Effect of ultrasound processing on anthocyanins and color of red grape juice

Grape juice samples were sonicated with processing variables of amplitude level (24.4–61.0 μm) and treatment time (0–10 min) at a constant frequency of 20 kHz and pulse durations of 5 s on and 5 s off. A full factorial experimental design with regression modeling was employed to investigate the main effects of amplitude level and treatment time on anthocyanins and color parameters. Significant effects of sonication on major anthocyanins cyanidin-3-O-glucosides (CA), malvanidin-3-O-glucosides (MA) and delphinidin-3-O-glucosides (DA), color values (L*, a*, b*) and color index (CI) were observed. Prediction models were found to be significant (p < 0.05) with low standard errors and high coefficients of determination (R²). Model predictions for critical quality parameters of anthocyanins (CA; MA; DA), color values (L*, a*, b*), TCD and CI inactivation were closely correlated to the experimental results obtained. Significant retention of anthocyanin content in grape juice was observed for CA (97.5 %); MA (48.2 %) and DA (80.9%) during sonication. CI and other color combinations (L*a*b*, L*a*/b* and L*b*/a*) were found to be strongly correlated with anthocyanin content. This study shows that sonication could be employed for as a preservation technique for fruit juice processing where anthocyanin retention is desired.     

The role of the hydrolysis and zirconium concentration on the structure and anticorrosion performances of a hybrid silicate sol-gel coating

In sol-gel chemistry, hydrolysis is the key step in the formation of the reactive hydroxide groups that are responsible for the formation of inorganic networks via the occurrence of condensation reactions. Though previous studies have investigated the effect of the hydrolysis conditions on the structure of organically modified silicates (ormosils), no study, to our knowledge, has investigated this variable on the structure of hybrid materials prepared by combinations of an ormosil and a transition metal (TM). Here, we propose to investigate this effect in a hybrid material composed of 3-trimethoxysilylpropylmethacrylate and a zirconium complex. To also highlight the effects of the precursor’s concentrations on the hydrolysis and condensation reactions of the hybrid materials, their relative content was altered along with the hydrolysis degree. The anticorrosion barrier properties were identified by characterisation of coatings deposited on AA2024-T3 substrates and correlation between the structure and the anticorrosion properties of the coatings were performed based on results obtained from structural characterisations (DLS, FTIR, ²⁹Si-NMR, DSC, AFM and SEM) and corrosion testing (EIS and NSS). It is demonstrated that competition in the formation of siloxane and Si-O-Zr bonds takes place and can be controlled by the degree of hydrolysis and the concentration of the zirconium complex. This effect was found to dramatically alter the morphology of the coatings and their subsequent anticorrosion performances. At short-term exposure times, it is found that the most condensed materials exhibited a higher corrosion resistance while over longer periods the performances were found to level. This article highlighted the critical impact of the hydrolysis degree and zirconium concentration on the connectivity of hybrid sol-gel coatings and the impact this has on corrosion performances.

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Total synthesis of dermostatin A

The concise total synthesis of dermostatin A is described. Highlights include a two-directional application of the asymmetric acetate aldol method developed in our lab, a novel diastereotopic-group-selective acetal isomerization for terminus differentiation, and a selective cross-metathesis reaction between a terminal olefin and a trienal. A study of the scope and viability of similar cross-metathesis reactions is also described. The synthesis is convergent and utilizes fragments of roughly equal complexity.     

Damage to DNA in bacterioplankton: a model of damage by ultraviolet radiation and its repair as influenced by vertical mixing

A model of UV-induced DNA damage in oceanic bacterioplankton was developed and tested against previously published and novel measurements of cyclobutane pyrimidine dimers (CPD) in surface layers of the ocean. The model describes the effects of solar irradiance, wind-forced mixing of bacterioplankton and optical properties of the water on net DNA damage in the water column. The biological part includes the induction of CPD by UV radiation and repair of this damage through photoreactivation and excision. The modeled damage is compared with measured variability of CPD in the ocean: diel variation in natural bacterioplankton communities at the surface and in vertical profiles under different wind conditions (net damage as influenced by repair and mixing); in situ incubation of natural assemblages of bacterioplankton (damage and repair, no mixing); and in situ incubation of DNA solutions (no repair, no mixing). The model predictions are generally consistent with the measurements, showing similar patterns with depth, time and wind speed. A sensitivity analysis assesses the effect on net DNA damage of varying ozone thickness, colored dissolved organic matter concentration, chlorophyll concentration, wind speed and mixed layer depth. Ozone thickness and mixed layer depth are the most important factors affecting net DNA damage in the mixed layer. From the model, the total amplification factor (TAF; a relative measure of the increase of damage associated with a decrease in ozone thickness) for net DNA damage in the euphotic zone is 1.7, as compared with 2.1-2.2 for irradiance weighted for damage to DNA at the surface.     

