Transport of ionizable drugs and proteins in crosslinked poly(acrylic acid) and poly(acrylic acid-co-2-hydroxyethyl methacrylate) hydrogels. I. Polymer characterization

The purpose of this investigation was to define the polymer structure and elucidate the swelling behavior of ionizable hydrophilic polymers (hydrogels) in water and buffered media. Poly(acrylic acid) (PAA) and poly(acrylic acid-co-2-hydroxyethyl methacrylate) [P(AA-co-HEMA)] hydrogels were synthesized with varying degrees of hydrophilicity and crosslinking and were designed as potential bioadhesive controlled-release dosage forms. The thermal initiation procedure employed during polymerization was optimized to eliminate unreacted residuals. Equilibrium and dynamic swelling studies were undertaken to determine the polymer mesh size and molecular weight between crosslinks of the hydrogels in the ionized and nonionized states. The PAA hydrogel mesh sizes ranged from 100 to 400 Å over pH values of 3–7, whereas the P(AA-co-HEMA) hydrogel mesh sizes were between 13 and 140 Å. These results demonstrated the significance of the swelling medium pH on the hydrated state of the polymers relative to crosslinking or copolymerization composition. © 1996 John Wiley & Sons, Inc.     

Serum beta-carotene and antioxidant micronutrients in children with cancer. The 'Cancer in Children and Antioxidant Micronutrients' French Study Group

Serum antioxidant vitamins A (retinol) and E (alpha-tocopherol), beta-carotene, zinc and selenium for 418 children with newly diagnosed malignancy were compared with those of 632 cancer-free controls. Incident cancer cases and controls were 1-16 years old and recruited in 1986-1989. Age- and sex-adjusted serum concentrations of retinol, beta-carotene and alpha-tocopherol were significantly inversely associated with cancer. In similar models, the odds ratio (OR) comparing the highest with the lowest quintile was 2.06 (95% confidence interval [CI] 1.40-3.02) for retinol, 3.87 (95% CI: 2.54-5.90) for beta-carotene, 2.15 (95% CI: 1.48-3.10) for alpha-tocopherol, 1.29 (95% CI: 0.75-2.23) for selenium, and 1.94 (95% CI: 1.17-2.23) for zinc. The cancer sites that were associated with serum beta-carotene were, in general, leukaemia, lymphoma, central nervous system, bone and renal tumours. Moreover, leukaemia was associated with low mean serum levels of retinol, selenium and zinc. Subjects with lymphoma, bone and renal tumours also had lower mean retinol and alpha-tocopherol levels than controls. Brain tumour patients had low vitamin E levels. Low serum values of antioxidant vitamins were associated with childhood neoplasm occurrence. Some site-specific effect was reported. Low peripheral nutrient levels are not considered as cancer promoters but rather as an impairment of the body's defence mechanism occurring during the cancer-related metabolic and nutritional disturbances and inflammation processes.     

Adhesives based on polyurethane graft multiblock copolymers: Tack,rheology and first morphological analyses

In this contribution, we report on the characterization of novel polyurethane graft-copolymers containing poly(n-butyl acrylate) side chains and, when extended, crystallizable polycaprolactone segments. Based on the previously reported synthesis, we attempt in the present work to correlate polymer structure and properties of segmented polyurethanes focussing on its potential interest as pressure-sensitive adhesive nanomaterial. For that purpose, thermomechanical analyses were coupled with complementary tack tests, rheology experiments and atomic force microscopy (AFM) imaging. Parameters such as relative hard and soft segments fraction or the introduction of crystallisable fragments that can play an important role on the adhesive comportment are described as well.     

Polyurethane fibrous membranes tailored by rotary jet spinning for tissue engineering applications

Polymeric membranes have gained popularity as fibrous structures for tissue regeneration. This research focuses on the rotary jet spinning (RJS) process combined with a polymer as a strategy for designing membranes. To this end, RJS-polyurethane (RJS-PU) membranes with different microstructures were produced. Considering the effects of solution properties on fiber production, the viscosity of PU solutions was evaluated. Membrane morphology was studied based on scanning electron microscopy and 2D fast Fourier transform analysis. The chemical and thermal properties were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis, respectively. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide and Live/Dead cell assays were performed to determine the material cytotoxicity by assessment of the profile of proliferation and cell viability. The results indicated that the combination of PU and RJS was an effective one for the production of fibrous structures for tissue engineering applications, demonstrating good compatibility with the cultured osteoblastic cell line. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48455.     

Physicochemical and sensory evaluation of wine brandies aged using oak and chestnut wood simultaneously in wooden barrels and in stainless steel tanks with staves

This study provides innovative information on the simultaneous use of Limousin oak and chestnut wood in the ageing of wine brandy. Ageing was performed in 650‐L wooden barrels and in 3000‐L stainless steel tanks with staves over a 2‐year period. Effect of both kinds of wood in the brandy features depended on the ageing technology. Stainless steel tanks with staves originated lower enrichment of the brandy in dry extract (0.89 vs. 1.25 g L^?1), total phenolics (22.33 vs. 29.40) and low molecular weight extractable compounds (119.83 vs. 231.65 mg L^?1), but promoted a faster evolution of the analytical colour (lower L*, higher C*, a* and b*) and sensory colour (topaz and greenish vs. golden). The aroma and flavour profiles of the brandy were not significantly influenced by the ageing technology. Therefore, it is a promising option for both ageing technologies because it ensures the quality of brandy, together with a lower cost of the wood and exemption of the blending operation.     

