Polysaccharide Hydroxyapatite (Nano)composites and Their Biomedical Applications: An Overview of Recent Years.

Hydroxyapatite can combine with polysaccharide originating biomaterials with special applications in the biomedical field. In this review, the synthesis of (nano)composites is discussed, focusing on natural polysaccharides such as alginate, chitosan, and pectin. In this way, advances in recent years in the development of preparing materials are revised and discussed. Therefore, an overview of the recent synthesis and applications of polyssacharides@hydroxyapatites is presented. Several studies based on chitosan@hydroxyapatite combined with other inorganic matrices are highlighted, while pectin@hydroxyapatite is present in a smaller number of reports. Biomedical applications as drug carriers, adsorbents, and bone implants are discussed, combining their dependence with the nature of interactions on the molecular scale and the type of polysaccharides used, which is a relevant aspect to be explored.

Hydrogel Based on Nanoclay and Gelatin Methacrylate Polymeric Matrix as a Potential Osteogenic Application.

A nanocomposite hydrogel has potentially applicability in the induction of osteogenesis. The hydrogel was synthesized using 1% gelatin methacrylate (GelMA), a biodegradable and bioactive polymer containing the structure of gelatin, denatured collagen derived from the extracellular bone matrix, and 6% laponite (Lap), a synthetic phyllosilicate of nanosized particles. Initially, 0.6 g of Lap was added to deionized water, and then a solution of GelMA/Igarcure was added under stirring and UV light for crosslinking. The spectra in the Fourier-transform infrared region showed bands that indicate the interaction between gelatin and methacrylate anhydride. X-ray diffraction patterns confirmed the presence of Lap and GelMA in the hydrogel. The thermogravimetric analysis suggested an increase in the thermal stability of the hydrogel with the presence of clay mineral. Rheological analysis showed that the hydrogel had a viscosity that allowed its injectability. The hydrogel did not show acute toxicity at any of the concentrations tested according to the Artemia salina lethality test. It showed cell viability more significant than 80% in the MTT test, which makes it suitable for in vivo osteogenic induction tests. The cell differentiation test showed the differentiation of stem cells into osteogenic cells. It indicates a material with the potential for osteogenic induction and possible application in bone tissue engineering.

Montmorillonite with essential oils as antimicrobial agents, packaging, repellents, and insecticides: an overview.

Essential oils (EOs) are complex natural mixtures of secondary plant metabolites that function as biocides and therapeutic agents. They are extensively used in bactericidal, virucidal, fungicidal, antiparasitic, insecticidal, pharmaceutical, and cosmetic products. However, certain characteristics, such as the volatility of EOs, hinder their widespread use. To mitigate this limitation, several studies have investigated combinations of EOs with natural materials, including clay minerals. Clay minerals are abundant in nature, biocompatible, and non-toxic to the environment and humans. Clay minerals such as montmorillonite possess available sites where EO molecules can interact. The combination of EOs with clay minerals produces new materials for various applications including antibacterial, antifungal, insecticidal/repellent, and active packaging materials. Therefore, this review focuses on the immobilization of several types of EOs in raw and modified montmorillonites. The applications of the described systems were evaluated and demonstrated the synergism of the properties of the isolated components as a function of different EOs incorporated in the silicate matrix.

Clay Mineral Minerals as a Strategy for Biomolecule Incorporation: Amino Acids Approach.

The potential use of amino acids by ruminal microorganisms converting them into microbial protein for ruminants makes it challenging to supplement these nutrients in an accessible form in animals' diets. Several strategies to protect amino acids from ruminal degradation were reported, producing amino acids available for the protein used in the intestine called "bypass." The intercalation of biomolecules in clay mineral minerals has gained notoriety due to its ability to support, protect, transport, physicochemical properties and non-toxicity. This study aimed to investigate the incorporation of L-lysine (Lys), L-methionine (Met), and L-tryptophan (Trp) amino acids in the clay minerals sepiolite (Sep) and Veegum® (Veg) using the adsorption method. The characterization techniques of X-ray diffraction and infrared spectroscopy indicated the presence of biomolecules in the inorganic matrices. Elemental and thermal analyzes monitored the percentages of incorporated amino acids. They showed better incorporation capacities for Veg, such as Met-Veg < Lys-Veg < Trp-Veg and Lys-Sep < Met-Sep < Trp-Sep for sepiolite, except for the incorporation of Met. Matrices provide a promising alternative for planning the administration of biomolecules, using essential amino acids as models, and may offer an alternative to improve functional diet strategies.

