The influence of nanocellulosic fiber,extracted from <Emphasis Type="Italic">Helicteres isora</Emphasis>, on thermal,wetting and viscoelastic properties of poly(butylene succinate) composites

In this study, the thermal, wetting and viscoelastic properties of biodegradable poly(butylene succinate)–isora nanofibril (PBS–INF) composites were investigated. Optical polarizing microscopy showed that incorporating INF in PBS enhanced the number of nucleation sites while also reducing its spherulitic size. Wide-angle X-ray diffraction results showed the influence of INF on the crystal structure of PBS. Dynamic mechanical analysis results revealed increases in storage and loss moduli with increasing INF content. Differential scanning calorimetry analysis showed that incorporating INF facilitated crystallization at higher temperatures. INF slightly enhanced the melting behavior of PBS matrix. Thermogravimetric analysis results demonstrated no definitive change in the thermal stability of PBS upon inclusion of INF. Contact angle studies showed enhancement in the hydrophilic nature of PBS–INF composites. Overall, INF had a positive influence on the thermophysical properties of PBS providing a feasibility for using PBS–INF composites in automotive interiors, food packaging and related applications.     

ZIF‐Induced d‐Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d‐band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg_cat^?1 h^?1 under ambient conditions. The strategy lowers electrocatalyst d‐band position to weaken H adsorption and concurrently creates electron‐deficient sites to kinetically drive NRR by promoting catalyst–N₂ interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44‐fold compared to without ZIF (ca. 1 %). The Pt/Au‐N_ZIF interaction is key to enable strong N₂ adsorption over H atom.     

Information flow due to controlled interference in entangled systems

We point out that controlled quantum interference corresponds to measurement in an incomplete basis and implies a nonlocal transfer of classical information. A test of whether such a generalized measurement is permissible in quantum theory is presented. An erratum to this article is available at .     

Generation and characterization of ionic and neutral [HS-P-OH]<Superscript>+/·</Superscript> and S=P(OH)<Stack><Subscript>2</Subscript><Superscript>+/·</Superscript></Stack> in the Gas Phase by Tandem Mass Spectrometry and Computational Chemistry

Dissociative electron ionization of diethyl dithiophosphate (I) and O,O′-diethyl methylphosphonothioate (II) generates moderately abundant m/z 81 ions of composition [P, O, S, H₂]⁺. From tandem mass spectrometry experiments and theoretical calculations at the B3LYP/6-31G(d,p), G2, and G2 (MP2) levels it is concluded that the majority of the ions have the structure of HS-P-OH⁺ (1a ⁺) and it is separated by high-energy barriers from its isomers P(= S)OH₂⁺ (1b ⁺), P(= O)SH₂⁺ (1c ⁺), HP(= S)OH⁺ (1d ⁺), and HP(= O)SH⁺ (1e ⁺). Low-energy (metastable) ions 1a ⁺ dissociate via losses of H₂O and H₂S to yield m/z 63 (PS⁺) and m/z 47 (PO⁺) product ions, respectively. These reactions involve isomerization of 1a ⁺ into the stable isomers 1b ⁺ and 1c ⁺. Neutralization-reionization experiments confirm the theoretical prediction that radical 1a ^· is a stable species in the gas-phase. Variable-time NR experiments indicated that only a small fraction of metastable 1a ^· radicals dissociate in the 0.4–4.6 μs time window, while most dissociations occurred on a shorter time scale. RRKM calculations were performed to investigate unimolecular dissociation kinetics of 1a ^· which were found to be in agreement with the fragmentation observed in the NR spectrum. The 70-eV electron ionization of (I) and diethyl chlorothiophosphate (III) yields m/z 97 ions, predominantly of the structure S = P(OH)₂⁺ (2a ⁺). This conclusion follows from tandem mass spectrometry experiments and theoretical calculations. The calculations predict that (2a ⁺) is separated by high-energy barriers from its isomers O = P(SH)OH⁺ (2b ⁺), S = P(= O)OH₂⁺ (2c ⁺), and O = P(= O)SH₂⁺ (2d ⁺). Neutralization-reionization experiments confirmed that 2a ^· radical is a kinetically stable species on the time scale of up to 5 μs, which is in agreement with ab initio calculations. However, owing to a mismatch of Franck-Condon factors a large fraction of 2a ^· dissociates by loss of SH^· yielding O=P-OH.     

