Polyglycerol‐Based Copper Chelators for the Transport and Release of Copper Ions in Biological Environments

Here, the synthesis and characterization of three improved nanosystems is presented based on amino functionalized hyperbranched polyglycerol (hPG; M_w = 16.8 kDa) as potential copper(ii ) chelators. The ligands, N‐methyl‐N‐picolylglycine amide, 2,6‐pyridine dicarboxylic acid monoamide, and cyclam tetraacetic acid (TETA) monoamide, are covalently attached to the polymer with amide bonds. In this paper, the Cu(ii ) loading capacity, the stability of the Cu(ii )‐loaded carriers at different pHs, with competing ligands and in human serum, as well as the transport of Cu(ii ) in biological systems are investigated. For the first time, a different cytotoxicity of functionalized polymer nanoparticles with and without Cu(ii ) is observed. The cyclam‐based carrier combines the highest loading capacity (29 Cu ions/nanoparticle), best stability with respect to pH and EDTA (45% remaining Cu after 24 h), lowest cytotoxicity (IC₅₀ > 100 × 10^?6m (unloaded), 1500 × 10^?6m Cu(ii ); Cu:carrier 29:1), and the highest stability in human serum.

     

Mesoporous Porphyrin-Silica Nanocomposite as Solid Acid Catalyst for High Yield Synthesis of HMF in Water

Solid acid catalysts occupy a special class in heterogeneous catalysis for their efficiency in eco-friendly conversion of biomass into demanding chemicals. We synthesized porphyrin containing porous organic polymers (PorPOPs) using colloidal silica as a support. Post-modification with chlorosulfonic acid enabled sulfonic acid functionalization, and the resulting material (PorPOPS) showed excellent activity and durability for the conversion of fructose to 5-hydroxymethyl furfural (HMF) in green solvent water. PorPOPS composite was characterized by N₂ sorption, FTIR, TGA, CHNS, FESEM, TEM and XPS techniques, justifying the successful synthesis of organic networks and the grafting of sulfonic acid sites (5 wt%). Furthermore, a high surface area (260 m²/g) and the presence of distinct mesopores of ~15 nm were distinctly different from the porphyrin containing sulfonated porous organic polymer (FePOP-1S). Surprisingly the hybrid PorPOPS showed an excellent yield of HMF (85%) and high selectivity (>90%) in water as compared to microporous pristine-FePOP-1S (yield of HMF = 35%). This research demonstrates the requirement of organic modification on silica surfaces to tailor the activity and selectivity of the catalysts. We foresee that this research may inspire further applications of biomass conversion in water in future environmental research.     

Spatial trends in uranium distribution in groundwaters of Southwest Punjab,India - A hydrochemical perspective

A hydrochemical study was undertaken in uranium impacted districts of southwest Punjab for evaluating the spatial and vertical trends as well as correlations with other hydrochemical parameters. Results infer that U is present in all samples (12.2–621 µg l⁻¹) and 90% are contaminated. Contour diagram depicts contamination in entire region excepting some pockets in central part of the study area. Shallow zones (<50 m bgl) show higher U compared to deeper ones. Hydrochemistry infers a common source of U for both shallow and deep zones and alkalinity as the governing factor for U mobilization from the sediments.

     

Synthesis and evaluation of novel tetrapropoxycalix[4]arene enones and cinnamates for protection from ultraviolet radiation

A series of novel calix[4]arene enones (5-7) and cinnamates (12-14) have been synthesized and evaluated for ensuring protection from ultraviolet radiation (UVR). Spectroscopic analyses has revealed that compound 6 absorbs ultraviolet radiations between 280 and 350 nm with an absorption maximum at 312 nm. Its molar absorption coefficient (ε) (>5 × 10(4)M(-1)cm(-1)) and bandwidth are larger than those for the commercially used sun protectants (oxybenzone (OB), 2-ethylhexyl 4-methoxycinnamate (OMC) and avobenzone). The in vitro Sun Protection Factor (SPF) measurement revealed an SPF of 5.2 at 2% concentration of 6 in home made emulsion formulations while combination of 2% each of 6 and OMC gave an SPF of 8.8. Lower sun protection seems to be compensated by significant protection from more harmful UVA radiations (UVA/UVB absorbance ratio of 0.62).     

Solvent degradation of nylon-6 and its effect on fiber morphology of electrospun mats

In this work, we studied solvent-induced polymer degradation and its effect on the morphology of electrospun fibers. Nylon-6 in formic acid solvent was allowed to degrade by simply allowing it to stand for a long time, and nanofibrous mats were fabricated by taking a fraction of this solution at different time intervals via electrospinning under the same electrospinning conditions. FE-SEM images of the mats indicate that the nanofiber diameter gradually decreased with the standing time of solution, and large numbers of true nano fibers (<50 nm in diameter) were obtained. MALDI-TOF analysis revealed that the formation of low-molecular weight ions was caused by solvent degradation. FT-IR, DSC, XRD, and TGA analyses of electrospun mats showed that some physical properties, such as bond strength, crystallinity, and thermal stability also depended on solvent degradation. The obtained sub-nanofibrous mat has potential applications in different bioengineering fields.     

