Long-Term In Vitro Adhesive Properties of Two Universal Adhesives to Dentin.

The composition of universal adhesives, as well as the adhesive strategy, may influence bonding effectiveness and durability. This study aimed to evaluate the microtensile bond strength (µTBS) and nanoleakage (NL), immediately and after 6-month aging, and in situ degree of conversion (DC), of two universal adhesives (Scotchbond Universal Adhesive, SBU; Xeno Select, XEN) applied with etch-and-rinse (ER) and self-etch (SE) strategies, in comparison with a two-step SE adhesive (Clearfil SE Bond, CSE). Dentin surfaces of fifty human third molars were randomly assigned to the following adhesives: two universal adhesives, SBU and XEN, applied in ER or SE mode and CSE, used as control. Teeth were sectioned into beams to be tested under µTBS, half of them after 24 h, and the rest after 6 months of water aging. Selected beams from each tooth were used for NL evaluation and in situ DC quantification. SBU and CSE showed significantly higher mean µTBS and lower nanoleakage than XEN, regardless of the evaluation time and adhesion strategy. XEN-SE yielded the lowest degree of conversion. Therefore, adhesive properties of universal adhesives to dentin are material dependent, regardless of the adhesion strategy, exhibiting XEN a significantly worse performance than SBU.

Layer-by-layer vaginal films for acyclovir controlled release to prevent genital herpes.

Genital herpes is one of the most common sexually transmitted infections worldwide. It mainly affects women, as the rate of sexual transmission from male-to-female is higher than from female-to-male. The application of vaginal antivirals drugs could reduce the prevalence of genital herpes and prevent future infections. Layer-by-layer vaginal films were prepared by the solvent evaporation method using iota-carrageenan, hydroxypropyl methylcellulose and the polymethacrylates Eudragit® RS PO and Eudragit® S100, for the controlled release of acyclovir. The films were characterized by texture analysis and Raman spectroscopy. Swelling, mucoadhesion, and drug release studies were conducted in simulated vaginal fluid. The results show that Layer-by-Layer films exhibited adequate mechanical properties. The structuring of the layer-by-layer films allowed the controlled release of acyclovir and produced a prolonged mucoadhesion residence time of up to 192 h. The films formed in layer 2 by the combination of Eudragit® RS PO and S100 showed a controlled release of acyclovir for eight days, and adequate mechanical properties. These promising formulations for the prevention of genital herpes deserve further evaluation.

Silicon Oxycarbide Porous Particles and Film Coating as Strategies for Tenofovir Controlled Release in Vaginal Tablets for HIV Prevention.

Sustained release of antiretroviral drugs is currently the most encouraging strategy for the prevention of the sexual transmission of HIV. Vaginal tablets based on hydrophilic gelling polymers are an interesting dosage form for this purpose, since they can be developed to modify the release of the drug depending on the tablet swelling. Tenofovir is a drug with proven activity in the prevention of HIV-1 infection, and it is possible to have it loaded in the surface of γ-aminopropyl trimethoxy silane-functionalized oxycarbide particles. These particles can be incorporated into the tablets, thus providing a sustained release of the drug. Moreover, the presence of the particles modifies the microstructure of the gel formed, as observed in scanning electron microscopy and Hg porosimetry studies, resulting into a gel with a narrow pore size distribution between 10 and 100 µm. This implies a lower volume of fluid incorporated into the gel during swelling studies, and therefore improved mucoadhesion times in ex vivo test. The coating of the formulations with Eudragit® RS modifies the swelling behavior of the tablets, which not only is decreased in magnitude but also extended in time, and as consequence the drug release is also prolonged for up to 7 days.

Easy and Efficient Recovery of EMIMCl from Cellulose Solutions by Addition of Acetic Acid and the Transition from the Original Ionic Liquid to an Eutectic Mixture.

