Supramolecular Synthons in Designing Low Molecular Mass Gelling Agents: L‐Amino Acid Methyl Ester Cinnamate Salts and their Anti‐Solvent‐Induced Instant Gelation

Easy access to a class of chiral gelators has been achieved by exploiting primary ammonium monocarboxylate ( PAM ), a supramolecular synthon. A combinatorial library comprising of 16 salts, derived from 5 l ‐amino acid methyl esters and 4 cinnamic acid derivatives, has been prepared and scanned for gelation. Remarkably, 14 out of 16 salts prepared (87.5 % of the salts) show moderate to good gelation abilities with various solvents, including commercial fuels, such as petrol. Anti‐solvent induced instant gelation at room temperature has been achieved in all the gelator salts, indicating that the gelation process is indeed an aborted crystallization phenomenon. Rheology, optical and scanning electron microscopy, small angle neutron scattering, and X‐ray powder diffraction have been used to characterize the gels. A structure‐property correlation has been attempted, based on these data, in addition to the single‐crystal structures of 5 gelator salts. Analysis of the FT‐IR and ¹H NMR spectroscopy data reveals that some of these salts can be used as supramolecular containers for the slow release of certain pest sex pheromones. The present study clearly demonstrates the merit of crystal engineering and the supramolecular synthon approach in designing new materials with multiple properties.     

Boundary element method for wave trapping by a multi-layered trapezoidal breakwater near a sloping rigid wall

This study examines the multiple layers in a rubble mound breakwater and their effect on reflection and dissipation of incoming ocean waves. The numerical model is developed using multi-domain boundary element method for oblique water wave trapping near a sloping wall by a multi-layered trapezoidal porous structure, which is utilized to model armour, filter and core layers while examining the hydrodynamics in different configurations. Both, the constant element and linear element approaches to boundary element method are discussed. The cases of bottom-standing porous structures as being submerged and fully extended are considered. The wave hydrodynamics over the structure is described by the reflection and dissipation coefficients along with the forces acting on the sloping wall, and is influenced by wave and structural parametrics of the system. The influence of armour layer in different configurations is highlighted for various structural and wave parameters.

     

Theoretical study of excited state proton transfer in pyrrole-2-carboxylic acid

Pyrrole 2-carboxylic acid (PCA) shows dual emission (310 nm and 430 nm) in water on photo-excitation, which indicates that more than one species is in the excited state. This paper reports on the quantum chemical analysis of pyrrole 2-carboxylic acid (PCA) in the light of a possible excited state proton transfer. Dipole moment, excited state energy and findings in molecular orbital calculations (HOMO, LUMO) establish that PCA is a likely candidate for transfer of a proton from the pyrrole moiety to the C=O of carboxylic moiety (possible zwitterionic form) in the excited state. Overall, the computed predicted results of intramolecular and intermolecular excited state proton transfer corroborates the experimental results.     

Vacuum Ultraviolet Absorption Spectrum of Difluoromethane Reinvestigated

The vacuum ultraviolet (VUV) absorption spectrum of difluoromethane (CH₂F₂) was studied using synchrotron radiation from the storage ring Indus-1, Indore, India. Spectra were recorded in the spectral region 1050–1500 Å (～8.3–11.8 eV) at a resolution of 1.5 Å. Three absorption band systems were observed in this region. Overall features observed are in good agreement with previously published work. Some discrepancies in assignments of the observed vibronic bands carried out by previous workers have been resolved. The observed bands have been classified in terms of Rydberg series.     

Doubling Förster Resonance Energy Transfer Efficiency in Proteins with Extrinsic Thioamide Probes: Implications for Thiomodified Nucleobases

Designing a potential protein–ligand pair is pivotal, not only to track the protein structure dynamics, but also to assist in an atomistic understanding of drug delivery. Herein, the potential of a small model thioamide probe being used to study albumin proteins is reported. By monitoring the Förster resonance energy transfer (FRET) dynamics with the help of fluorescence spectroscopic techniques, a twofold enhancement in the FRET efficiency of 2-thiopyridone (2TPY), relative to that of its amide analogue, is observed. Molecular dynamics simulations depict the relative position of the free energy minimum to be quite stable in the case of 2TPY through noncovalent interactions with sulfur, which help to enhance the FRET efficiency. Finally, its application is shown by pairing thiouracils with protein. It is found that the site-selective sulfur atom substitution approach and noncovalent interactions with sulfur can substantially enhance the FRET efficiency, which could be a potential avenue to explore in the design of FRET probes to study the structure and dynamics of biomolecules.     

A first principle study of hydrogen storage in titanium-doped small carbon clusters (C2nTin,n = 2–6)

Structural Chemistry - Hydrogen storage in Ti-doped small carbon clusters, C2nTin (n = 2–6), has been studied using density functional theory. Using the principle of maximum hardness (η)...     