pH-dependent binding of guests in the cavity of a polyhedral coordination cage: reversible uptake and release of drug molecules

A range of organic molecules with acidic or basic groups exhibit strong pH-dependent binding inside the cavity of a polyhedral coordination cage. Guest binding in aqueous solution is dominated by a hydrophobic contribution which is compensated by stronger solvation when the guests become cationic (by protonation) or anionic (by deprotonation). The Parkinson''s drug 1-amino-adamantane (‘amantadine’) binds with an association constant of 10⁴ M^–1 in the neutral form (pH greater than 11), but the stability of the complex is reduced by three orders of magnitude when the guest is protonated at lower pH. Monitoring the uptake of the guests into the cage cavity was facilitated by the large upfield shift for the ¹H NMR signals of bound guests due to the paramagnetism of the host. Although the association constants are generally lower, guests of biological significance such as aspirin and nicotine show similar behaviour, with a substantial difference between neutral (strongly binding) and charged (weakly binding) forms, irrespective of the sign of the charged species. pH-dependent binding was observed for a range of guests with different functional groups (primary and tertiary amines, pyridine, imidazole and carboxylic acids), so that the pH-swing can be tuned anywhere in the range of 3.5–11. The structure of the adamantane-1-carboxylic acid complex was determined by X-ray crystallography: the oxygen atoms of the guest form CH···O hydrogen bonds with one of two equivalent pockets on the internal surface of the host. Reversible uptake and release of guests as a function of pH offers interesting possibilities in any application where controlled release of a molecule following an external stimulus is required.     

From Intercalation to Groove Binding: Switching the DNA‐Binding Mode of Isostructural Transition‐Metal Complexes

The interaction with duplex DNA of a small library of structurally related complexes that all contain a d⁶‐metal ion coordinated to either the 2,2 ′ :4,4 ′′ :4 ′ ,4 ′′′ ‐quaterpyridyl ligand or its methylated derivative are reported. This library is made up of a mixture of newly synthesised and previously reported systems. Despite their structural similarities the complexes display an almost 20‐fold variation in binding affinities. Although effects due to the overall charge of the complexes are apparent, the differences in binding characteristics are deeper than this; indeed, in a number of cases, changes in overall charge have little effect on binding affinity. Intriguingly, despite interacting with DNA through unfused ring systems, although two of the complexes studied are groove binders, the majority are non‐classical intercalators. A rationale for these effects has been obtained through a combination of experimental and computational studies.     

Multicomponent kinetic determinations using multivariate calibration techniques

Multivariate calibration techniques for use in multicomponent kinetic-based determinations are reviewed. Multivariate calibration is a chemometric tool that continues to grow in popularity among analytical chemists. Multicomponent kinetic methods depend on differences in rates of reactions or processes to distinguish among the components. Kinetic profiles or a combination of kinetic profiles and spectra are commonly used. Because of their ability to process large quantities of data, multivariate calibration techniques are well suited for kinetic-based determinations. The concepts and principles of multivariate calibration are discussed first. Classical least squares regression, principal component regression, partial least squares regression and artificial neural networks are the multivariate calibration techniques considered here in detail. Recent examples of the application of these techniques to multicomponent kinetic determinations are reviewed. Both single and multiwavelength kinetic data are considered.     

The implementation of a self-consistent constricted variational density functional theory for the description of excited states

We present here the implementation of a self-consistent approach to the calculation of excitation energies within regular Kohn-Sham density functional theory. The method is based on the n-order constricted variational density functional theory (CV(n)-DFT) [T. Ziegler, M. Seth, M. Krykunov, J. Autschbach, and F. Wang, J. Chem. Phys. 130, 154102 (2009)] and its self-consistent formulation (SCF-CV(∞)-DFT) [J. Cullen, M. Krykunov, and T. Ziegler, Chem. Phys. 391, 11 (2011)]. A full account is given of the way in which SCF-CV(∞)-DFT is implemented. The SCF-CV(∞)-DFT scheme is further applied to transitions from occupied π orbitals to virtual π(?) orbitals. The same series of transitions has been studied previously by high-level ab initio methods. We compare here the performance of SCF-CV(∞)-DFT to that of time dependent density functional theory (TD-DFT), CV(n)-DFT and ΔSCF-DFT, with the ab initio results as a benchmark standard. It is finally demonstrated how adiabatic TD-DFT and ΔSCF-DFT are related through different approximations to SCF-CV(∞)-DFT.     

Superdeformed bands in153Ho

In a recent experiment carried out with theEurogam Phase II γ-ray spectrometer three new superdeformed (SD) bands have been established in¹⁵³Ho. The properties of these SD bands are discussed in terms of proton particle-hole excitations and are compared to the SD bands in the adjacent nuclei. This is the first observation of SD structures in aZ=67 nucleus.