An experimental Raman and theoretical DFT study on the self-association of acrylonitrile

The liquid structure of acrylonitrile (propenenitrile) has been investigated using Raman spectroscopy and density functional theory (DFT) ab initio calculations with the 6-311++G** basis set. Two different and complementary experimental approaches were undertaken: FT-Raman spectra of 13 acrylonitrile solutions in carbon tetrachloride (concentration range=0.25-12.0 mol.L-1) were studied in detail including principal component analysis (PCA) of the CN stretching band. Furthermore, dispersive Raman spectra of neat acrylonitrile were obtained at eight different temperatures from 238 up to 343 K. The complex and asymmetric acrylonitrile Raman CN stretching band can be decomposed into two components attributed to monomeric and self-associated forms. Ab initio results fully support this assignment and suggest that the self-associated complex is a nonplanar trimer held together by dipole-dipole interactions. At ambient temperature, the composition of acrylonitrile can be expressed as a mixture of 25% monomers and 75% trimers. Close to the boiling point, trimers still represent 65% of the liquid composition. The corresponding enthalpy of association was estimated to be -22+/-2 kJ.mol-1.     

Photophysics of a xanthenic derivative dye useful as an "on/off" fluorescence probe

The photophysical behavior of a new fluorescein derivative has been explored by using absorption and steady-state and time-resolved fluorescence measurements. The influence of ionic strength, as well as total buffer concentration, on both the absorbance and fluorescence has been investigated. The apparent acidity constant of the dye determined by absorbance is almost independent of the added buffer and salt concentrations. A semiempirical model is proposed to rationalize the variations in the apparent pKa values. The excited-state proton-exchange reaction around the physiological pH becomes reversible upon addition of phosphate buffer, inducing a pH-dependent change of the steady-state fluorescence and decay times. Fluorescence decay traces, collected as a function of total buffer concentration and pH, were analyzed by global compartmental analysis, yielding the following values of the rate constants describing excited-state dynamics: k01 = 1.29 x 10(10) s(-1), k02 = 4.21 x 10(8) s(-1), k21 approximately 3 x 10(6) M(-1) s(-1), k12B= 6.40 x 10(8) M(-1) s(-1), and k21B = 2.61 x 10(7) M(-1) s(-1). The decay rate constant values of k01, k21, k21B, along with the low molar absorption coefficient of the neutral form, mean that coupled decays are practically monoexponential at buffer concentrations higher than 0.02 M and any pH. Thus, the pH and buffer concentration can modulate the main lifetime of the dye.     

TG,DTA and X-ray thermodiffraction study of wall paintings from the fifteenth century

Journal of Thermal Analysis and Calorimetry - In this work, it is reported that thermal analysis techniques such as TG, DTA and X-ray thermodiffraction, performed in air or nitrogen atmosphere, are...     

The Singular Molecular Conformation of Humic Acids in Solution Influences Their Ability to Enhance Root Hydraulic Conductivity and Plant Growth

Some studies have reported that the capacity of humic substances to improve plant growth is dependent on their ability to increase root hydraulic conductivity. It was proposed that this effect is directly related to the structural conformation in solution of these substances. To study this hypothesis, the effects on root hydraulic conductivity and growth of cucumber plants of a sedimentary humic acid and two polymers—polyacrylic acid and polyethylene glycol—presenting a molecular conformation in water solution different from that of the humic acid have been studied. The results show that whereas the humic acid caused an increase in root hydraulic conductivity and plant growth, both the polyacrylic acid and the polyethylene glycol did not modify plant growth and caused a decrease in root hydraulic conductivity. These results can be explained by the different molecular conformation in water solution of the three molecular systems. The relationships between these biological effects and the molecular conformation of the three molecular systems in water solution are discussed.     

Valorization of Bio-Residues from the Processing of Main Portuguese Fruit Crops: From Discarded Waste to Health Promoting Compounds

Food processing generates a large amount of bio-residues, which have become the focus of different studies aimed at valorizing this low-cost source of bioactive compounds. High fruit consumption is associated with beneficial health effects and, therefore, bio-waste and its constituents arouse therapeutic interest. The present work focuses on the main Portuguese fruit crops and revises (i) the chemical constituents of apple, orange, and pear pomace as potential sources of functional/bioactive compounds; (ii) the bioactive evidence and potential therapeutic use of bio-waste generated in the processing of the main Portuguese fruit crops; and (iii) potential applications in the food, nutraceutical, pharmaceutical, and cosmetics industries. The current evidence of the effect of these bio-residues as antioxidant, anti-inflammatory, and antimicrobial agents is also summarized. Conclusions of the revised data are that these bio-wastes hold great potential to be employed in specific nutritional and pharmaceutical applications.     