Essential Oils as Novel Anthelmintic Drug Candidates

Helminths, with an estimated 1.5 billion annual global infections, are one of the major health challenges worldwide. The current strategy of the World Health Organization to prevent helminth infection includes increasing hygienic awareness, providing better sanitation and preventative anthelmintic drug therapy in vulnerable populations. Nowadays, anthelmintic drugs are used heavily in livestock, both in case of infection and as a preventative measure. However, this has led to the development of resistance against several of the most common drugs, such as levamisole, ivermectin and thiabendazole. As many as 70% of the livestock in developed countries now has helminths that are drug resistant, and multiple resistance is common. Because of this, novel anthelmintics are urgently needed to help combat large-scale production losses. Prior to this review, no comprehensive review of the anthelmintic effects of essential oils and their components existed. Multiple review articles have been published on the uses of a single plant and its extracts that only briefly touch upon their anthelmintic activity. This review aims to provide a detailed overview of essential oils and their components as anthelmintic treatment against a wider variety of helminths.     

Neocinnamomum caudatum Essential Oil Ameliorates Lipopolysaccharide-Induced Inflammation and Oxidative Stress in RAW 264.7 Cells by Inhibiting NF-κB Activation and ROS Production

Neocinnamomum caudatum (Lauraceae) plant is used in the traditional system of medicine and is considered a potential source of edible fruits, spices, flavoring agents and biodiesel. The leaves, bark and roots of the species are used by local communities for the treatment of inflammatory responses, such as allergies, sinusitis and urinary tract infections. However, there is no scientific evidence to support the molecular mechanism through which this plant exerts its anti-inflammatory effect. The aim of the current research was to characterize the chemical constituents of bark (NCB) and leaf (NCL) essential oil of N. caudatum and to elucidate its anti-inflammatory action in lipopolysaccharide (LPS)-treated RAW 264.7 cells. Essential oils extracted by hydrodistillation were further subjected to gas chromatography mass spectrometry (GC-MS) analysis. The major constituents in bark essential oil identified as β-pinene (13.11%), α-cadinol (11.18%) and α-pinene (10.99%), whereas leaf essential oil was found to be rich in β-pinene (45.21%), myrcene (9.97%) and α-pinene (9.27%). Treatment with NCB and NCL at a concentration of 25 µg/mL exerted significant anti-inflammatory activity by significantly reducing LPS-triggered nitric oxide (NO) production to 45.86% and 61.64%, respectively, compared to the LPS-treated group. In the LPS-treated group, the production of proinflammatory cytokines, such as tumor necrosis factor (TNF)-α, interleukin (IL)-6 and IL-1β, decreased after treatment with essential oil, alleviating the mRNA levels of inducible nitric oxide synthase (iNOS) and cyclooxygenase (COX)-2. The essential oil also inhibited the production of intracellular ROS and attenuated the depletion of mitochondrial membrane potential in a concentration-dependent manner. Pretreatment with NCB also reduced nuclear factor kappa-B (NF-κB)/p65 translocation and elevated the levels of endogenous antioxidant enzymes in LPS-induced macrophages. The present findings, for the first time, demonstrate the anti-inflammatory potential of both bark and leaf essential oils of N. caudatum. The bark essential oil exhibited a significantly more important anti-inflammatory effect than the leaf essential oil and could be used as a potential therapeutic agent for the treatment of inflammatory diseases.     

GC-MS and GC-FTIR identification of volatile radiolytic products in water-nitrobenzene-carbon tetrachloride two phase systems

Various volatile products formed in the -radiolysis of water-nitrobenzene-carbon tetrachloride two phase systems have been identified using GC-MS and GC-FTIR systems. The conditions for the separation of the products are described in detail. It was found that product formation is dependent on the composition of the systems. In case when the volume ratio of carbon tetrachloride is higher, chlorobenzene appears to be one of the major radiolytic products. This means that substitution of the nitro group by chlorine atom occurs in the presence of water. Substitution of the nitro group and hydrogen atom by chlorine atom and/or HO free radical is also observed, depending on the composition of the mixture. Formation of phenyl isocyanate is proposed to be the result of interaction of dichlorocarbene and nitrobenzene. The mechanism of some main product formation is described briefly.This paper constitutes part of the Ph.D. thesis of M. K. SAHOO and was presented at the 9th Czecho-Slovak Spectroscopic Conference with International Participation, eské Budjovice, C.S.F.R., June 22–24, 1992.     

3 + 2]-cycloaddition of nonstabilized azomethine ylides. 10. An efficient strategy for the construction of x-Azatricyclo[m.n.0. 0

Various new structural entities related to x-azatricyclo[m.n.0. 0(a)()(,)(b)()]alkanes are constructed by the intramolecular [3 + 2] dipolar cycloaddition of nonstabilized cyclic azomethine ylides. The ylide is generated by the sequential double desilylation of N-alkyl alpha,alpha'-bis(trimethylsilyl)cyclic amines using Ag(I)F as a one-electron oxidant.