Quantitative analysis in field-flow fractionation using ultraviolet-visible detectors: an experimental design for absolute measurements

In previous works, it has been shown that a standard ultraviolet-visible detection system can be used for quantitative analysis of heterogeneous systems (dispersed supermicron particles) in field-flow fractionation (FFF) by single peak area measurements. Such an analysis method was shown to require either experimental measurements (standardless analysis) or an accurate model (absolute analysis) to determine the extinction efficiency of the particulate samples. In this work, an experimental design to assess absolute analysis in FFF through prediction of particles' optical extinction is presented. Prediction derives from the semiempirical approach by van de Hulst and Walstra. Special emphasis is given to the restriction of the experimental domain of instrumental conditions within which absolute analysis is allowed. Validation by statistical analysis and a practical application to real sample recovery studies are also given.     

Staphylococcus aureus bicomponent gamma-hemolysins, HlgA, HlgB, and HlgC, can form mixed pores containing all components

Staphylococcal gamma-hemolysins are bicomponent toxins forming a protein family with leucocidins and alpha-toxin. Two active toxins (AB and CB) can be formed combining one of the class-S components, HlgA or HlgC, with the class-F component HlgB. These two gamma-hemolysins form pores with marked similarities to alpha-toxin in terms of conductance, nonlinearity of the current-voltage curve, and channel stability in the open state. AB and CB pores, however, are cation-selective, whereas alpha-toxin is anion-selective. gamma-Hemolysins' pores are hetero-oligomers formed by three or four copies of each component (indicated as 3A3B and 3C3B or 4A4B and 4C4B). Point mutants located on a beta-strand of the class-S component that forms part of the protomer-protomer contact region can prevent oligomer assembly. Interestingly, these mutants inhibit growth of pores formed not only by their natural components but also by nonstandard components. This lead to the hypothesis that mixed ABC pores could also be formed. By studying the conductance of pores, assembled in the presence of all three components (in different ratios), it was observed that the magnitudes expected for mixed pores were, indeed, present. We conclude that the gamma-hemolysin/leucocidin bicomponent toxin family may form a larger than expected number of active toxins by cross-combining various S and F components.     

A study of the epoxidation of 6-deoxyhex-5-enopyranosides. 1,5-Dicarbonyl derivatives and novel synthetic routes to D-xylo-hexos-5-ulose and D-lyxo-hexos-5-ulose

The work described deals with the isolation and characterization of epoxides from 6-deoxyhex-5-enopyranosides and preliminary exploration of their synthetic potential. Prolonged epoxidation reaction times led to their hydrolysis in situ and gave novel protected D-hexos-5-ulose derivatives (sugar 1,5-dicarbonyls). Some reactions of the hexos-5-uloses were studied, and in some cases septanoside (seven-membered-ring saccharide) derivatives were isolated. Novel routes to D-xylo-hexos-5-ulose and D-lyxo-hexos-5-ulose, of interest as intermediates in the synthesis and biosynthesis of inositols and aza sugars, are also described. The structures of the epoxides and novel hexos-5-uloses were established by NMR and X-ray crystallographic methods.     

Outer product analysis of electronic nose and visible spectra: application to the measurement of peach fruit characteristics

Visual aspect and aroma are among the most important features of fruit that determine consumer preferences. Electronic nose and spectroscopic techniques have shown positive results in evaluating some basic analytical parameters of fruit and global features such as the cultivar.In this paper, we illustrate and discuss a study aimed at evaluating the improvement derived by the fusion of visible spectra and electronic nose data. These experiments were performed on a population of yellow peaches belonging to two cultivars. Each sample was measured by visible optical spectroscopy and by electronic nose. In addition, a number of reference parameters were also measured by conventional destructive methodologies.Collected data were analysed individually and then fused together in order to classify the two cultivars and to estimate the reference parameters. Data fusion was performed building the outer product matrix for each measurement. The set of matrices was then successively unfolded and analysed by conventional chemometrics tools.Results were improved using outer products, for instance in classification average percentage errors of 25, 10, and 7 for electronic nose, spectra, and outer product, respectively was achieved. Regression analysis provides the evidence of a substantial orthogonal appearance of the datasets, which offer former hidden information on fruit classification.     

A theory of nonvertical triplet energy transfer in terms of accurate potential energy surfaces: the transfer reaction from pi,pi* triplet donors to 1,3,5,7-cyclooctatetraene

Triplet energy transfer (TET) from aromatic donors to 1,3,5,7-cyclooctatetraene (COT) is an extreme case of "nonvertical" behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated (Arrhenius) process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces (PES) of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion parameter gamma=(2g(2)/kappa(1))(1/2) in which g stands for the norm of the energy gradient in the PES of the acceptor triplet state and kappa(1) is a combination of vibrational force constants of the ground-state acceptor in the gradient direction. The application of the model to existing experimental data for the triplet energy transfer reaction to COT from a series of pi,pi(*) triplet donors, provides a detailed interpretation of the parameters that determine the transfer rate constant. In addition, the model shows that the observed decrease of the acceptor electronic excitation energy is due to thermal activation of C=C bond stretchings and C-C bond torsions, which collectively change the ground-state COT bent conformation (D(2d)) toward a planar triplet state (D(8h)).     