A mild and efficient acetylation of alcohols, phenols and amines with acetic anhydride using La(NO3)3·6H2O as a catalyst under solvent-free conditions

A wide variety of alcohols, phenols and amines are efficiently and selectively converted into the corresponding acetates by treatment with acetic anhydride in the presence of catalytic amounts of La(NO₃)₃·6H₂O under solvent-free conditions at room temperature. The method is compatible with acid sensitive hydroxyl protecting groups such as TBDMS, THP, OBz, OBn, Boc and some isopropylidenes and offers excellent yields of the mono acetates of 1,3-, 1,4- and 1,5-diols.     

Sulfonic acid–functionalized Wang resin (Wang-OSO3H) as polymeric acidic catalyst for the ecofriendly multicomponent synthesis of polyhydroquinolines via Hantzsch condensation

An efficient and green approach has been developed for the synthesis of polyhydroquinoline derivatives via Hantzsch condensation reaction directly from corresponding substituted aromatic and aliphatic aldehydes, β-keto compounds, active methylene compounds, and ammonium chloride using recyclable polymer-supported sulfonic acid catalyst under aqueous conditions. Environmental acceptability, operational simplicity, low cost, excellent functional group compatibility, and high yields are the important features of this protocol.     

Boron Nitride Nanosheets Improve Sensitivity and Reusability of Surface‐Enhanced Raman Spectroscopy

Surface enhanced Raman spectroscopy (SERS) is a useful multidisciplinary analytic technique. However, it is still a challenge to produce SERS substrates that are highly sensitive, reproducible, stable, reusable, and scalable. Herein, we demonstrate that atomically thin boron nitride (BN) nanosheets have many unique and desirable properties to help solve this challenge. The synergic effect of the atomic thickness, high flexibility, stronger surface adsorption capability, electrical insulation, impermeability, high thermal and chemical stability of BN nanosheets can increase the Raman sensitivity by up to two orders, and in the meantime attain long‐term stability and extraordinary reusability not achievable by other materials. These advances will greatly facilitate the wider use of SERS in many fields.     

Molecular design of corrole‐based D‐π‐A sensitizers for dye‐sensitized solar cell applications

First principles calculations based on density functional theory (DFT) have been performed to design a new set of donor‐corrole‐bridge‐acceptor type systems based on the gallium corroles for dye‐sensitized solar cell applications. The design strategy for these systems is based on the benchmark studies done on the experimentally tested aluminum, gallium, and tin metallocorroles. Unfortunately, corrole analogues display poor light to current conversion efficiencies in spite of their desirable photophysical properties. Thus, improving the efficiency of corrole analogues has become a major challenge and ways to identify solutions to this is of outstanding fundamental importance. This study shows the lack of charge directionality toward anchoring group as plausible reason for the poor efficiencies of reported corrole systems, which enabled us to fine‐tune the electronic and optical properties of new D‐π‐A type systems, COR1‐COR4. The molecular geometries, electronic structure, and binding orientation of these systems on TiO₂ surface were investigated using DFT, TD‐DFT, and PBC methods. When compared with the reported corroles, COR1‐COR4 have a smaller band gaps, red‐shifted absorption spectra with higher extinction coefficients (10⁵ M^?1 cm^?1) and improved nonlinear optical properties. Importantly, results revealed that these dyes bind with two‐arm mode to TiO₂ surface and the density of states of the dye@TiO₂ elucidate strong coupling between the dyes and TiO₂ surface. We anticipate that the unique photophysical properties of these sensitizers will trigger the experimental efforts to yield a new generation of sensitizers based on corrole macrocyle. © 2015 Wiley Periodicals, Inc.