Catechins as Model Bioactive Compounds for Biomedical Applications.

Research regarding polyphenols has gained prominence over the years because of their potential as pharmacological nutrients. Most polyphenols are flavanols, commonly known as catechins, which are present in high amounts in green tea. Catechins are promising candidates in the field of biomedicine. The health benefits of catechins, notably their antioxidant effects, are related to their chemical structure and the total number of hydroxyl groups. In addition, catechins possess strong activities against several pathogens, including bacteria, viruses, parasites, and fungi. One major limitation of these compounds is low bioavailability. Catechins are poorly absorbed by intestinal barriers. Some protective mechanisms may be required to maintain or even increase the stability and bioavailability of these molecules within living organisms. Moreover, novel delivery systems, such as scaffolds, fibers, sponges, and capsules, have been proposed. This review focuses on the unique structures and bioactive properties of catechins and their role in inflammatory responses as well as provides a perspective on their use in future human health applications.

Kaolinite/cashew gum bionanocomposite for doxazosin incorporation and its release.

Incorporation of drugs in clay minerals has been widely proposed for the controlled-release or increased solubility of drugs. In this context, a bionanocomposite based on kaolinite and cashew gum (Kln/Gum) was synthesized and characterized by X-ray diffraction (XRD), thermal analysis (TG/DTA), and Fourier transform infrared spectroscopy (FTIR). The bionanocomposite was applied to the incorporation and further release of doxazosin mesylate (DB). The influence of solution pH (1-3), adsorbent dose (20-50 mg), initial drug concentration (20.0-70.0 mg L-1), contact time (15-300 min), and temperature (25, 35, and 45 °C) were systematically evaluated. Equilibrium was reached around 60 min, with a maximum adsorption capacity of 31.5 ± 2.0 mg g-1 at a pH of 3.0 and 25 °C. Hydrogen bonding contributed to DB incorporation on the Kln/Gum. In addition, DB maximum amounts of 16.80 ± 0.58 and 77.00 ± 2.46% were released at pH values of 1.2 and 7.4, respectively. These results indicated that the Kln/Gum bionanocomposite is an effective and promising material for the incorporation/release of drugs with similar structures to DB.

Thiabendazole/bentonites hybrids as controlled release systems.

Clay minerals are commonly used in pharmaceutical products as excipients and active agents. New drug vehicles based on clay minerals have been developed. In this work, sodium (BentNa), calcium (BentCa) and magnesium (BentMg) exchanged bentonites were used for the sorption of thiabendazole (TBZ), and their potential use as controlled release systems was evaluated. Pristine bentonite and exchanged bentonites were characterized by X-ray diffraction, infrared spectroscopy, thermogravimetry and transmission electron microscopy (TEM), and the influence of the different parameters such as pH, contact time and initial concentration of the drug was investigated. The maximum adsorption reached after 45 min period with 2000 mg L-1 of thiabendazole to BentNa and after 105 min with 1300 mg L-1 to BentCa and BentMg, respectively. The maximum adsorbed quantities of thiabendazole were 164.4; 152.3 and 133.3 mg g-1 for BentNa, BentCa and BentMg, respectively. The emission profiles obtained for the bentonite/drug hybrids were similar when simulated body fluids were used and these emission profiles were fitted according to the Korsmeyer-Peppas kinetic model.

Going through the wine fining: Intimate dialogue between organics and clays.

