Synthesis of boron dipyrromethene fluorescent probes for bioorthogonal labeling

Seven 5-substituted 3-hydrazinyl derivatives of 3a, 4a-diaza-4,4-difluoro-8-phenyl boron dipyrromethene (BODIPY) were prepared for use as bioorthogonal fluorescent labels of aldehydes and ketones. The absorption energies can be tuned to absorb visible light over a large span of wavelengths by changing the nature of the 5-substituent. Optical properties of hydrazones formed with the 5-chloro derivative are affected by the nature of the electrophile such that aliphatic and aromatic hydrazones can be differentiated from each other and from unreacted fluorophore.     

Photoconductive novel mesomorphic oxotitanium phthalocyanines

The synthesis and photoconductivity properties of the alkylthia and triethyleneoxysulfonyl substituted oxotitanium(IV) phthalocyanines (1a and 2a) are reported for the first time. The new compounds have been characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopy, electronic spectroscopy and mass spectroscopy. The mesogenic properties of these new materials were studied by differential scanning calorimetry and optical microscopy. The electrical dark conductivities (σ_d) and photoconductivities (σ_ph) of deposited films of 1a and 2a were investigated in various media with different concentrations of oxygen. Molecular oxygen increases photoconductivities (σ_ph) significantly. The photoconductivity mechanism and formation of Pc⁺ which is positive charge carrier under the light irradiation of the phthalocyanine molecules are demonstrated using the theoretical calculations. The geometries of the oxotitanium(IV) phthalocyanines (TiOPc) are optimized with PM3 semi-empirical method, and their visible absorption maxima are calculated with ZINDO/S method. The results agree well with the observed values. It was found that for the calculation of visible absorption of neutral and positively charged substituted TiOPc molecules using ZINDO/S method could rapidly yield excellent results. Dipole moment, HOMO, LUMO energies and atomic charges are also calculated for clarification of the oxygen effect on the photoconductivity using PM3 and ZINDO/S methods.     

Natural occurrence of ochratoxin A in dried figs

Ochratoxin A (OTA) contamination in dried figs was investigated using high performance liquid chromatography (HPLC) with fluorescence detection after extraction with methanol and orthophosphoric acid and clean up by an immunoaffinity column. The limit of detection for OTA was 0.12 microg kg(-1). One hundred and fifteen samples were taken during the drying stage from 7 different districts in the Aegean Region in 2003 and 2004. Fifty-five (47.2%) of the 115 samples were found to contain detectable levels of ochratoxin A, ranging from 0.12 to 15.31 microg kg(-1). However, the OTA level for a majority of the samples was low, with only 4 samples containing OTA exceeding 1 microg kg(-1). The calculated overall median for the OTA level was below the limit of detection and the overall mean was estimated as 0.52 microg kg(-1). Frequency of ochratoxin A contamination in dried figs harvested in 2003 and 2004 are 47 and 50%, respectively. Highest contamination ratio was determined in dried figs from Erbeyli (60%), followed by Selcuk (56%), and Ortaklar (50%).     

Simultaneous Identification of Spectral Properties and Sizes of Multiple Particles in Solution with Subnanometer Resolution

We report an unsurpassed solution characterization technique based on analytical ultracentrifugation, which demonstrates exceptional potential for resolving particle sizes in solution with sub‐nm resolution. We achieve this improvement in resolution by simultaneously measuring UV/Vis spectra while hydrodynamically separating individual components in the mixture. By equipping an analytical ultracentrifuge with a novel multi‐wavelength detector, we are adding a new spectral discovery dimension to traditional hydrodynamic characterization, and amplify the information obtained by orders of magnitude. We demonstrate the power of this technique by characterizing unpurified CdTe nanoparticle samples, avoiding tedious and often impossible purification and fractionation of nanoparticles into apparently monodisperse fractions. With this approach, we have for the first time identified the pure spectral properties and band‐gap positions of discrete species present in the CdTe mixture.     

On the Modeling of CO2 EUA and CER Prices of EU‐ETS for the 2008–2012 Period

Increased consumption of fossil fuels in industrial production has led to a significant elevation in the emission of greenhouse gases and to global warming. The most effective international action against global warming is the Kyoto Protocol, which aims to reduce carbon emissions to desired levels in a certain time span. Carbon trading is one of the mechanisms used to achieve the desired reductions. One of the most important implications of carbon trading for industrial systems is the risk of uncertainty about the prices of carbon allowance permits traded in the carbon markets. In this paper, we consider stochastic and time series modeling of carbon market prices and provide estimates of the model parameters involved, based on the European Union emissions trading scheme carbon allowances data obtained for 2008–2012 period. In particular, we consider fractional Brownian motion and autoregressive moving average–generalized autoregressive conditional heteroskedastic modeling of the European Union emissions trading scheme data and provide comparisons with benchmark models. Our analysis reveals evidence for structural changes in the underlying models in the span of the years 2008–2012. Data‐driven methods for identifying possible change‐points in the underlying models are employed, and a detailed analysis is provided. Our analysis indicated change‐points in the European Union Allowance (EUA) prices in the first half of 2009 and in the second half of 2011, whereas in the Certified Emissions Reduction (CER) prices three change‐points have appeared, in the first half of 2009, the middle of 2011, and in the second half of 2012. These change‐points seem to parallel the global economic indicators as well. Copyright © 2016 John Wiley & Sons, Ltd.     

