a pseudodisc shape and are capable of behaving as supergelators in nonpolar solvents, forming self-standing gels with very high thermal and mechanical stability. Notably the self-assembly of these molecules, which do not possess any hydrogen-bonding motifs normally observed in most reported supergelators, is driven purely by π-stacking interactions of the constituent molecules. The d-spacing ratios estimated from XRD analysis of OXD derivatives possessing longer alkyl chains show that the molecules are arranged in a columnar fashion in the mesogens and the self-assembled nanofibers formed in the gelation process.

Star-shaped molecules consisting of a 1,3,4-oxadiazole core derivatized with alkoxy-substituted phenyl ethynylenes, FD12 (dodecyl) and FD16 (hexadecyl) were synthesized. These molecules exhibited enantiotropic columnar mesophases over a wide temperature range, with the liquid crystalline phases exhibiting strong blue fluorescence. On cooling, FD12 transformed into a transparent glass at room temperature wherein the liquid crystalline texture was retained. The glassy film remained stable over a period of one year and exhibited blue luminescence with an absolute quantum yield of 26%. The oxadiazole derivatives formed stable luminescent gels in decane and study of their morphology by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicated formation of interlocked network of self-assembled fibers. X-ray diffraction (XRD) analysis of the xerogel of these derivatives indicated oblique columnar ordering of the molecules within the fibers. The length of the alkyl substituent was observed to have a significant effect on the absorption and fluorescence properties of the gels, which was attributable to the role of the alkyl substituents in controlling the nature of the molecular packing within the self -assembled fibers of the gels.

We have recently mapped the protein interaction network of methicillin-resistant Staphylococcus aureus (MRSA), which revealed its scale-free organization with characteristic presence of highly connected hub proteins that are critical for bacterial survival. Here we report the discovery of inhibitors that are highly potent against one such hub target, staphylococcal pyruvate kinase (PK). Importantly, the developed compounds demonstrate complete selectivity for the bacterial enzyme compared to all human orthologues. The lead 91nM inhibitor IS-130 has been identified through ligand-based cheminformatic exploration of a chemical space around micromolar hits initially generated by experimental screening. The following crystallographic study resulted in identification of a tetrameric MRSA PK structure where IS-130 is bound to the interface between the protein's subunits. This newly described binding pocket is not present in otherwise highly similar human orthologues and can be effectively utilized for selective inhibition of bacterial PK. The following synthetic modifications of IS-130, guided by structure-based molecular modeling, resulted in the development of MRSA PK inhibitors with much improved antimicrobial properties. Considering a notable lack of recent reports on novel antibacterial targets and cognate antibacterial compounds, this study provides a valuable perspective on the development of a new generation of antimicrobials. Equally noteworthy, the results of the current work highlight the importance of rigorous cheminformatics-based exploration of the results of high-throughput experiments.

Aryl pyrimidones are pharmacologically relevant compounds whose optical properties have only been partially explored. We report the synthesis and optical characterization of a series of aryl- and diaryl-2(1H)-pyrimidones. The electronic transitions of these chromophores are modulated by the extent of conjugation between the pendant phenyl ring and the pyrimidone core as well as the presence of electron-donating auxochromes. Monoprotonation of the pyrimidone ring results in large hyperchromic and bathochromic shifts as well as switching of fluorescence making these phenyl pyrimidones of interest as sensory materials., (© 2011 American Chemical Society)

Charge-transfer (CT) complexes composed of a π-electron-poor naphthalene diimide (NDI) derivative combined with a series of π-electron-rich donors were investigated. Solutions of the CT complexes are nonemissive; however, solid-state complexes and aqueous suspensions display emission that is dependent on the energy of the HOMO of the electron donor. Crystallographic analysis of a pyrene-NDI complex reveals columnar packing and a high degree of frontier molecular orbital (FMO) overlap that likely contributes to the observed optical properties. The fluorescent CT particles are utilized as imaging agents; additional luminescent CT complexes may be realized by considering FMO energies and topologies.