Pincer-Supported Gallium Complexes for the Catalytic Hydroboration of Aldehydes,Ketones and Carbon Dioxide

Gallium hydrides stabilised by primary and secondary amines are scarce due to their propensity to eliminate dihydrogen. Consequently, their reactivity has received limited attention. The synthesis of two novel gallium hydride complexes HGa(THF)[ON(H)O] and H₂Ga[μ²-ON(H)O]Ga[ON(H)O] ([ON(H)O]²⁻=N,N-bis(3,5-di-tert-butyl-2-phenoxy)amine) is described and their reactivity towards aldehydes and ketones is explored. These reactions afford alkoxide-bridged dimers through 1,2-hydrogallation reactions. The gallium hydrides can be regenerated through Ga−O/B−H metathesis from the reaction of such dimers with pinacol borane (HBpin) or 9-borabicyclo[3.3.1]nonane (9-BBN). These observations allowed us to target the catalytic reduction of carbonyl substrates (aldehydes, ketones and carbon dioxide) with low catalyst loadings at room temperature.     

Elastic AlignedSENSE for Dynamic MR Reconstruction: A Proof of Concept in Cardiac Cine

Numerous methods in the extensive literature on magnetic resonance imaging (MRI) reconstruction exploit temporal redundancy to accelerate cardiac cine. Some of them include motion compensation, which involves high computational costs and long runtimes. In this work, we proposed a method—elastic alignedSENSE (EAS)—for the direct reconstruction of a motion-free image plus a set of nonrigid deformations to reconstruct a 2D cardiac sequence. The feasibility of the proposed approach was tested in 2D Cartesian and golden radial multi-coil breath-hold cardiac cine acquisitions. The proposed approach was compared against parallel imaging compressed sense (sPICS) and group-wise motion corrected compressed sense (GWCS) reconstructions. EAS provides better results on objective measures with considerable less runtime when an acceleration factor is higher than 10×. Subjective assessment of an expert, however, invited proposing the combination of EAS and GWCS as a preferable alternative to GWCS or EAS in isolation.     

A simple method for self-attenuation correction in <Superscript>210</Superscript>Pb activity measurement in a well-type HPGe detector

A simple method for ²¹⁰Pb determination in a well-type detector for matrix with apparent densities ranging from ρ = 0.430 g cm^?3 to ρ = 2.037 g cm^?3 is presented. Ten spiked samples of ²¹⁰Pb were prepared to obtain the detector efficiency as a quadratic function of the matrix density. Then this equation was validated and successfully used to measure ²¹⁰Pb concentration activity in other samples. The equation proposed in this work is specific for each germanium detector; however it is proposed an extrapolation of the method to other well-type germanium detector by preparing a spiked sample and determining the efficiency for ²¹⁰Pb.     

By-products of the cider production: an alternative source of nutrients to produce bacterial cellulose

In the present work a culture process to produce bacterial cellulose (BC) using by-products of the cider production from the Basque Country was investigated. The apple pomace was mixed with sugar cane (AR/SC medium) and the mixture was found to be a potential carbon source for Gluconacetobacter medellinensis strain ID13488 since higher cellulose production was observed with respect to the commercial Hestrin and Shramm medium (H–S). The culture media were characterized in terms of pH, oxygen and sugars consumption. The expression level of the operon bcs (genes involved in BC biosynthesis) in apple residue containing medium respect to standard H–S medium was determined. It was found that in AR/SC medium the expression levels of bcsA gene, wich is the first gene of the bcs operon, was increased in 1.5-fold respect to the H–S media which correlates with the fact that BC production in AR/SC media is higher than in H–S media. The physico-chemical and mechanical properties, microstructure, crystallinity and water holding capacity of the biosynthesized BC membranes were analyzed and it was found that, in general, the BC obtained from AR/SC medium presented superior properties than that obtained from H–S medium. In this study an economic method for BC production is proposed with suitable properties for many applications.