Reactivity Studies of Iridium Pyridylidenes [TpMe2Ir(C6H5)2(C(CH)3C(R)NH] (R=H,Me, Ph)

The reactivity of a series of iridium? pyridylidene complexes with the formula [Tp^Me2Ir(C₆H₅)₂(C(CH)₃C(R)N H] ( 1 a – 1 c ) towards a variety of substrates, from small molecules, such as H₂, O₂, carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e^? unsaturated [Tp^Me2Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H₂ is heterolytically split to give hydride? pyridylidene complexes, whilst CO, CO₂, and H₂C?O provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five‐membered metallacycles with an IrCH₂CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four‐membered iridacycles with the IrC(?CH₂)N moiety. C₆H₅(C?O)H and C₆H₅C?CH react with formation of Ir? C₆H₅ and Ir? C?CPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a – 1 c against O₂ is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported.     

Gap formulas for closed linear relations

A classical formula for the gap between two densely defined closed operators in a Hilbert space is extended to the case of linear relations. Copyright © 2014 John Wiley & Sons, Ltd.     

Determination of estrogens in environmental water samples using 1,3‐dipentylimidazolium hexafluorophosphate ionic liquid as extraction solvent in dispersive liquid–liquid microextraction

In this work, the potential of a symmetric dialkyl‐substituted ionic liquid (IL), 1,3‐dipenthylimidazolium hexafluorophosphate ([PPIm][PF₆]), as extraction solvent in dispersive liquid–liquid microextraction (DLLME) has been studied for the analysis of a group of three natural (estriol, 17β‐estradiol, and 17α‐estradiol) and four synthetic (17α‐ethynylestradiol, diethylstibestrol, dienestrol, and hexestrol) estrogenic compounds as well as one mycotoxin with estrogenic activity (zearalenone) in different types of water samples (Milli‐Q, mineral, and wastewater). Separation, determination, and quantification were developed by HPLC‐DAD and a fluorescence detector (FD) connected in series. Factors influencing the IL‐DLLME procedure (sample pH, amount of IL, type and volume of disperser solvent, ionic strength, and assistance of vortex agitation) were investigated and optimized by means of a step‐by‐step approach. Once the optimum extraction conditions were established (10 mL of water at pH 8, 60 mg of [PPIm][PF₆], 500 μL of ACN as disperser solvent and vortex agitation for 1 min), the calibration curves of the whole method (IL‐DLLME‐HPLC‐DAD/FD) were obtained and precision and accuracy were evaluated. It was demonstrated that the developed methodology was repeatable, accurate, and selective with limits of detection in the 0.30–0.57 μg/L and 13.8–37.1 μg/L range for FD and DAD, respectively. Relative recovery values were higher than 85% for the different types of water samples and the Student's t test demonstrated that there were not significant differences between the added and the found concentration.     

Methodology for measuring the thermal conductivity of insulating samples with small dimensions by heat flow meter technique

Journal of Thermal Analysis and Calorimetry - Nowadays, developing advanced, highly insulating materials for minimizing heat losses in buildings is of utmost relevance. Thus, there is a constant...     

Isolation and Immobilization of Influenza Virus-Specific N-SA-α-2,3-Gal Receptors Using Magnetic Nanoparticles Coated with Chitosan and Maackia amurensis Lectin

Avian influenza viruses preferentially bind to sialic acid alpha-2,3-galactose (N-SA-α-2,3-Gal) receptors on epithelial cells. Herein, we describe a procedure we have developed for isolation of N-SA-α-2,3-Gal receptors from porcine trachea using magnetic nanoparticles (NPs) coated with chitosan (NP-Ch) and functionalized with Maackia amurensis lectin (NP-lectin). Magnetic nanoparticles were coated with chitosan in a one-step co-precipitation, and then M. amurensis lectin was immobilized covalently using glutaraldehyde. Lectin coated nanoparticles were incubated with sialic acid enriched fraction of tracheal homogenate, and N-SA-α-2,3-Gal receptor was extracted under magnetic field in two cycles. The presence of 66.4 kDa protein was determined by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The interaction of immobilized receptor (NP-Ch-R) with M. amurensis lectin (NP-Ch-R-L) was demonstrated by Fourier transform infrared spectrometry (FTIR) and thermogravimetric analysis (TGA).     