Wine chemistry inspires and challenges with its complexity and intriguing composition. In this context, the composites based on the use of a model protein, a polyphenol of interest and montmorillonite in a model hydroalcoholic solution have been studied. A set of experimental characterization techniques highlighted the interactions between the organic and the inorganic parts in the composite. The amount of the organic part was determined by ultraviolet-visible (UV-VIS) and thermal analysis. X-ray diffraction (XRD) and transmission electronic microscopy (TEM) informed about the stacking/exfoliation of the layers in the composites. Vibrational and nuclear magnetic resonance spectroscopies methods stressed on the formation of a complex between the protein and the polyphenol before adsorption on the clay mineral. The mobility/rigidity of the organic parts were determined by fluorescence time resolved spectroscopy. Changes in the secondary structure of the protein occured upon complexation with polyphenol on clay mineral due to strong interactions. Although not representating faithfully enological conditions, these results highlight the range and nature of mechanisms possibly involved in wine fining.

Silylation of leached-vermiculites following reaction with imidazole and copper sorption behavior.

Organically modified vermiculites were synthesized by previous silylation of three leached vermiculites, V0.3Cl, V0.5Cl and V0.8Cl, under anhydrous conditions following reaction with imidazole (Im), which acted as chelating agent for copper retention. Elemental analysis, X-ray diffraction, infrared spectroscopy, scanning electronic microscopy, transmission electron microscopy, (29)Si and (13)C NMR and nitrogen adsorption/desorption measurements were used to characterize pristine, leached and organofunctionalized solids. X-ray photoelectron spectroscopy (XPS) was used to evaluate the surface after copper sorption. Parameters such as contact time, pH and initial cation concentration for the adsorption of Cu(II) ions were investigated. The adsorption equilibrium data were fitted using the Langmuir isotherm model and the monolayer adsorption capacities were 2.38, 2.52 and 2.69mmolg(-1) for V0.5Cl-Im, V0.3Cl-Im and V0.8Cl-Im, respectively, at pH 6.0 and 298K for a time reaction of 80min. The sorption rates were described by pseudo-second-order kinetics. The chloropropyl imidazole vermiculites are promising adsorbents for the rapid removal of Cu(II) ions from aqueous solution.

Neck Circumference Is Independently Associated with Cardiometabolic Risk Factors: Cross-Sectional Analysis from ELSA-Brasil.

BACKGROUND: Neck circumference (NC) is a simple anthropometric measurement that may be linked with cardiometabolic risk factors. We analyzed the association between NC and a range of cardiometabolic risk factors. METHODS: In a cross-sectional and sex-specific analysis of the ELSA-Brasil study (15,105 civil servants aged 35-74 years), we excluded participants with diabetes, taking antihypertensive and/or lipid-lowering drugs. Cardiometabolic risk factors were homeostasis model assessment of insulin resistance (≥ 75th percentile), low high-density lipoprotein (HDL; <50 mg/dL for women and <40 mg/dL for men), high triglycerides ≥ 150 mg/dL, systolic blood pressure ≥ 130 mmHg, or diastolic blood pressure ≥ 85 mmHg. Logistic regression models were built to analyze the association between individual and clustered risk factors and 1-standard deviation (SD) increase in NC after adjustments for age, smoking, alcohol, body mass index, and waist circumference. RESULTS: We analyzed 8726 participants (56.3% women), with a mean age of 49.2 ± 8.0 years. Mean NC was 38.9 ± 2.6 cm for men and 33.4 ± 2.6 cm for women. Fully adjusted odds ratios (ORs) [95% confidence intervals (CIs)] per 1-SD increase in NC in men and women were, respectively, 1.32 (1.16-1.51) and 1.47 (1.31-1.64) for insulin resistance; 1.24 (1.11-1.39) and 1.25 (1.11-1.40) for raised blood pressure; 1.50 (1.33-1.70) and 1.51 (1.33-1.70) for high triglycerides; and 1.22 (0.92-1.61) and 1.54 (1.23-1.86) for low HDL. Fully adjusted ORs (95% CI) of three or more clustered risk factors per 1-SD increase in NC in men and women were 1.54 (1.34-1.79) and 1.71 (1.41-2.06). CONCLUSION: NC is significantly and independently associated with cardiometabolic risk factors in a well-defined apparently healthy population.