Comparative evaluation of various total antioxidant capacity assays applied to phenolic compounds with the CUPRAC assay

It would be desirable to establish and standardize methods that can measure the total antioxidant capacity level directly from vegetable extracts containing phenolics. Antioxidant capacity assays may be broadly classified as electron transfer (ET)- and hydrogen atom transfer (HAT)-based assays. The majority of HAT assays are kinetics-based, and involve a competitive reaction scheme in which antioxidant and substrate compete for peroxyl radicals thermally generated through the decomposition of azo compounds. ET-based assays measure the capacity of an antioxidant in the reduction of an oxidant, which changes colour when reduced. ET assays include the ABTS/TEAC, CUPRAC, DPPH, Folin-Ciocalteu and FRAP methods, each using different chromogenic redox reagents with different standard potentials. This review intends to offer a critical evaluation of existing antioxidant assays applied to phenolics, and reports the development by our research group of a simple and low-cost antioxidant capacity assay for dietary polyphenols, vitamins C and E, and human serum antioxidants, utilizing the copper(II)-neocuproine reagent as the chromogenic oxidizing agent, which we haved named the CUPRAC (cupric ion reducing antioxidant capacity) method. This method offers distinct advantages over other ET-based assays, namely the selection of working pH at physiological pH (as opposed to the Folin and FRAP methods, which work at alkaline and acidic pHs, respectively), applicability to both hydrophilic and lipophilic antioxidants (unlike Folin and DPPH), completion of the redox reactions for most common flavonoids (unlike FRAP), selective oxidation of antioxidant compounds without affecting sugars and citric acid commonly contained in foodstuffs and the capability to assay -SH bearing antioxidants (unlike FRAP). Other similar ET-based antioxidant assays that we have developed or modified for phenolics are the Fe(III)- and Ce(IV)-reducing capacity methods.     

Functional zinc(II) phthalocyanines bearing Schiff base complexes as oxidation catalysts for bleaching systems

Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost‐effective, energy‐saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) ( 2 ), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) ( 3 ) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) ( 4 ) as tri‐nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2 , 3 , 4 was performed through the reaction of a Schiff base‐substituted phthalocyanine using MnCl₂?4H₂O, CoCl₂?6H₂O or FeCl₃?6H₂O salts in basic condition in dimethylformamide. Fourier transform infrared, ¹H NMR, ¹³C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds 2 , 3 , 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2 , 3 , 4 /H₂O₂ combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2 , 3 , 4 exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and stability of BODIPY‐based fluorescent polymer brushes at different pHs

We report a simple strategy for the grafting of poly(methacrylic acid) [poly(MAA)] brushes from silicon substrate by surface‐initiated RAFT polymerization and the subsequent coupling of BODIPY to these brushes to render them fluorescent. The poly(MAA) brushes were first generated by functionalization of hydrogen‐terminated silicon substrate with methyl‐10‐undecenoate which both leads to the formation of an organic layer covalently linked to the surface via Si? C bonds without detectable reaction of the carboxylate groups and couples to the polymerization initiator, followed by surface‐initiated RAFT polymerization of tert‐butyl methacrylate from these substrate‐bound initiator centers, and finally conversion of tert‐butyl groups to carboxylic acid groups. The poly(MAA) brushes were then made fluorescent by grafting a BODIPY derivative via an ester linkage. The stability of the BODIPY‐based fluorescent polymer brushes in buffer solutions at pH 6.0 to 12.0 with added salt was investigated by ellipsometry, fluorescence microscopy, grazing angle‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy. The results of these measurements indicated that the organic molecule‐initiator bond (ester linkage) is unstable and can be hydrolyzed resulting in detaching of the immobilized polymer from the silicon substrate. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3586–3596     

Development and validation of an LC‐MS/MS method for simultaneous quantitative analysis of free and conjugated bisphenol A in human urine

Bisphenol A (BPA) is an environmental endocrine‐disrupting chemicals that is widely used in common consumer products. There is an increasing concern regarding human exposure to BPA owing to the potential adverse effects associated with its estrogenic activity. For assessing environmental exposure to BPA, it is essential to have a sensitive, accurate and selective analytical method, especially one that can detect low BPA levels in complex sample matrices. In this study, we developed and validated an accurate, sensitive, and robust liquid chromatography–tandem mass spectrometry method for simultaneous quantification of free BPA and BPA β‐d ‐glucuronide (BPA‐gluc) concentrations in human urine with only a single injection. Calibration curves were linear over a concentration range of 1–100 ng/mL for BPA and 10–1000 ng/mL for BPA‐gluc. The levels of the analytes were determined quantitatively with HPLC/ESI‐MS/MS by using negative electrospray ionization in the select ion monitoring mode and a pentaflouraphenyl propyl column. The validated method was applied to the analysis of spot urine specimens collected from randomly selected healthy human subjects. Copyright © 2013 John Wiley & Sons, Ltd.