Thermally Twistable,Photobendable, Elastically Deformable,and Self‐Healable Soft Crystals

The first example of a smart crystalline material, the 2:1 cocrystal of probenecid and 4,4′‐azopyridine, which responds reversibly to multiple external stimuli (heat, UV light, and mechanical pressure) by twisting, bending, and elastic deformation without fracture is reported. This material is also able to self‐heal on heating and cooling, thereby overcoming the main setbacks of molecular crystals for future applications as crystal actuators. The photo‐ and thermomechanical effects and self‐healing capabilities of the material are rooted in reversible trans–cis isomerization of the azopyridine unit and crystal‐to‐crystal phase transition. Fairly isotropic intermolecular interactions and interlocked crisscrossed molecular packing secure high elasticity of the crystals.     

Volumetric Investigations on Molecular Interactions of Glycine/<Emphasis Type="SmallCaps">l</Emphasis>-alanine in Aqueous Citric Acid Solutions at Different Temperatures

Apparent molar volumes \((\phi_{V})\) of glycine/l-alanine in water and in aqueous citric acid (CA) solutions of varying concentrations, i.e. (0.05, 0.10, 0.20, 0.30, 0.40 and 0.50) mol·kg^?1 were determined from density measurements at temperatures T?=?(288.15, 298.15, 308.15, 310.15 and 318.15) K and at atmospheric pressure. Limiting partial molar volumes \((\phi_V^{\text{o}})\) and their corresponding partial molar volumes of transfer \((\Delta_{\text{tr}} \phi_{V} )\) have been calculated from the \(\phi_{V}\) data. The negative \(\Delta_{\text{tr}} \phi_{V}\) values obtained for glycine/l-alanine from water to aqueous CA solutions indicate the dominance of hydrophilic–hydrophobic/hydrophobic–hydrophilic and hydrophobic–hydrophobic interactions over ion/hydrophilic–dipolar interactions. Further, pair and triplet interaction coefficients, i.e. \((V_{\text{AB}} )\;{\text{and}}\; (V_{\text{ABB}} )\) along with hydration number \((n_{\text{H}} )\) have also been calculated. The effect of temperature on the volumetric properties of glycine/l-alanine in water and in aqueous CA solutions has been determined from the limiting partial molar expansibilities \((\partial \phi_{V}^{\text{o}} /\partial T)_{p}\) and their second-order derivative \((\partial^{2} \phi_{V}^{\text{o}} /\partial T^{2} )_{{P}}\). The apparent specific volumes \((\nu_{\phi} )\) for glycine and l-alanine tend to approach sweet taste behavior both in the presence of water and in aqueous CA solutions. The \(\nu_{\phi}\) values for glycine/l-alanine increase with increase in concentration of CA at all temperatures studied. This reveals that CA helps in enhancing the sweet taste behavior of glycine/l-alanine which also supports the dominance of hydrophobic–hydrophobic interactions.     

Some Geometric Properties of Analytic Functions Involving a New Fractional Operator

In this paper, we introduce and study a new fractional operator and its implications in terms of the Ruscheweyh derivative operator, the Sălăgean operator and a certain fractional differintegral operator. Some geometric properties of the analytic functions involving this operator are derived. We also consider some applications and derive certain corollaries of our main results. Some useful consequences and relationship of certain results with known results are also pointed out.

     

Vibrational spectroscopic investigation of poly(p‐phenylene sulfide)

Poly(p‐phenylene sulfide) (PPS) is an important polymer of engineering interest particularly useful in the electronics and automotive industries. Normal mode analysis including phonon dispersion has been performed to understand completely the vibrational spectra of this polymer. Various characteristic features of the dispersion curves have been reported. Crossing/Repulsion between various pairs of modes at certain phase values have been explained as arising due to internal symmetry in the energy momentum space. The heat capacity is calculated as a function of temperature via density‐of‐states in the range 220–360 K. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2353–2367, 2009     

Vibrational Dynamics,Phonon Dispersion and Specific Heat in Gas Permeable Poly(4-Methyl-2-Pentyne)

Poly(4-methyl-2-pentyne) (PMP) is an amorphous glassy disubstituted acetylene based polymer. The excellent gas-separation and mechanical properties of these polymers have stipulated their use as membrane material for vapor and gas separation. PMP is among the hydrocarbon disubstituted polyacetylenes which have been synthesized to date. This polymer combines excellent gas and vapor permeability with good resistance to organic solvents. As was shown recently, PMP offers promise in the manufacture of nanocomposite membranes for the separation of various hydrocarbon mixtures. It is also of importance as its monomer, 4-methyl- 2-pentyne, can be easily derived from commercial compounds, 4-methyl-2-pentene or methyl isobutyl ketone, produced on a large scale. It is known that PMP exists in cis and trans configurations. Synthetic conditions, e.g., the used catalyst, temperature, solvent etc., of substituted polyacetylenes decide percentage of different configurations (cis or trans). Different geometries of macromolecules can influence the supramolecular structure of the polymer, which primarily defines its properties, such as solubility, permeability, sorption, etc. Qualitative assignments of few bands of IR spectra are reported earlier. We present here, complete normal mode analysis and dispersion curves for PMP using Wilson GF matrix method modified by Higgs using Urey-Bradley force field. Dispersion curves for PMP are drawn and salient features are discussed. Predicted values of specific heat via density-of-states are also reported.     