Immobilization of ethylene sulfide in aminated cellulose for removal of the divalent cations.

Cellulose (Cel) was first chemically modified with thionyl chloride to increase its reactivity. In the next step CelCl was reacted with ethylenediamine (CelEn) and subsequently reacted with ethylene sulfide to obtain a solid substance, CelEnEs. The modification reactions were confirmed by elemental analysis, TG, XRD, (13)C NMR and FTIR. The chemically modified biopolymer CelEnEs had an order of divalent metal sorption of Pb(2+)>Cd(2+)>Ni(2+)>Co(2+)>Cu(2+)>Zn(2+), and the maximum adsorption capacities were found to be 6.282±0.023, 5.783±0.015, 5.561±0.017, 4.694±0.013, 1.944±0.062 and 1.733±0.020 mmol g(-1), respectively. The equilibrium data were fitted to Langmuir, Freundlich and Temkin models, and in general, the experimental data best fit the Freundlich model. This newly synthesized biopolymer proved to be a chemically useful material for cations removal from aqueous solution.

Cation removal using cellulose chemically modified by a Schiff base procedure applying green principles.

Pentane-2,4-dione (acetylacetone) molecules were covalently incorporated under several different conditions to ethylene-1,2-diamine (en)-modified cellulose, using polar solvents or without solvents. The quantitative amount of en incorporated was given from 0.37+/-0.01 to 3.03+/-0.01 mmol of nitrogen per gram of cellulose, depending on the synthetic routes and after Schiff base formation this percentage was reduced by 1.38-6.12%. The synthetic routes indicated that lower solvent volumes produced higher amounts of en incorporation. However, the highest degree of pendant groups on the polymeric cellulose structure was obtained from a solvent-free reaction route. This procedure was applied for synthesizing all Schiff bases, causing a decrease in the amount of nitrogen. The available basic centers on the best covalently bonded biopolymer were investigated for adsorption of divalent copper, cobalt, nickel, and zinc from aqueous solution, with a capacity order of Cu2+ > Co2+ > Ni2+ > Zn2+.

Differential survival benefit of universal HAART access in Brazil: a nation-wide comparison of injecting drug users versus men who have sex with men.

OBJECTIVE: Brazil accounts for approximately 70% of injection drug users (IDUs) receiving highly active antiretroviral therapy (HAART) in low-income/middle-income countries. We evaluated the impact of HAART availability/access on AIDS-related mortality among IDUs versus men who have sex with men (MSM). DESIGN: Nation-wide analysis on Brazilian IDU and MSM diagnosed with AIDS in 2000-2006. METHODS: Four national information systems were linked, and Cox regression was used to assess impact of HAART availability/access on differential AIDS-related mortality. RESULTS: Among 28,426 patients, 6777 died during 87,792 person-years of follow-up. Compared with MSM, IDU were significantly less likely to be receiving HAART, to have ever had determinations for CD4 or viral load. After controlling for confounders, IDU had a significantly higher risk of death (adjusted hazard ratio: 1.94; 95% confidence interval: 1.84 to 2.05). Among the subset that had at least 1 CD4 and viral load determination, higher risk of death among IDU persisted (hazard ratio: 1.82; 95% confidence interval: 1.58 to 2.11). Nonwhite ethnicity significantly increased this risk, whereas prompt HAART uptake after AIDS diagnosis reduced the risk of death. After controlling for spatially correlated survival data, AIDS-related mortality remained higher in IDU than in MSM. CONCLUSIONS: Despite free/universal HAART access, differential AIDS-related mortality exists in Brazil. Efforts are needed to identify and eliminate these health disparities.

Hydroxyapatite organofunctionalized with silylating agents to heavy cation removal.

