Disposable Screen‐Printed Edge Band Ultramicroelectrodes for Use as Nitric Oxide Gas Sensor in Designing an Easily Applicable Method for Real Sample Analysis of Nitrite with Superior Selectivity and Sensitivity

We report here an easily applicable method for the quantification of nitrite (NO₂^?) in real samples. This approach simplified the two steps of sample preparation and detection into a 2‐in‐1 single step process. Samples were digested in sulfuric acid and the as‐generated nitric oxide (NO) was detected by an electrochemical sensor in the gas phase. It eliminated almost all of the interferents in the solution phase and hence resulted in a highly selective determination of nitrite suitable for food samples with complicated matrix. We successfully demonstrated the determination of nitrite in sausage and vegetables and further validated the results with an AOAC official reference method.     

Elastic piezoelectric aerogels from isotropic and directionally ice-templated cellulose nanocrystals: comparison of structure and energy harvesting

We report the preparation of highly compressible and elastic piezoelectric aerogels of carboxylated cellulose nanocrystals (CNCs). Aqueous CNC dispersions containing polyethyleneimine and crosslinker were frozen isotropically to yield isotropic aerogels, while oriented aerogels were prepared by directional freezing. These aerogels were highly flexible and porous (~?85% void fraction), exhibiting greater than 90% recovery at 50% compressive strain even after 100 compression–decompression cycles. Since such aerogels with low bulk modulus and high anisotropy would be an ideal platform for leveraging the piezoelectric properties of CNCs, we used them to prepare piezoelectric nanogenerator devices and determined their energy transduction behavior. Anisotropic aerogels led to an enhanced open-circuit voltage of 840 mV (at ~?8 N applied force), which is over 2.6 times higher than isotropic aerogels (320 mV). The energy density of anisotropic aerogels was around 52 nW/cm², representing outstanding piezoelectric performance for cellulose-based aerogels. Such aerogels with high compressibility, elastic recovery and exceptional piezoelectric performance could have potential applications in sensors, wearable electronics, etc.

     

Influence of anellation in N-heterocyclic carbenes: novel quinoxaline-anellated NHCs trapped as transition metal complexes

The synthesis, NMR-, and crystal structure data of novel electron-deficient quinoxaline anellated imidazol-2-ylidene precursors and complexes thereof are reported and compared with related less electron-withdrawing or non-anellated N-heterocyclic carbenes and complexes to illustrate anellation effects.     

Silica-immobilized piperazine: A sustainable organocatalyst for aldol and Knoevenagel reactions

Silica-supported piperazine was found to be an efficient catalyst for aldol reactions of aromatic aldehydes and ketones with straightforward product isolation and catalyst reuse. Furthermore, the catalyst is active in Knoevenagel-type reactions to afford coumarin derivatives, using 2-methyltetrahydrofuran (2-MeTHF) as a novel bio-based solvent.     

Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst

The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure).     

Thermal stimuli-responsive behavior of pyrene end-functionalized PDMS through tunable Π–Π interactions

Pyrene end-functionalized, telechelic poly(dimethyl siloxane) (PDMS) materials were synthesized and their response to different thermal stimuli was evaluated. The incorporation of pyrene end groups introduces strong π–π interactions that facilitated a broad range of thermally responsive properties, in some circumstances forming pyrene nanocrystals that serve as physical crosslinks leading to elastic materials. By synthesizing different chain lengths, samples exhibiting a 7 orders of magnitude change in storage modulus in response to thermal stimuli were produced by modifying only the end-groups (0.6 wt % of all polymer segments). Repeated thermal cycling during rheological experiments revealed that π–π interaction and crystallization/melting kinetics of pyrene chain-ends plays a key role in their thermal responsiveness. The properties of these materials were tuned by adding free pyrene, neat PDMS, or graphene oxide (GO) nanoparticles, making them attractive for many applications (e.g., tunable damping materials, heat/light sensors, conductive gels, or light repositionable adhesives). For example, nanocomposites containing 1 wt % GO caused the melting temperature for pyrene crystal domains to more than double, and even induced pyrene end-group crystallization in samples that did not exhibit crystals in neat form. It is hypothesized that these features originate from π–π interactions between pyrene ends and GO surfaces. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 159–168     

Piezoelectric Energy Harvesting from a Ferroelectric Hybrid Salt [Ph3MeP]4[Ni(NCS)6] Embedded in a Polymer Matrix

Organic–inorganic hybrid ferroelectrics are an exciting class of molecular materials with promising applications in the area of energy and electronics. The synthesis, ferroelectric and piezoelectric energy harvesting behavior of a 3d metal ion‐containing A₄BX₆ type organic–inorganic hybrid salt [Ph₃MeP]₄[Ni(NCS)₆] ( 1 ) is now presented. P‐E hysteresis loop studies on 1 show a remnant ferroelectric polarization value of 18.71 μC cm^?2, at room temperature. Composite thermoplastic polyurethane (TPU) devices with 5, 10, 15 and 20 wt % compositions of 1 were prepared and employed for piezoelectric energy harvesting studies. A maximum output voltage of 19.29 V and a calculated power density value of 2.51 mW cm^?3 were observed for the 15 wt % 1 ‐TPU device. The capacitor charging experiments on the 15 wt % 1 ‐TPU composite device shows an excellent energy storage performance with the highest stored energies and measured charges of 198.8 μJ and 600 μC, respectively.     

The ionization constants of somep-alkylthio- andp-alkylsulphonyl-anilines

The ionization constants of somep-alkylthio- andp-alkylsulphonyl anilines have been determined by the spectrophotometric method at 30°. The results have been interpreted by invoking an electron pair acceptor type conjugation of the sulphur atom with thep-amino group. The pK_a values of thep-alkylthioanilines are of the order, methyl > ethyl > isopropyl >t-butyl. In the case ofp-alkylsulphonylanilines, the order is, methyl > ethyl < isopropyl. The higher strength ofp-isopropyl-sulphonylaniline compared to its ethyl analogue, is attributed to the steric effect.     

Molecular Dynamics Approach to Probe the Allosteric Inhibition of PTP1B by Chlorogenic and Cichoric Acid

Protein tyrosine phosphatase 1B (PTP1B), a major negative regulator of the insulin and leptin signaling pathway, is a potential target for therapeutic intervention against diabetes and obesity. The recent discovery of an allosteric site in PTP1B has created an alternate strategy in the development of PTP1B targeted therapy. The current study investigates the molecular interactions between the allosteric site of PTP1B with two caffeoyl derivatives, chlorogenic acid (CGA) and cichoric acid (CHA), using computational strategies. Molecular docking analysis with CGA and CHA at the allosteric site of PTP1B were performed and the resulting protein-ligand complexes used for molecular dynamics simulation studies for a time scale of 10 ns. Results show stable binding of CGA and CHA at the allosteric site of PTP1B. The flexibility of the WPD loop was observed to be constrained by CGA and CHA in the open (inactive), providing molecular mechanism of allosteric inhibition. The allosteric inhibition of CGA and CHA of PTP1B was shown to be favorable due to no restriction by the α-7 helix in the binding of CGA and CHA at the allosteric binding site. In conclusion, our results exhibit an inhibitory pattern of CGA and CHA against PTP1B through potent binding at the allosteric site.