Conformational changes of functionalised indole receptors upon their interaction with anions

The conformational analysis of four C2-amido and C7-ureido functionalised indole anion receptors was performed by a combination of heteronuclear NMR spectroscopy and ab initio quantum mechanical calculations. NOE experiments showed that anti–anti conformation across C2–C2α and C7–N7α bonds is predominant in acetone solution in the absence of anions. Upon anion binding to receptors, syn–syn conformation becomes predominant. The conformational changes upon anion binding are in good agreement with energetic preferences established by ab initio calculations. Chemical shift changes induced by interaction of anions suggest that binding of chloride and bromide anions occurs primarily to H1 and H7α protons. Nitrate anions favour interaction with H7α and H7γ ureido protons, whereas acetate anions interact strongly with all four available hydrogen bond donor groups.     

Compound-specific isotope analysis of benzotriazole and its derivatives

Compound-specific isotope analysis (CSIA) is an important tool for the identification of contaminant sources and transformation pathways, but it is rarely applied to emerging aquatic micropollutants owing to a series of instrumental challenges. Using four different benzotriazole corrosion inhibitors and its derivatives as examples, we obtained evidence that formation of organometallic complexes of benzotriazoles with parts of the instrumentation impedes isotope analysis. Therefore, we propose two strategies for accurate $\delta^{13}$ C and $\delta^{15}$ N measurements of polar organic micropollutants by gas chromatography isotope ratio mass spectrometry (GC/IRMS). Our first approach avoids metallic components and uses a Ni/Pt reactor for benzotriazole combustion while the second is based on the coupling of online methylation to the established GC/IRMS setup. Method detection limits for on-column injection of benzotriazole, as well as its 1-CH $_{3}$ -, 4-CH $_{3}$ -, and 5-CH $_{3}$ -substituted species were 0.1–0.3 mM and 0.1–1.0 mM for δ¹³C and δ¹⁵N analysis respectively, corresponding to injected masses of 0.7–1.8 nmol C and 0.4–3.0 nmol N, respectively. The Ni/Pt reactor showed good precision and was very long-lived ( $>$ 1000 successful measurements). Coupling isotopic analysis to offline solid-phase extraction enabled benzotriazole-CSIA in tap water, wastewater treatment effluent, activated sludge, and in commercial dishwashing products. A comparison of $\delta ^{13}$ C and $\delta ^{15}$ N values from different benzotriazoles and benzotriazole derivatives, both from commercial standards and in dishwashing detergents, reveals the potential application of the proposed method for source apportionment.     

Measurement of the decayτ? →ρ?ντ

An analysis of the decay ^--0 v has been performed using the ARGUS detector at the DORIS II storage ring. The branching ratio has been determined to be Br(^--0 v =(22.6±0.4±0.9)%. The shape of the ^-0 invariant mass spectrum is found to be in good agreement with the predictions obtained using the conserved vector current (CVC) hypothesis, suggesting that the ^-0 system is produced in aJ ^P=1^– state. An analysis of the measured decay angular distribution of the pions with respect to the flight direction of the ^-0 system demonstrates the vector nature of the coupling at the v vertex. With the assumption of zerov mass thev spin has been shown to be .Supported by the German Bundesministerium für Forschung und Technologie, under contract number 054DO51 P     

Crystallinity of poly(3‐hexylthiophene) in thin films determined by fast scanning calorimetry

Using fast scanning calorimetry, we determined the crystallinity of thin films of poly(3‐hexylthiophene) crystallized from the melt from measurements of the specific melting enthalpy. A broad range of film thicknesses from 10 µm down to 26 nm was covered. The sample mass was determined from measurements of the specific heat capacity in the molten state allowing a quantitative analysis of the heat flow data. Films with a thickness 400 nm slowly cooled from the melt showed the same crystallinity as bulk samples measured with conventional DSC. Below 350 nm the melting enthalpy decreased strongly. We assign this strongly reduced crystallinity to the restricted crystallization kinetics originating from hindered spherulitic growth under thin film confinement. A higher crystallinity could be partially regained by extended isothermal crystallization at elevated temperatures. Much faster cooling, with rates above about 100 Ks^?1 led to a partial suppression of crystallization even for thick films. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1791–1801     

