Smart optical probe for ‘equipment-free’ detection of oxalate in biological fluids and plant-derived food items

A reversible ‘turn-on’ sensor has been designed for ‘naked-eye’ detection of oxalate at nanomolar concentration (～12.5?nM) at pH 7.4. The sensory system shows a highly specific response towards oxalate among a wide range of antinutrients and biologically relevant anionic species. Mechanistic investigations indicate that oxalate can turn the pink-colored solution colorless by dissociating the preformed metal complex. Additionally, high specificity and good accuracy with recovery values ranging from 93.3 to 105.0% were obtained during oxalate estimation in spiked water and human urine samples, confirming the suitability of the present method in estimating trace-level of oxalate in complex matrices. With these results, quantitative estimations of endogenous oxalate were achieved in more than twenty-five different agricultural crops. Finally, low-cost, portable paper strips were developed for on-site detection of oxalate.     

A Rationally Designed Bimetallic Platinum (II)-Ferrocene Antitumor Agent Induces Non-Apoptotic Cell Death and Exerts in Vivo Efficacy

Despite phenomenal clinical success, the efficacy of platinum anticancer drugs is often compromised due to inherent and acquired drug resistant phenotypes in cancers. To circumvent this issue, we designed two heterobimetallic platinum (II)-ferrocene hybrids that display multi-pronged anticancer action. In cancer cells, our best compound, 2 , platinates DNA, produces reactive oxygen species, and has nucleus, mitochondria, and endoplasmic reticulum as potential targets. The multi-modal mechanism of action of these hybrid agents lead to non-apoptotic cell death induction which enables circumventing apoptosis resistance and significant improvement in platinum cross resistance profile. Finally, in addition to describing detail mechanistic insights, we also assessed its stability in plasma and demonstrate anticancer efficacy in an in vivo A2780 xenograft model. Strikingly, compared to oxaliplatin, our compound displays better tolerability, safety profile and efficacy in vivo.     

Synchronous fluorescence and excitation emission characteristics of transformer oil ageing

This paper describes the evaluation of synchronous fluorescence spectroscopy (SFS) and excitation emission matrix fluorescence (EEMF) spectroscopy as means of monitoring transformer oil degradation. When accelerated thermal ageing method is used, the onset of degradation of transformer oil on 17th day and transformer oil with polypropylene and cellulosic paper on 23rd and 27th days is sensitively reflected in the SFS and EEMF fluorescence spectral characteristics.     

Possible Influence of Layer Deformation and Chiral Segregation on Dielectric Modes in the Dark Conglomerate Liquid Crystal

Dielectric spectroscopy is used to investigate the structure, molecular dynamics, and relaxation phenomena in electric‐field‐induced switchable dark conglomerate (DC) phases in a bent‐core liquid crystal. The DC phases are obtained by applying a high‐frequency ac electric field in the B_1rev phase or by cooling under a dc or an ac field from the isotropic phase. Although the DC phases exhibit good electro‐optic switching properties, the dielectric parameters are different from those observed in typical lamellar SmCP phases and similar to those obtained in a non‐switchable DC phase. We therefore propose that the dielectric response and reduced intensity of the relaxation modes may be a general feature in DC phases and may owe its origin to the deformed layer structure in which certain molecular motions are impeded. Further, we find that in the field‐induced DC phases derived from the isotropic phase, the dielectric modes are affected by chiral segregation promoted by the applied field.     

Fast,Direct, Low‐Cost Route to Scalable,Conductive, and Multipurpose Poly(3,4‐ethylenedixoythiophene)‐Coated Plastic Electrodes

Poly(3,4‐ethylenedioxythiophene) (PEDOT) films are deposited, using an electroless method, onto flexible plastic poly(ethylene terephthalate) (PET) substrates of approximately 20×6 cm². The sheet resistance of a PEDOT–PET film is approximately 600 Ω per square, and the nanoscale conductivity is 0.103 S cm^?1. A plastic electrochromic PEDOT–Prussian blue device is constructed. The device undergoes a color change of pale blue to deep violet–blue reversibly over 1000 cycles, thus demonstrating its use as a light‐modulating smart window. The PEDOT–PET film is also used in a quantum dot solar cell, and the resulting photoelectrochemical performance and work function indicate that it is also promising for photovoltaic cells. The high homogeneity of the PEDOT deposit on PET, the optimal balance between conductivity and optical transparency, and the demonstration of its use in an electro‐optical device and a solar cell, offer the opportunity to use this electrode material in a variety of low‐cost optoelectronic devices.     