Hydroxyapatite surface silylation with organosilane derivatives (H3CO)3SiR, R being the corresponding organic moieties CH2CH2CH2NH2, CH2CH2CH2NHCH2CH2NH2, and CH2CH2CH2NHCH2CH2NHCH2CH2NH2, was carried out to yield organofunctionalized nanomaterials, named HApR1, HApR2, and HApR3, respectively. The products were characterized by elemental analysis, infrared spectroscopy, X-ray diffraction, thermogravimetry, and (1P and 13C NMR in the solid state. The amounts of groups grafted onto surfaces were 0.75+/-0.05, 2.35+/-0.14, and 2.48+/-0.18 mmolg(-1) for HApRx (x=1,2,3) surfaces, respectively. Linear correlations between elemental analysis, mass loss, (31)P chemical shift data, and the characteristics of the chain of each alkoxysilane were observed. The organic basic centers distributed onto the external surface have the ability to adsorb divalent copper and cobalt cations from aqueous solution. The degree of adsorption obtained from batchwise processes showed the best performance of these synthesized nanomaterials when compared with the pristine hydroxyapatite.

Removal of cadmium, zinc, manganese and chromium cations from aqueous solution by a clay mineral.

Vermiculite, a 2:1 clay mineral, was applied as adsorbent for removal of cadmium, zinc, manganese, and chromium from aqueous solutions. Parameters such as time of reaction, effect of pH and cation concentration were investigated. All isotherms were L type of the Gilles classification, except zinc (type S). The adsorbent showed good sorption potential for these cations. The experimental data was analyzed by Langmuir isotherm model showing reasonable adjustment. The quantity of adsorbed cations was 0.50, 0.52, 0.60, and 0.48 mmol g(-1) of Cd(2+), Mn(2+), Zn(2+), and Cr(3+), respectively.

Natural vermiculite as an exchanger support for heavy cations in aqueous solution.

The natural highly charged lamellar silicate vermiculite was investigated as an exchanger matrix in doubly distilled water solution to exchange magnesium inside the lamella with the heavy cations copper, nickel, cobalt, and lead at the solid/liquid interface. The extension of each exchange reaction was dependent on time of reaction, pH, and cation concentration. The maximum time presented the following order Pb2+ < Ni2+ < Cu2+ < Co2+, which corresponds to 12, 24, 48, and 72 h, respectively. The best performance was observed for nickel, as represented by the exchange capacity Nf, which gave values 0.59, 0.76, 0.84, and 0.93 mmol g(-1) for Pb2+ < Co2+ < Cu2+ < Ni2+, respectively. This capacity is dependent on pH interval variation from 1 to 9, being significantly increased in alkaline condition. The isotherm data were adjusted to a modified Langmuir equation and from the data the spontaneous Gibbs free energy was calculated. Linear correlations were obtained through Gibbs free energy or the maximum capacity against the cationic radius plot, with the lowest values for the largest cation lead. An exponential correlation was also observed for the maximum capacity versus enthalpy of hydration plot, indicating a difficulty of the less hydrated cation, lead, in exchanging with magnesium inside the lamellar space, as suggested by the proposed mechanism. The saturated matrices with cations presented a decrease in interlayer distance in comparison with the original vermiculite, which can be related to the hydrated phases, characteristic for each cation, with a lowest value for lead.

Thioglycolic acid grafted onto silica gel and its properties in relation to extracting cations from ethanolic solution determined by calorimetric technique.