A theoretical study of imine hydrocyanation catalyzed by halogen‐bonding

A detailed theoretical study of the mechanism and energetics of an organocatalysis based on C?N activation by halogen‐bonding is presented for the hydrocyanation of N‐benzylidenemethylamine. The calculations at the level of scalar‐relativistic gradient‐corrected density functional theory give an insight in this catalytic concept and provide information on the characteristics of four different monodentate catalyst candidates acting as halogen‐bond donors during the reaction. © 2015 Wiley Periodicals, Inc.     

Equilibration and “Thermalization” in the Adapted Caldeira–Leggett Model

I explore the processes of equilibration exhibited by the Adapted Caldeira–Leggett (ACL) model, a small unitary “toy model” developed for numerical studies of quantum decoherence between an SHO and an environment. I demonstrate how dephasing allows equilibration to occur in a wide variety of situations. While the finite model size and other “unphysical” aspects prevent the notions of temperature and thermalization from being generally applicable, certain primitive aspects of thermalization can be realized for particular parameter values. I link the observed behaviors to intrinsic properties of the global energy eigenstates, and argue that the phenomena I observe contain elements which might be key ingredients that lead to ergodic behavior in larger more realistic systems. The motivations for this work range from curiosity about phenomena observed in earlier calculations with the ACL model to much larger questions related to the nature of equilibrium, thermalization, and the emergence of physical laws.     

In vivo Raman spectroscopic analysis of the influence of UV radiation on carotenoid antioxidant substance degradation of the human skin

It is well known from the literature that carotenoid antioxidant substances decrease after the irradiation of the skin with UV light. Available literature has shown no information about the response time and total dynamics of degradation of carotenoid antioxidants after UV irradiation. The measurements were made with the HPLC method, which is time-consuming and does not give relevant information about the dynamics of degradation of carotenoids in the skin after UV irradiation. With the introduction of new noninvasive spectroscopic methods, it became possible to measure in vivo the behavior of carotenoid antioxidant substances, such as betacarotene and lycopene in the skin after UV light exposure. In the present study, the resonance Raman spectroscopy method was used as a fast and noninvasive optical method to measure the dynamics of degradation of beta-carotene and lycopene in living human skin after UV exposure. It was found that the beta-carotene and lycopene concentration in the skin does not decrease immediately after UV irradiation. There is a time delay, which varies from 30 up to 90 min for beta-carotene and from 0 up to 30 min for lycopene. A strong nonlinear correlation between the individual antioxidant level of volunteers and the magnitude of destruction of antioxidants in the skin was found.     

On Some Properties of Convex Matrix Sets Characterized by P -Matrices and Block P -Matrices

In this paper, we consider convex sets of real matrices and establish criteria characterizing these sets with respect to certain matrix properties of their elements. In particular, we deal with convex sets of P-matrices, block P-matrices and M-matrices, nonsingular and full rank matrices, as well as stable and Schur stable matrices. Our results are essentially based on the notion of a block P-matrix and extend and generalize some recently published results on this topic.     

Charge Transport Properties of Molecular Junctions Built from Dithiol Polyenes

We present a study of the charge transmission behavior of a series of dithiol polyenes in the context of molecular junctions. Using the Landauer theory and zero voltage approximation the Green’s functions of the inserted molecules are calculated from a fully ab initio wave function based procedure. Various possibilities in approximating the correlation space are explored and quantitatively evaluated. Our results show that the transmission behavior of a molecular junction is not a monotonic function of the length of the employed molecule. Moreover, we introduce the analytic solution of a suitable model system to countercheck the ab initio results and find a remarkable degree of correspondence.