Ionic liquids (ILs) and deep eutectic solvents (DESs) are the two most widely used neoteric solvents. Recently, our group described how the simple addition of acetic acid (AcOH) to 1-Ethyl-3-methylimidazolium chloride (EMIMCl) could promote the transition from the original IL to an eutectic mixture of EMIMCl and AcOH. Herein, we studied how cellulose regeneration and EMIMCl recovery from EMIMCl solutions of cellulose could be benefited by the significant differences existing between EMIMCl- and EMIMCl·AcOH-based mixtures and the easy switching from one to the other. Finally, we also demonstrated that the transition could also be accomplished by addition of acetic anhydride and water so that the process could be eventually useful for the achievement of highly acetylated cellulose.

Optimized hydration dynamics in mucoadhesive xanthan-based trilayer vaginal films for the controlled release of tenofovir.

Karaya gum, pectin and xanthan gum have been tested as candidates for manufacturing mucoadhesive trilayer films containing ethylcellulose and chitosan for the vaginal administration of the antiviral Tenofovir (TFV). The swelling profile correlated with the amount of mobile dipoles determined by impedance spectroscopy allows the determination of the hydration dynamics of these films. The fast water penetration has been demonstrated to favor the formation of polyelectrolyte complexes (PEC) via hydrogen or ionic bonds which would favor a controlled release. The incorporation of an inorganic drug release regulator induces the weakness of the polymeric chains thus enhancing the ionic mobility via the formation of low molecular weight PECs in films manufactured with karaya gum. Due to the different mechanical properties of the individual components, pectin-based films failed for a potential pharmaceutical formulation. However, mucoadhesive trilayer films produced with xanthan gum have demonstrated a moderate swelling, improved wettability and a controlled release of TFV.

Bigels as drug delivery systems: From their components to their applications.

Bigels are systems that usually result from mixing a hydrogel and an organogel: the aqueous phase is commonly formed by a hydrophilic biopolymer, whereas the organic phase comprises a gelled vegetable oil because of the presence of an organogelator. The proportion of the corresponding gelling agent in each phase, the organogel/hydrogel ratio, and the mixing temperature and speed all need to be taken into consideration for bigel manufacturing. Bigels, which are particularly useful drug delivery systems, have already been formulated for transdermal, buccal, and vaginal routes. Mechanical assessments and microscopy are the most reported characterization techniques. As we review here, their composition and unique structure confer promising drug delivery attributes, such as mucoadhesion, the ability to control drug release, and the possibility of including both hydrophilic and lipophilic drugs in the same system.

Preparation and Properties of Sustainable Brake Pads with Recycled End-of-Life Tire Rubber Particles.

Sustainable composite brake pads were processed by employing recycled end-of-life tire (ELT) rubber particles obtained by means of cryogenic grinding and ambient grinding. The effect of the grinding mechanism and concentration of ELT rubber particles was then reported. From the friction result test, better behavior in terms of coefficient of friction (COF) was obtained when 3% of ELT rubber particles were introduced into the composite. It was demonstrated that the size of the particles is not as determinant as the friction mechanism in the wear properties of the sustainable brake pads. Whereas, while increasing the ELT rubber particle size acts as detrimental to the COF either in the ambient or cryogenic grinding, at high friction distances, the better adhesion of the particles because of the rough surface of the particles subjected to ambient grinding enhances the long-life behavior of the composite brake pads.

Silane Modification of Mesoporous Materials for the Optimization of Antiviral Drug Adsorption and Release Capabilities in Vaginal Media.

Three different functionalities have been incorporated into mesoporous materials by means of a coupling reaction with the siloxanes 3-glycidoxypropyl-trimethoxysilane (GLYMO), 3-methacryloxypropyl-trimethoxysilane (MEMO), and 3-mercaptopropyl-trimethoxysilane (MPTMS). The disposition of the different functional groups, as well as the interaction mechanism, with the mesoporous substrate has been identified. The amount of the antiviral drug acyclovir (ACV) adsorbed depends not only on the available surface area but also on the chemical or physicochemical interactions between functionalities. The drug adsorption isotherm of the materials functionalized with GLYMO and MPTMS follow mechanisms dependent on the different surface coverage and the possibilities to establish physicochemical interactions between the drug molecule and the functionalities. On the contrary, when functionalizing with MEMO, the dominant adsorption mechanism is characteristic of chemically bonded adsorbates. The ACV release kinetics is best fitted to the Weibull model in all the functionalized materials. When the MTPMS is used as a functionalizing agent, the drug diffusion occurs at low kinetics and homogeneously along the mesoporous channels.