Structural and spectroscopic studies on 2-pyranones

Experimental methods of infrared, Raman and electronic absorption spectroscopy and DFT calculations using B3LYP functionals and 6-31G** and 6-311++G** basis sets have been used to understand the structural and spectral characteristics of 2-pyranones, 6-phenyl-4-methylsulfanyl-2-oxo-2H-pyran and 6-phenyl-4-methylsulfanyl-2-oxo-2H-pyran-3-carbonitrile in the electronic ground (S₀) and first excited (S₁) states. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). Based on TD-DFT calculations using 6-31+G**5D basis set, an assignment of absorption peaks in the UV–VIS region has been suggested. The S₁ state is found to be a ¹(π,π*) state. A complete vibrational analysis has been attempted on the basis of experimental infrared and Raman spectra and calculated frequency and intensity of the vibrational bands and potential energy distribution over the internal coordinates. Characteristic vibrational bands of the 2-pyranone ring and methylsulfanyl and carbonyl groups have been identified.     

Intriguing H-aggregate and H-dimer formation of coumarin-481 dye in aqueous solution as evidenced from photophysical studies

Photophysical properties of coumarin-481 (C481) dye in aqueous solution show intriguing presence of multiple emitting species. Concentration and wavelength dependent fluorescence decays and time-resolved emission spectra and area-normalized emission spectra suggest the coexistence of dye monomers, dimers, and higher aggregates (mostly trimers) in the solution. Because of the efficient intramolecular charge transfer (ICT) state to twisted intramolecular charge transfer (TICT) state conversion, the dye monomers show very short fluorescence lifetime of ~0.2 ns. Fluorescence lifetimes of dimers (~4.1 ns) and higher aggregates (~1.4 ns) are relatively longer due to steric constrain toward ICT to TICT conversion. Observed results indicate that the emission spectra of the aggregates are substantially blue-shifted compared to monomers, suggesting H-aggregation of the dye in the solution. Temperature-dependent fluorescence decays in water and time-resolved fluorescence results in water-acetonitrile solvent mixtures are also in support of the dye aggregation in the solution. Though dynamic light scattering studies could not recognize the dye aggregates in the solution due to their small size and low concentration, fluorescence up-conversion measurements show a relatively higher decay tail in water than in water-acetonitrile solvent mixture, in agreement with higher dye aggregation in aqueous solution. Time-resolved fluorescence results with structurally related non-TICT dyes, especially those of coumarin-153 dye, are also in accordance with the aggregation behavior of these dyes in aqueous solution. To the best of our knowledge, this is the first report on the aggregation of coumarin dyes in aqueous solution. Present results are important because coumarin dyes are widely used as fluorescent probes in various microheterogeneous systems where water is always a solvent component, and the dye aggregation in these systems, if overlooked, can easily lead to a misinterpretation of the observed results.     

ZIF‐8‐Nanocrystalline Zirconosilicate Integrated Porous Material for the Activation and Utilization of CO2 in Insertion Reactions

The conversion of CO₂ to useful chemicals, especially to atom economical products, is the best approach to utilize an excess of CO₂ present in the atmosphere. In this study, a metal‐organic framework (ZIF‐8) is integrated with nanocrystalline zirconosilicate zeolite to develop an integrated porous catalyst for CO₂ insertion reactions. The catalyst exhibits excellent activity for the CO₂ insertion reaction of epoxide to produce cyclic carbonate in neat condition without the addition of any co‐catalyst. The catalyst is stable and recyclable during the cyclic carbonate synthesis. Further, the catalyst also exhibits very good activity in another CO₂ insertion reaction to produce quinazoline‐2,4(1H, 3H)‐dione.     

An efficacious synthesis of N-1–, C-3–substituted indole derivatives and their antimicrobial studies

A novel series of 11 C-3– and N-1–substituted oxoacetamide indole derivatives were synthesized by reacting with various aromatic amines and alkyl halides. These compounds were characterized by using various spectral techniques, ie, ¹HNMR, ¹HNMR-D₂O, ¹³CNMR, UV, elemental analysis, IR, and mass spectrometery. In vitro, antimicrobial studies of resultant compounds were carried out against two bacterial strains, Pseudomonas aeruginosa and Pseudomonas oryzihabitans using disc plate method. All the tested compounds showed vital efficiency as antimicrobial agents against both the bacterial strains. The results revealed that synthesized indole derivative 2-(1-(3-bromopropyl)-1H-indol-3-yl)-N-(2-nitrophenyl)-2-oxoacetamide displayed the best antimicrobial activity as compared with all other synthesized compounds.