The creation of stimuli-responsive materials offers considerable challenges in the area of material science. The use of light as an external stimulus has particular advantages because it can bring about rapid transformations in remote regions in a very precise manner. Naturally occurring photoresponsive systems provide the motivation for developing corresponding artificial systems using molecular self-assembly to address issues such as quantum efficiency, selectivity, and amplification. A practical strategy for developing photoresponsive materials is to utilize molecules that can undergo considerable change in shape on photoisomerization. Although the photoisomerization of polyenes between their linear all-trans isomer and bent cis isomers has been extensively investigated in solution and in organized media because of its relevance to naturally occurring photoresponsive systems, its use in developing artificial photoresponsive systems has not been well explored. This feature article provides an overview of photoresponsive soft materials such as liquid crystals and gels with special emphasis on our recent studies related to the use of the butadiene chromophore for the design of such materials. The role of molecular self-assembly in controlling the photochemical and photophysical properties of these molecules is also discussed.

The syntheses of eight sulfonium compounds with structures related to the naturally occurring pyrrolizidine alkaloid, australine, in which the bridgehead nitrogen atom is replaced by a sulfonium ion, are described. The synthetic strategy relies on the intramolecular attack of a cyclic thioether across a terminal double bond in the presence of a suitable electrophile. We postulate that these compounds, having a permanent positive charge on the sulfur atom, will mimic the highly unstable oxacarbenium ion transition state in a glycosidase-catalyzed hydrolysis reaction. The conformational preferences of these compounds, based on analysis of 1H-1H vicinal coupling constants and 1D-NOESY data, are attributed to both steric and electrostatic interactions. These compounds will be used in the study of structure-activity relationships with glycosidase enzymes.

Three new europium complexes, [Eu(PBI)3.3H2O] (1), [Eu(PBI)3.2TOPO] (2), and [Eu(PBI)3.2TPPO.H2O] (3) (where HPBI, TOPO, and TPPO stand for 3-phenyl-4-benzoyl-5-isoxazolone, tri-n-octylphosphine oxide, and triphenylphosphine oxide, respectively), with different neutral ligands were synthesized and characterized by elemental analysis, Fourier transform infrared, (1)H NMR, thermogravimetric analysis, and photoluminescence (PL) spectroscopy. The coordination geometries of the complexes were calculated using the Sparkle/AM1 (Sparkle Model for the Calculation of Lanthanide Complexes within the Austin Model 1) model. The ligand-Eu3+ energy-transfer rates were calculated in terms of a model of the intramolecular energy-transfer process in lanthanide coordination compounds reported in the literature. The room-temperature PL spectra of the europium(III) complexes are composed of the typical Eu3+ red emission, assigned to transitions between the first excited state (5D0) and the multiplet (7F(0-4)). On the basis of emission spectra and lifetimes of the 5D0-emitting level, the emission quantum efficiency (eta) was determined. The results clearly show that the substitution of water molecules by TOPO leads to greatly enhanced quantum efficiency (i.e., 26% vs 92%) and longer 5D0 lifetimes (250 vs 1160 micros). This can be ascribed to a more efficient ligand-to-metal energy transfer and a less nonradiative 5D0 relaxation process. Judd-Ofelt intensity parameters (Omega2 and Omega4) were determined from the emission spectra for the Eu3+ ion based on the 5D0 --> 7F2 and 5D0 --> 7F4 electronic transitions, respectively, and the 5D0 --> 7F1 magnetic-dipole-allowed transition was taken as the reference. A point to be noted in these results is the relatively high value of the Omega2 intensity parameter for all of the complexes. This may be interpreted as being a consequence of the hypersensitive behavior of the 5D0 --> 7F2 transition. The dynamic coupling mechanism is, therefore, dominant, indicating that the Eu3+ ion is in a highly polarizable chemical environment.

The synthesis of a bicyclic sulfonium ion analogue of a naturally occurring indolizidine alkaloid, swainsonine, in which the bridgehead nitrogen atom is replaced by a sulfonium ion, has been achieved by a multistep synthesis starting from (2S,3S,4R)-2,3-dibenzyloxy-4-formaldehyde-thiolane. The synthetic strategy relies on the intramolecular displacement of a leaving group on a pendant acyclic chain by a cyclic thioether. This bicyclic sulfonium salt provides a candidate with which to further probe the hypothesis that a sulfonium salt carrying a permanent positive charge would be an effective glycosidase inhibitor.

Resolution of the racemic amino alcohol derivatives 1-6 is readily achieved to obtain enantiomerically enriched compounds using chiral 1,1'-bi-2-naphthol and boric acid in solvents such as CH(3)CN, THF, and MeOH. Purification of the diastereomeric mixture 7 has also been carried out following this method. The corresponding intermediate ammonium borate complexes were also characterized by X-ray diffraction methods.