Optimization of extraction and quantification technique for phenolics content of garlic (Allium sativum): An application for comparative phytochemical evaluation based on cultivar origin

A range of conventional, i.e. maceration, percolation, ultrasonic assisted, Soxhlet and Soxtec extraction (STE), to advanced extraction techniques of accelerated solvent extraction (ASE) was utilized for the first time in order to optimize the extract yield and recovery of phenolics—gallic acid (GA), rutin (RT) and quercetin (QT)—quantified via ultra-high performance liquid chromatography with diode array detector (UHPLC–DAD). The effect of solvents (n-hexane, dichloromethane and methanol) and temperature (60, 80 and 100°C) upon extraction yield, phenolic content and antioxidant activity (DPPH, ABTS and DPPH) was studied, and the method was validated in commercial food samples from Saudi Arabia, China and India. A high extract yield with percentage recovery was observed for STE (1221.10 mg/5 g; 24.42%) and ASE techniques (91.50 mg/1 g; 9.15%) in methanol at 100°C. UHPLC–DAD showed retention times (min) of 0.67, 1.93 and 1.90 for GA, RT and QT, respectively in the shortest runtime of 3 min. The yield for phenolics was higher for STE/ASE (ppm): 15.27/15.29 (GA), 85.24/37.56 (RT) and 52.20/33.40 (QT), respectively. In terms of antioxidant activities, low IC₅₀ values (μg/ml) of 1.09/1.18 (DPPH), 2.11/5.32 (ABTS) and 4.35/7.88 (phenazine methosulfate–nicotinamide adenine dinucleotide) were observed for STE and ASE, respectively. Multivariate analysis for STE showed a significant (P = 0.000) correlation for extraction type vs. extract yield and phenolics content; however, there was no significance for antioxidant activities vs. extraction type. ASE showed a positive correlation for solvent vs. extraction yield, phenolics and antioxidant activity; however, there was no correlation for extraction yield and DPPH activity. Principal component analysis for STE showed a major variability (52.02%) for extraction yield and phenolics in PC1 followed by PC2 (38.30%) for antioxidant activities. For ASE, PC1 (48.68%) showed a positive correlation for solvent vs. extraction yield and phenolics while PC2 (33.12%) showed a positive correlation for temperature and antioxidant activities. STE and ASE were the optimized extraction techniques for the garlic food sample while a significant effect of solvent and temperature was observed upon extraction yield, phenolics and antioxidant activity.     

Heck reaction with an alkenylidenecyclopropane: the formation of arylallylidenecyclopropanes

The palladium-tetraphosphine catalyzed arylation of an alkylidenecyclopropane gives a simple and direct access to 1-aryl-2-methyl-1-(2,2,3,3-tetramethylcyclopropylidene)propenes. This reaction tolerates several functional groups on the aryl bromides. Even heteroaryl bromides have been used successfully. This reaction probably proceeds via a classical oxidative addition of the aryl bromide to palladium, insertion of the CCMe₂ bond in the Ar-Pd bond followed by β-elimination to give the dienes.     

Calibrating a J2 plasticity material model using a 2D inverse finite element procedure

Material models are the key ingredients to accurately capture the global mechanical response of structural systems. The use of finite element analysis has proven to be effective in simulating nonlinear engineering applications. However, the choice of the appropriate material model plays a big role in the value of the numerical predictions. Such models are not expected to exactly reproduce global experimental response in all cases. Alternatively, the measured global response at specific domain or surface points can be used to guide the nonlinear analysis to successively extract a representative material model. By selecting an initial set of stress–strain data points, the load–displacement response at the monitoring points is computed in a forward incremental analysis without iterations. This analysis retains the stresses at the integration points. The corresponding strains are not accurate since the computed displacements are not anticipated to match the measured displacements at the monitoring points. Therefore, a corrective incremental displacement analysis is performed at the same load steps to adjust for displacements and strains everywhere by matching the measured displacements at the monitoring points. The stress–strain vectors at the most highly stressed integration point are found to establish an improved material model. This model is used within a multi-pass incremental nonlinear finite element analysis until the discrepancy between the measured and the predicted structural response at the monitoring points vanishes. The J2 flow theory of plasticity is used as a constitutive framework to build the tangent elastic–plastic matrices. The applicability of the proposed approach is demonstrated by solving 2D inverse continuum problems. The comparisons presented support the effectiveness of the proposed approach in accurately calibrating the J2 plasticity material model for such problems.     