Insights into the Microstructural Evolution Occurring during Pyrolysis of Metal-Modified Ceramers Studied through Selective SiO2 Removal.

Silicon oxycarbide ceramers containing 5% aluminum, zirconium, and cobalt with respect to the total Si amount are prepared from a commercial polysiloxane and molecular precursors and pyrolyzed at temperatures ranging from 500 to 1000 °C. HF etching is carried out to partially digest the silica phase, thus revealing structural characteristics of the materials, which depend upon the incorporated heteroatom. From the structural and textural characterization, it was deduced that when Al enters into the ceramer structure, the crosslinking degree is increased, leading to lower carbon domain size and carbon incorporation as well. On the contrary, the substitution by Zr induced a phase-separated SiO2-ZrO2 network with some degree of mesoporosity even at high pyrolysis temperatures. Co, however, forms small carbidic crystallites, which strongly modifies the carbonaceous phase in such a way that even when it is added in a small amount and in combination with other heteroatoms, this transient metal dominates the structural characteristics of the ceramer material. This systematic study of the ceramer compounds allows the identification of the ultimate properties of the polymer-derived ceramic composites.

Smart vaginal bilayer films of Tenofovir based on Eudragit® L100/natural polymer for the prevention of the sexual transmission of HIV.

In the absence of an effective vaccine, vaginal microbicides are essential for preventing the sexual transmission of HIV to women. Antiretroviral vaginal films have emerged as promising choices, especially those offering mucoadhesivity and controlled drug release. Tenofovir-loaded bilayer films based on Eudragit® L100 (EL100) and a biopolymer - gum arabic, karaya gum, pectin or tragacanth gum - were developed in a single-stage process. Cytotoxicity studies in three human cell lines indicated no toxicity of the excipients at the concentrations tested. Raman spectroscopy and SEM confirmed the formation of the two layers and their anchoring. Texture analysis showed no major differences between the batches. The swelling of the film is conditioned by its biopolymer nature and by the amount of EL100, which acts as structuring agent thus enhancing swelling. Tragacanth gum-based batches showed high mucoadhesion regardless the amount of EL100. The controlled release of Tenofovir in simulated vaginal fluid was faster in the presence of simulated seminal fluid due to the dissolution of EL100. Films containing 400 mg of EL100 and tragacanth gum are promising candidates for future studies, as they could sexually safeguard women from HIV for at least one week and ensure greater protection during intercourse.

Silicon Oxycarbide and Silicon Oxycarbonitride Materials under Concentrated Solar Radiation.

The potential application of silicon oxycarbonitride (SiOCN), silicon oxycarbide (SiOC) and silicon oxycarbide-SiC (SiOC-SiC) for photothermal devices such as volumetric solar absorbers has been studied evaluating the response to thermal shock from a Fresnel lens. The accelerated ageing test comprises fast heating (32 °C min-1) and cooling rates (27 °C min-1) from 100 to 1000 °C and dwelling times of 10 min. Porous materials (SiOCNp and SiOCp) failed the thermal shock tests; they were massively degraded by the formation of a large depression in the focus of solar radiation. Dense materials (SiOCd and SiOC-SiCd) withstood 100 cycles of thermal shock ageing tests due to the formation of a protective silica layer. The absorptance values for dense materials remained fairly constant before and after thermal shock tests: from 94.5 to 94.3% for SiOCd and from 93.3 to 93.3% for SiOC-SiCd. These preliminary studies indicate their potential for high-temperature solar receiver applications.

One-Pot Hydrothermal Synthesis of Victoria Green (Ca3Cr2Si3O12) Nanoparticles in Alkaline Fluids and Its Colour Hue Characterisation.