Thioglycolic acid was immobilized onto silica gel surface using 3-aminopropyltrimethoxysilane as precursor silylating agent to yield silica. The amount of thioglycolic acid immobilized was 1.03 mmol per gram of silica. This new surface displayed a chelating moiety containing nitrogen, sulfur, and oxygen basic centers which are potentially capable of extracting cations from ethanolic solution, such as MCl3 ( M=Fe, Cr, and Mo). This process of extraction was carried out by the batch method when similar chemisorption isotherms were observed for all cations. The data were adjusted to a modified Langmuir equation. The sequence of the maximum retention capacity was Cr(III) > Mo(III) > Fe(III). The same adsorption was determined by calorimetric titration and the enthalpic values of -35.75 +/- 0.02, 32.90 +/- 0.15, and -84.08 +/- 0.12 kJmol(-1) for chromium, molybdenum, and iron, respectively, were obtained. From the calculated Gibbs free energy -23.4 +/- 0.2, -27.2 +/- 0.2, and -32.7 +/- 0.3 kJmol(-1), the variations in entropy obtained were 42 +/- 1, 201 +/- 1, 172 +/- 1 JK(-1)mol(-1) for the same sequence. All thermodynamic values are in agreement with the spontaneity of the proposed cation-basic center interactions for these chelating processes.

Silica gel containing sulfur, nitrogen and oxygen as adsorbent centers on surface for removing copper from aqueous/ethanolic solutions.

Silica gel was modified firstly with aminepropyltrimethoxisilane obtaining the matrix named as SILNH(2). The SILNH(2) silica reacted subsequently with thioglycolic acid Sil-Ntga. The elemental analysis showed the presence of 0.98mmolg(-1) of organic moieties immobilized on silica. Infrared and (13)C NMR spectroscopic data in conjunction with thermogravimetric measurements are in agreement with the suggested functionalization. The ion adsorption properties of the silica Sil-Ntga were studied using copper ions in aqueous/ethanolic solutions in concentrations ranging from 4.0x10(-3) to 5.0x10(-2)moldm(-3) at different temperatures. The new modified silica showed a good sorption ability for copper at lower temperatures and its reuse capacity was demonstrated.

New thiol adsorbent grafted on silica gel: synthesis, characterization and employment for heavy metal adsorptions.

Silica gel surface has been modified in two reaction steps: (i) the silylating agent 3-mercaptopropyltrimetoxysilane was firstly immobilized to give a surface Sil-SH and (ii) this precursor incorporated an ethylene sulfide molecule to obtain the surface denoted Sil-SSH. This material was characterized by elemental analysis, IR spectroscopy, thermogravimetry, solid state 13C and 29Si NMR, and surface area measurement. These materials were employed as adsorbents for divalent heavy cations from aqueous solutions at room temperature and the isotherms were adjusted to a modified Langmuir equation. The maxima number of moles adsorbed were 1.0, 1.5, 1.6, 2.2, 2.4 and 3.3 mmol g(-1) for Co, Cu, Ni, Cd, Pb, and Hg, respectively.

Silylating Agents Grafted onto Silica Derived from Leached Chrysotile.

Silica from leached chrysotile fibers (SILO) was silanized with trialkoxyaminosilanes to yield inorganic-organic hybrids designated SILx (x=1-3). The greatest amounts of the immobilized agents were quantified as 2.14, 1.90, and 2.18 mmol g(-1) on SIL1, SIL2, and SIL3 for -(CH(2))(3)NH(2),-(CH(2))(3)NH(CH(2))(2)NH(2), and -(CH(2))(3)NH(CH(2))(2)NH(CH(2))(2)NH(2) groups attached to the inorganic support. The infrared spectra for all modified silicas showed the absence of the Si-OH deformation mode, originally found at 950 cm(-1), and the appearance of asymmetric and symmetric C-H stretching bands at 2950 and 2840 cm(-1). Other important bands associated with the organic moieties were assigned to nu(as)(NH) at 3478 and nu(sym)(NH) at 3418 cm(-1). The NMR spectrum of the solid precursor material suggested two different kinds of silicon atoms: silanol and siloxane groups, between -90 and 110 ppm; however, additional species of silicon that contain the organic moieties bonded to silicon at -58 and -66 ppm appeared after chemical modification. These modified silicas showed a high adsorption capacity for cobalt and copper cations in aqueous solution, in contrast to the original SILO matrix, confirming the unequivocal anchoring of silylating agents on the silica surface. Copyright 2001 Academic Press.