Asymmetric hydrogenation - influence of the structure of carbohydrate derived catalysts on the relative enantioselectivity QH/Me regarding acid and ester substrates and its inversion - selectivity increase in water by amphiphiles

4,6-O-Benzylidene protected 2,3-bis(O-diphenylphosphino)-δ-glycopyranoside rhodium(I) chelate precatalysts 1-4 e,f showed for the hyrogenation of methyl (Z)-2-N-acylamidoacrylates 6-8 a stepwise decrease of the enantioselectivity with increasing number of axially oriented hexopyranoside substituents. The decrease is even stronger for the analogous substrate acids 6h-8h resulting in an unusual low relative enantioselectivity Q=q_H/q_Me of 0.3 for the precatalysts 4e and 4f. Deprotected, 4,6-OH-group bearing catalysts 1-4g,h generally show smaller differences of %ee in methanol or benzene, however, not in water. Under addition of amphiphiles a in comparison with blanks b the relative enantioselectivity Q=q_a/q_b clearly increases for both groups of catalysts - in most cases to Q-values between 3 up to 8 - independent of a neutral or ionic nature of the amphiphile.     

Generation and reactivity of 3‐carbethoxy‐5‐phenyl‐5H,7H‐thiazolo[3,4‐c]oxazol‐4‐ium‐1‐olate

3‐Carbethoxy‐5‐phenyl‐5H,7H‐thiazolo[3,4‐c]oxazol‐4‐ium‐1‐olate was generated from (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazolidine‐4‐carboxylic acid and its reactivity studied. This münchnone showed low reactivity as dipole although from the reaction with dimethyl acetylenedicarboxylate the corresponding (3R)‐3‐phenyl‐17H,3H‐pyrrolo[1,2‐c]thiazole‐5,6,7‐tricarboxylate could be isolated. The thermolysis of (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazolidine‐4‐carboxylic acid in refluxing acetic anhydride led to the synthesis of N‐(1‐ethoxycarbonyl‐2‐phenylvinyl)‐2‐phenyl‐4‐thioxo‐1,3‐thiazolidine. The structure of methyl (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazoliddine‐4‐carboxylate was determined by X‐ray crystallography.     

GO-SWCNT Buckypapers as an Enhanced Technology for Water Decontamination from Lead

Water decontamination is an important challenge resulting from the incorrect disposal of heavy metal waste into the environment. Among the different available techniques (e.g., filtration, coagulation, precipitation, and ion-exchange), adsorption is considered the cheapest and most effective procedure for the removal of water pollutants. In the last years, several materials have been tested for the removal of heavy metals from water, including metal-organic frameworks (MOFs), single-walled carbon nanotubes (SWCNTs), and graphene oxide (GO). Nevertheless, their powder consistency, which makes the recovery and reuse after adsorption difficult, is the main drawback for these materials. More recently, SWCNT buckypapers (SWCNT BPs) have been proposed as self-standing porous membranes for filtration and adsorption processes. In this paper, the adsorption capacity and selectivity of Pb²⁺ (both from neat solutions and in the presence of other interferents) by SWCNT BPs were evaluated as a function of the increasing amount of GO used in their preparation (GO-SWCNT buckypapers). The highest adsorption capacity, 479 ± 25 mg g⁻¹, achieved for GO-SWCNT buckypapers with 75 wt.% of graphene oxide confirmed the effective application of such materials for cheap and fast water decontamination from lead.     

Polymerization-Driven Photoluminescence in Alkanolamine-Based C-Dots

Carbonized polymer dots (CPDs), a peculiar type of carbon dots, show extremely high quantum yields, making them very attractive nanostructures for application in optics and biophotonics. The origin of the strong photoluminescence of CPDs resides in a complicated interplay of several radiative mechanisms. To understand the correlation between CPD processing and properties, the early stage formation of carbonized polymer dots has been studied. In the synthesis, citric acid monohydrate and 2-amino-2-(hydroxymethyl)propane-1,3-diol have been thermally degraded at 180 °C. The use of an oil bath instead of a more traditional hydrothermal reactor has allowed the CPD properties to be monitored at different reactions times. Transmission electron microscopy, time-resolved photoluminescence, nuclear magnetic resonance, infrared, and Raman spectroscopy have revealed the formation of polymeric species with amide and ester bonds. Quantum chemistry calculations have been employed to investigate the origin of CPD electronic transitions. At short reaction times, amorphous C-dots with 80 % quantum yield, have been obtained.     

A metallic furnace atomizer in hydride generation atomic absorption spectrometry: Determination of bismuth and selenium

A flow injection hydride generation system with a metal furnace atomizer (Inconel 600® alloy) was employed for Bi and Se determination. The presented methods have linear ranges up to 200 and 500 μg L^− 1 for Bi and Se, respectively, with good linearities (r² = 0.9997 and 0.9974, respectively). The limits of quantification obtained according to IUPAC recommendations were 2.3 μg L^− 1 for Bi and 6 μg L^− 1 for Se, and the relative standard deviations (N = 6) based on Bi and Se analytical responses from real samples were 2.7% and 10%, respectively. Accuracy evaluations were based on certified materials such as SRM 361, SRM 363, and SRM 364 (steel alloys) for Bi, Mess-3 (marine sediment), SRM 397 (human hair), and Bio-Rad2 — 69042 (urine) for Se. Good agreements between the results were obtained at the 95% confidence level, according to the t-test.