Neighboring group participation in the additions of iodonium and bromonium ions to N-alkoxycarbonyl-2-azabicyclo[2.2.n]alk-5-enes (n = 1,2)

Additions of iodonium-X reagents to N-alkoxycarbonyl-2-azabicyclo[2.2.1]hept-5-enes and the homologous 2-azabicyclo[2.2.2]oct-5-enes have been found to mirror the outcomes of additions of bromonium-X reagents. Only rearranged products were observed for reactions of either of these halonium ion reagents with the azabicylo[2.2.1]hept-5-enes. For the azabicyclo[2.2.2]oct-5-enes, nitrogen participation in addition of IOH or BrOH was dependent on the N-alkoxycarbonyl group. With larger N-Boc, N-Cbz, or N-Troc protecting groups, unrearranged 5-anti-hydroxy-6-syn-I(or Br)-2-azabicyclo[2.2.2]octanes were formed by nucleophilic attack at C(5) on syn-halonium ions. The structure of N-methyl-8-anti-bromo-4-anti-hydroxy-2-azabicyclo[3.2.1]octane has been reassigned by X-ray analysis.     

Terpenoid composition and antifungal activity of three commercially important essential oils against Aspergillus flavus and Aspergillus niger

Hydro-distilled essential oils extracted from three commercially important aromatic plants were analysed by capillary gas chromatography-flame ionization detector and gas chromatography/quadrupole mass spectrometry and subjected to antifungal activity. Fifteen compounds, which accounted for 97.8% of Acorus calamus root oil composition have been identified. Besides the major constituent (Z)-asarone (81.1-92.4%), (Z)-methyl isoeugenol (1.8-2.1%), (Z)-isoelemicin (1.2-1.3%), (E)-asarone (1.0-2.6%), (E)-methyl isoeugenol (0.2-0.4%), (Z)-β-ocimene (0.2-0.4%), elemicin (0.2-0.3%), linalool (0.1-0.9%) and kessane (t-0.2%) were identified. Monoterpenes constituted the main fraction of Origanum vulgare essential oil attaining 90.5% of the total oil composition. p-Cymene (10.3%) was the major component of the monoterpene hydrocarbon fraction while thymol (53.2%) and carvacrol (3.9%) were the most abundant oxygenated monoterpenes among the 33 identified constituents. Cinnamomum tamala leaf oil contained (E)-cinnamaldehyde as the principal component. Quantitative variations in (Z)-cinnamaldehyde (5.8-7.1%), linalool (6.4-8.5%) and (E)-cinnamyl acetate (4.7-5.2%) were significant. The antifungal activity of the hydro-distilled essential oils of A. calamus, O. vulgare and C. tamala were evaluated against Aspergillus flavus and Aspergillus niger. Disc diffusion method was used for the determination of the inhibitory effect. O. vulgare essential oil exhibited the highest activity. Moreover, all three essential oils inhibit the growth of A. flavus and A. niger.     

Combined hydrogen production and storage with subsequent carbon crystallization

We provide evidence of low-temperature hydrogen evolution and possible hydrogen trapping in an anthracite coal derivative, formed via reactive ball milling with cyclohexene. No molecular hydrogen is added to the process. Raman-active molecular hydrogen vibrations are apparent in samples at atmospheric conditions (300 K, 1 bar) for samples prepared 1 year previously and stored in ambient air. Hydrogen evolves slowly at room temperature and is accelerated upon sample heating, with a first increase in hydrogen evolution occurring at approximately 60 degrees C. Subsequent chemical modification leads to the observation of crystalline carbons, including nanocrystalline diamond surrounded by graphene ribbons, other sp2-sp3 transition regions, purely graphitic regions, and a previously unidentified crystalline carbon form surrounded by amorphous carbon. The combined evidence for hydrogen trapping and carbon crystallization suggests hydrogen-induced crystallization of the amorphous carbon materials, as metastable hydrogenated carbons formed via the high-energy milling process rearrange into more thermodynamically stable carbon forms and molecular hydrogen.     

Power-independent technique to extract the dispersion parameters of an optical fiber using four wave mixing

Conventional methods which extract dispersion parameters of an optical fiber using four wave mixing rely on the measurement of optical power in the generated wavelengths, and hence are prone to measurement errors. We propose and demonstrate a power-independent method to extract the dispersion curve of a fiber using four wave mixing (FWM). The analytical equations that have been traditionally used to estimate the phase mismatch in FWM are modified to cater to low-dispersion fibers, and are verified. Experiments to obtain the dispersion curve of a low-dispersion and highly nonlinear fiber are discussed and the results are analyzed. Limitations of any FWM-based method to extract the dispersion curve of a fiber are presented for the first time.     

Liquid phase benzylation of toluene using benzyl alcohol over iron promoted sulfated zirconia

Concentrated (0.2 M) aqueous solutions of HP-acids, such as H_3+x+mPV^IV _mV^V _x-mMo_12-xO₄₀ and their analogues with an excess VO²⁺ cation, are oxidized by dioxygen at 343 K and atmospheric pressure through intermediate active complexes (IAC) [H_x+m-1PV^IV _mV^V _x-mMo_12-xO₄₀ ^{4 -}] · [VO²⁺]_y · O₂, where m + y ≥ 3. The electron transfer to the coordinated O₂ molecule inside AC is the limiting stage at high m. At low m, the formation of IAC becomes the limiting stage that results in a sharp decrease in the oxidation rate. This revised version was published online in August 2006 with corrections to the Cover Date.