Effect of preparative conditions on the surface characteristics of mixed zirconium and titanium oxides

The surface characteristics of mixed zirconium and titanium oxides prepared from different starting materials are investigated. One mode of preparation entailed the use of zirconium sulfate and titanium oxysulfate as starting materials and ammonium hydroxide as precipitating agent. The produced oxides were washed to different extents to obtain samples with different sulfate content. A second preparative mode used zirconium oxychloride and titanous chloride as starting materials also with ammonium hydroxide as precipitating agent. The oxidation of the titanous to the titanic form for these oxides was carried out by means of oxygen gas. Resulting samples were heat treated at 400 °C and 600 °C, and textural characteristics determined from the adsorption of N₂ at 77 K, complemented by infrared and thermal studies. The samples precipitated from the oxychloride and chloride salts of zirconium and titanium, as well as those precipitated from the sulfate and oxysulfate salts and washed free of the sulfate ions displayed quite similar textural characteristics. The unheated samples and those heat-treated at 400 °C were mesoporous, with some microporosity, and relatively large surface areas in the order of 200–300 m²/g. Heat treatment to 600 °C led to a relative decrease in surface area, in the order of 100 m²/g, and to the disappearance of microporosity. The mixed zirconium and titanium oxides with a sulfate content of ≈17% displayed significantly lower surface areas, smaller than 10 m²/g, with a prevalence of micro and mesoporosity. Infrared and thermal studies indicated the presence of differently bounded sulfato groups, which seem to have a blocking effect on the pores, resulting in the observed smaller surface areas.     

Palladium‐catalysed Suzuki cross‐coupling of primary alkylboronic acids with alkenyl halides

The Suzuki reaction of primary alkylboronic acids with alkenyl halides proceeds nicely using the air‐stable catalyst PdCl(C₃H₅)(dppb), Cs₂CO₃ as base and toluene or xylene as solvent. A minor effect of the substituent position of the alkenyl bromide was observed. Quite similar yields were observed in the presence of α‐ or β‐substituted alkenyl bromides such as 2‐bromobut‐1‐ene or 1‐bromo‐2‐methylprop‐1‐ene with this catalyst. This reaction proceeded with a variety of alkylboronic acids such as 2‐phenylethylboronic acid or n‐octylboronic acid. Lower yields of coupling products were obtained in the presence of an alkenyl chloride. Copyright © 2008 John Wiley & Sons, Ltd.     

N-Vinylformamide – Building Block for Novel Polymer Structures

Abstract

N-Vinylformamide (NVF, N-ethenylformamide) is a precursor to amide and amine functional polymers and to other monomers, oligomers, and functional polymers. NVF shows attractive physical and toxicological properties and high reactivity, both in polymerization and in subsequent hydrolysis to cationic and reactive amine functional polymers or oligomers. NVF radical polymerization readily yields water soluble homopolymers with molecular weights from 10⁴ to >10⁶. Copolymerizability is similar to other vinyl amides. Unexpectedly, NVF will also undergo cationic oligomerization. Hydrolysis of polymers and copolymers with base or acid is facile, although reactions with neighboring groups (e.g., with coacrylate ester groups to give lactams) complicate copolymer hydrolysis.

Reaction of NVF at the unusually acidic NH group allows reaction with isocyanates to give vinylacylureas or Michael addition to acrylates to give a family of new N-vinylformamidopropionate esters. These esters in turn react with functional amines to generate new families of divinyl, vinyl/alcohol functional, or vinyl/amino functional comonomers. Applications for NVF and its derived monomers and polymers appear numerous, in particular in radiation cure coatings, based on their good physical and toxicological properties.     

A Biomimetic Catalytic Aerobic Functionalization of Phenols

The importance of aromatic C? O, C? N, and C? S bonds necessitates increasingly efficient strategies for their formation. Herein, we report a biomimetic approach that converts phenolic C? H bonds into C? O, C? N, and C? S bonds at the sole expense of reducing dioxygen (O₂) to water (H₂O). Our method hinges on a regio‐ and chemoselective copper‐catalyzed aerobic oxygenation to provide ortho‐quinones. ortho‐Quinones are versatile intermediates, whose direct catalytic aerobic synthesis from phenols enables a mild and efficient means of synthesizing polyfunctional aromatic rings.     

Towards the numerical simulation of the horizontal slug front

Steps towards the numerical simulation of the flow behind the slug front in horizontal slug flow performed with a streamfunction-vorticity representation of the mean flow and an energy dissipation model for the turbulence are discussed. The flow field consists of two vortices, one saddle point and four stagnation regions. Attention is focused on the following boundary conditions: moving wall jet, moving wall, free jet velocity discontinuity and vertical liquid-gas open surface. A dissipation flux boundary condition is suggested to simulate the interaction of the turbulent eddies with the open surface. A method to assess the necessity to use a transport model equation for the dissipation rather than a geometric specification of a length is suggested. Three different ways to characterize the mixing zone length are proposed.     

Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry

Elucidating single-atom effects on the fundamental properties of nanoparticles is challenging because single-atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu₅₈H₂₀PET₃₆(PPh₃)₄]²⁺ ( Cu₅₈ ; PET: phenylethanethiolate; PPh₃: triphenylphosphine) nanocluster—an atomically precise nanoparticle—that can be transformed into the surface-defective analog [Cu₅₇H₂₀PET₃₆(PPh₃)₄]⁺ ( Cu₅₇ ). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu₅₇ . Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu₅₈ , Cu₅₇ shows promising activity for click chemistry, particularly photoinduced [3+2] azide-alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu₅₇ after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single-surface atom modification on nanoparticle properties but also showcases single-atom surface modification as a powerful means for designing nanoparticle catalysts.