Synthesis of a truncated tetradenolide

The enantiopure synthesis of a truncated tetradenolide is presented. Starting from the versatile Chiron 7,3-lactone-xylofuranose derivative (7,3-LXF), the enantiomerically pure synthesis of the title compound is obtained in six steps with a 40% overall yield.     

Distance-Dependent Electron Transfer Kinetics in Axially Connected Silicon Phthalocyanine-Fullerene Conjugates

The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine-C₆₀ dyads has been investigated. For this, two C₆₀-SiPc-C₆₀ dyads, 1 and 2 , varying in their donor-acceptor distance, have been newly synthesized and characterized. In the case of C₆₀-SiPc-C₆₀ 1 where the SiPc and C₆₀ are separated by a phenyl spacer, faster electron transfer was observed with k_cs equal to 2.7×10⁹ s⁻¹ in benzonitrile. However, in the case of C₆₀-SiPc-C₆₀ 2 , where SiPc and C₆₀ are separated by a biphenyl spacer, a slower electron transfer rate constant, k_cs=9.1×10⁸ s⁻¹, was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by ∼4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ∼3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of ³SiPc* as the end product and suggested the final lifetime of the charge separated state to be in the 3–20 ns range. Energy level diagrams established to comprehend these mechanistic details indicated that the comparatively high-energy SiPc^.+-C₆₀^.− charge separated states (1.57 eV) populated the low-lying ³SiPc* (1.26 eV) prior returning to the ground state.     

Dissipation of the herbicide active ingredient glyphosate in natural water samples in the presence of biofilms

Dissipation of the herbicide active ingredient glyphosate was investigated in natural waters. To assess combined effects, glyphosate was applied in its pure form (glyphosate isopropylammonium salt) and in preparation Roundup Classic® formulated with polyethoxylated tallowamines (POEA). Standing and running surface water samples originated from Lake Balaton and River Danube between early May and mid-June of 2015. The kinetics of dissipation of glyphosate, measured by high-performance liquid chromatography combined with UV-VIS absorbance detection or tandem mass spectrometry, was investigated under laboratory conditions in aquaria with or without the presence of biofilms. The quantity and the biofilm structure of algal biomass were determined by in vivo fluorimetry and scanning electron microscopy. The presence of POEA affected the dissipation of glyphosate, and dissipation profiles differed in the investigated natural waters. Significantly higher initial concentrations of glyphosate were measured in River Danube for treatment with formulated glyphosate (101.4 ± 6.2 µg L^?1), than with glyphosate alone (79.9 ± 6.6 µg L^?1), and dissipation to a residual level (57.6 ± 1.4 µg L^?1) consequently took longer (approximately by 1 day). Degradation of glyphosate from the initial level (91.24 ± 5.9 µg L^?1) in Lake Balaton was not detected. Phytotoxic effects of glyphosate, particularly if enhanced by a formulant on algal biomass, were observed. Thus, 5–18% and 11–33% of algal biomass reduction was determined in River Danube upon treatments with glyphosate and Roundup Classic®, respectively. Corresponding biomass decreases in Lake Balaton were 1.3–13% and 9–14%, respectively, accompanied by an overall decay in the algal biofilms. In River Danube, treatments resulted in the occurrence of 1.4–5.8% of green algae in the algal biomass in 28 days, while green algae were not detected in the untreated control. The results indicate that glyphosate is capable of modifying the structure of the algal community and to induce increased secretion of extracellular polymeric substances matrix in the biofilms assessed.     

Spectral Criteria for Design of an Optical Modulator Based on Frustrated Total Internal Reflection

The spectral study of an optical modulator based on the frustrated total internal reflection is presented under static and dynamic conditions. An optical modulator based on macroscopic moving parts makes spectrometers voluminous and has low compactness. The use of static or quasi-static optical modulators, such as the one proposed in this paper, avoids these problems. The study under static conditions reveals that the modulator equalises the spectral emittance of a black body. The modulation efficiency is defined by comparing the modulator with an ideal square chopper. Study under dynamic conditions reveals spectral criteria that must be met in the design of the mechanical system of the modulator to shift the maximum value of the modulation efficiency to the desired wavelength.