Steady state and time-resolved fluorescence study of isoquinoline: reinvestigation of excited state proton transfer

In the present work we report some hitherto unnoticed features in the steady state and time-resolved measurements of isoquinoline in water and trifluoroethanol (TFE). Absorption spectra reveal that in water, neutrals as well cationic species are present. Emission spectrum shows structured features at shorter wavelengths accompanied with a broad band around 375 nm, which correspond to neutrals and cations respectively. However, time-resolved data indicate that protonation does not take place in the excited state in water. On the contrary, in stronger hydrogen bonding solvent TFE, distribution of decay components is observed and at longer wavelengths a small rise time is present. This is ascribed to neutral and cation-like species present in the ground as well as in the excited state. The difference in the results is explained in terms of different excited state potential energy surfaces for water and TFE; particularly, the presence of a rather small barrier for protonation in case of TFE.     

Composition and antibacterial activity of essential oil from Scutellaria grossa Wall ex Benth

The chemical composition of the steam volatile oil of the whole aerial part of Scutellaria grossa Wall ex Benth. (Lamiaceae), obtained by steam distillation, has been analysed by capillary GC and GC-MS. The oil was found to be rich in oxygenated monoterpenes (88.6%). A total of 50 constituents were identified, representing 94.4% of the total oil composition. Linalool (37.0%) and 1-octen-3-ol (32.0%) were found to be the principal constituents. The antibacterial activity of the oil was determined against 10 bacterial strains by measuring the growth inhibitory zones. The oil showed significant antibacterial activity against Gram-positive bacteria, Bacillus subtilis and Enterococcus faecalis, and the Gram-negative, Klebsiella pneumoniae and Salmonella enterica enterica. A minimum inhibitory concentration of 31.25?μL mL(-1) was observed against E. faecalis.     

Enhanced optoelectronic properties with aromatic bridges: A computational study on N-methyl pyridinium and phenolate types of push-pull zwitterions

A series of zwitterions with varying bridges, connecting N-methyl pyridinium acceptor, with phenolate donor, are investigated using various methodologies like, HF, B3LYP, CAM-B3LYP and ωB97xD. In this systematic study effects of various mono aromatic rings as bridges, on the response properties like, the dipole moments (μ), polarizabilities (α), hyperpolarizabilities (β) and adiabatic absorptions were analyzed using CPHF and TDDFT (or TDHF) theories. Compared to many traditional bridges, as well as without a bridge, enhanced nonlinear optical (2ND order NLO) responses were observed for these aromatically bridged zwitterions (with benzene ring as bridge ~5.3 times and ~7.9 times enhanced hyperpolarizabilities were observed compared to either the ethylene bridge or without any bridge cases, respectively). Also, many significant differences and large enhancements in response properties were observed compared to our earlier works on non-zwitterionic system (~4.3 times enhanced hyperpolarizability—benzene as bridge case). For some bridge cases, 10- to 15-fold enhanced hyperpolarizabilities were observed compared to without any bridge case. This work reports a class of non-TICT chromophores, promoting bridge aromaticity control on structure–property correlation, as a suitable and efficient chromophore design strategy to create a wide range of function molecular chromophores. Also, unidirectional natures of response properties and large dipole moments can make these zwitterions suitable 1D-molecular materials for various contemporary technological applications, as poled polymer-based materials.     

Photonic-chip-based tunable slow and fast light via stimulated Brillouin scattering

We report the first (to our knowledge) demonstration of photonic chip based tunable slow and fast light via stimulated Brillouin scattering. Slow, fast, and negative group velocities were observed in a 7 cm long chalcogenide (As(2)S(3)) rib waveguide with a group index change ranging from ~-44 to +130, which results in a maximum delay of ~23 ns at a relatively low gain of ~23 dB. Demonstration of large tunable delays in a chip scale device opens up applications such as frequency sensing and true-time delay for a phased array antenna, where integration and delays ~10 ns are highly desirable.     

Simultaneous synthesis of TiO2 microrods in situ decorated with Ag nanoparticles and their bactericidal efficiency

In this study, we report a simple and cost-effective method for in situ decoration of Ag NPs onto nanoporous TiO₂ microrods by one medium (ethylene glycol) that can produce two different morphologies. In order to investigate the morphology, phase composition, crystalline structure, and chemical state (valency) of samples before and after annealing in air at different temperatures, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were performed. The present results show that the size, morphology and crystallinity of both Ag NPs and TiO₂ microrod substrate depend on the post-annealing treatment temperatures. The annealed Ag–TiO₂ NP/microrod composites show large inhibition zones against E. coli bacteria. The obtained Ag–TiO₂ composites have the potential for use as a novel antibacterial material and in water treatment applications.