The Oxidative Fermentation of Ethanol in Gluconacetobacter diazotrophicus Is a Two-Step Pathway Catalyzed by a Single Enzyme: Alcohol-Aldehyde Dehydrogenase (ADHa)

Gluconacetobacter diazotrophicus is a N₂-fixing bacterium endophyte from sugar cane. The oxidation of ethanol to acetic acid of this organism takes place in the periplasmic space, and this reaction is catalyzed by two membrane-bound enzymes complexes: the alcohol dehydrogenase (ADH) and the aldehyde dehydrogenase (ALDH). We present strong evidence showing that the well-known membrane-bound Alcohol dehydrogenase (ADHa) of Ga. diazotrophicus is indeed a double function enzyme, which is able to use primary alcohols (C2–C6) and its respective aldehydes as alternate substrates. Moreover, the enzyme utilizes ethanol as a substrate in a reaction mechanism where this is subjected to a two-step oxidation process to produce acetic acid without releasing the acetaldehyde intermediary to the media. Moreover, we propose a mechanism that, under physiological conditions, might permit a massive conversion of ethanol to acetic acid, as usually occurs in the acetic acid bacteria, but without the transient accumulation of the highly toxic acetaldehyde.     

Bead-based competitive fluorescence immunoassay for sensitive and rapid diagnosis of cyanotoxin risk in drinking water

Due to the increased occurrence of cyanobacterial blooms and their toxins in drinking water sources, effective management based on a sensitive and rapid analytical method is in high demand for security of safe water sources and environmental human health. Here, a competitive fluorescence immunoassay of microcystin-LR (MCYST-LR) is developed in an attempt to improve the sensitivity, analysis time, and ease-of-manipulation of analysis. To serve this aim, a bead-based suspension assay was introduced based on two major sensing elements: an antibody-conjugated quantum dot (QD) detection probe and an antigen-immobilized magnetic bead (MB) competitor. The assay was composed of three steps: the competitive immunological reaction of QD detection probes against analytes and MB competitors, magnetic separation and washing, and the optical signal generation of QDs. The fluorescence intensity was found to be inversely proportional to the MCYST-LR concentration. Under optimized conditions, the proposed assay performed well for the identification and quantitative analysis of MCYST-LR (within 30 min in the range of 0.42-25 μg/L, with a limit of detection of 0.03 μg/L). It is thus expected that this enhanced assay can contribute both to the sensitive and rapid diagnosis of cyanotoxin risk in drinking water and effective management procedures.     

Phenolic Compounds from the Leaves of Vitis labrusca and Vitis vinifera L. as a Source of Waste Byproducts: Development and Validation of LC Method and Antichemotactic Activity

The cultivation of Vitis (Vitaceae) grape varieties is one of the most important economic activities in agribusiness in southern Brazil. Vitis varieties are rich in polyphenolic compounds with several pharmacological and biological activities, such as antioxidant action. In this context, this study analyzed qualitatively and quantitatively the anthocyans and flavonoids found in the leaves of grape varieties Vitis vinifera and Vitis labrusca. For this purpose, vine leaf extracts were prepared and the chemical profile of each was characterized by LC/MS-MS. Two high performance liquid chromatography-validated methods were performed using UV/VIS-LC-DAD detector to quantify phenolic compounds. The main anthocyanins isolated from vine leaves were cyanidin-3-O-glucoside and peonidin-3-O-glucoside. The flavonoids identified were rutin, quercetin-3-O-galactoside, quercetin-3-O-glucoside, and quercetin-3-O-glucuronide, which was the predominant compound. The Waters X-Terra® RP18 column allowed the effective separation of quercetin-3-O-glucuronide from the other flavonoids for the first time, besides the partial separation of quercetin-3-O-galactoside from quercetin-3-O-glucoside. Furthermore, another phenolic compound was confirmed by MS spectrometry, using direct infusion, as being trans-caftaric acid. The present study also investigates the antichemotactic activity in vitro of grape crude extracts, fractions, and isolated compounds. It was demonstrated that almost all fractions and isolated compounds showed increased antichemotactic effect in response to LPS with a more pronounced values of IC₅₀ for anthocyanins fraction, rutin, quercetin-3-O-galactoside, and trans-caftaric acid (0.9, 1.6, 3.7, and 5.1 ng/mL, respectively).     

Nanopatterning in Langmuir-Blodgett monolayers of a thermoresponsive double hydrophilic block copolymer studied by atomic force microscopy

The microphase-separation of Langmuir-Blodgett (LB) monolayers of a rhodamine B (RhB) end-labeled double hydrophilic block copolymer (DHBC), RhB-Poly(N,N-dimethylacrylamide)-b-poly(N,N-diethylacryl-amide) (RhB-PDMA(207)b-PDEA177) and the 1:1 segmental mixture of PDEA and RhB-PDMA homopolymers was followed by AFM. The DHBC LB films revealed a loose distribution of nano-aggregates with variable geometries below the lower critical solution temperature (LCST) of PDEA (32 degrees C) and low surface pressure (3 mN m(-1)). By increasing either the temperature above the LCST of PDEA or the surface pressure beyond the immersion regime of PDMA in the subphase (7 mN m(-1)) a dense nanopatterning was obtained. The absence of a corresponding regular nanopatterning in LB films of mixed homopolymers with the same composition highlights the role of the covalent bonding between PDEA and PDMA on the self-segregation of the two blocks at the air-water interface.