One-pot hydrothermal preparation of Ca3Cr2Si3O12 uvarovite nanoparticles under alkaline conditions was investigated for the first time. The experimental parameters selected for the study considered the concentration of the KOH solvent solution (0.01 to 5.0 M), the agitation of the autoclave (50 rpm), and the nominal content of Si4+ (2.2-3.0 mole). Fine uvarovite particles were synthesised at 200 °C after a 3 h interval in a highly concentrated 5.0 M KOH solution. The crystallisation of single-phase Ca3Cr2Si3O12 particles proceeded free of by-products via a one-pot process involving a single-step reaction. KOH solutions below 2.5 M and water hindered the crystallisation of the Ca3Cr2Si3O12 particles. The hydrothermal treatments carried out with stirring (50 rpm) and non-stirring triggered the crystallisation of irregular anhedral particles with average sizes of 8.05 and 12.25 nm, respectively. These particles spontaneously assembled into popcorn-shaped agglomerates with sizes varying from 66 to 156 nm. All the powders prepared by the present method exhibited CIE-L*a*b* values that correspond to the Victoria green colour spectral space and have a high near infrared reflectance property. The particle size and structural crystallinity are factors affecting the Victoria pigment optical properties, such as CIE-L*a*b* values, green tonality, and near-infrared reflectance.

Amino Functionalized Micro-Mesoporous Hybrid Particles for the Sustained Release of the Antiretroviral Drug Tenofovir.

The sustained release of an antiretroviral agent to women mucosa has been proved as an excellent strategy to reduce the sexual transmission of HIV. Hybrid micro-mesoporous particles have been synthesized and functionalized with a silane coupling agent followed by loading the antiretroviral tenofovir. It has been observed that the disposition of the silane molecule on the surface of the particles determines the interaction mechanism with the antiretroviral molecule loaded independently on the surface area of the particles. In this sense, available and free amino groups are required to achieve a smart pH-responsive material, a condition that is only achieved in those materials containing a silane chemisorbed monolayer. Moreover, the modulation of the release kinetics attributed to the presence of the silane monolayer covering the mesopores has been confirmed by fitting the releasing curves to the first order and Weibull models. The developed micro-mesoporous particles have been demonstrated to be excellent smart-release vehicles for antiviral agents and can be safely used in polymer mucoadhesive vaginal gels.

Carrageenan-Based Acyclovir Mucoadhesive Vaginal Tablets for Prevention of Genital Herpes.

Women are the most affected by genital herpes, which is one of the most common sexually transmitted infections, affecting more than 400 million people worldwide. The application of vaginal microbicides could provide a safe method of protection. Acyclovir is a safe and effective medication for vaginal administration, and numerous benefits have been observed in the treatment of primary or recurrent lesions due to genital herpes. Vaginal tablets based on a combination of the polymers iota-carrageenan and hydroxypropyl methylcellulose were developed for the controlled release of acyclovir. Swelling, mucoadhesion and drug release studies were carried out in simulated vaginal fluid. The tablets, containing a combination of iota-carrageenan and hydroxypropyl methylcellulose, have an adequate uptake of the medium that allows them to develop the precise consistency and volume of gel for the controlled release of acyclovir. Its high mucoadhesive capacity also allows the formulation to remain in the vaginal area long enough to ensure the complete release of acyclovir. These promising formulations for the prevention of genital herpes deserve further evaluation.

Development and In Vitro/Ex Vivo Characterization of Vaginal Mucoadhesive Bilayer Films Based on Ethylcellulose and Biopolymers for Vaginal Sustained Release of Tenofovir.

Young women in sub-Saharan Africa have the highest risk of human immunodeficiency virus (HIV) acquisition through sexual contact of all groups. Vaginal controlled release of antiretrovirals is a priority option for the prevention of sexual transmission of the virus in women. In this manuscript, bilayer films were prepared based on ethylcellulose and a natural polymer (xanthan or tragacanth gum) plasticized with glycerol and tributylcitrate for tenofovir-controlled release. The mechanical properties and microstructure of the blank films were characterized by texture analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The loaded films were evaluated in simulated vaginal fluid through release and swelling studies and ex vivo mucoadhesion assessments. The results show that the preparation method produced bilayer films with adequate mechanical properties. The contribution of both layers allowed the sustained release of tenofovir and a mucoadhesion time of up to 360 h. The toxicity of the materials was evaluated in three cell lines of vaginal origin. The films constituted by ethylcellulose and xanthan gum in a 2:1 proportion (EX2-D) showed the longest mucoadhesion time, with 15 days of tenofovir-controlled release, zero toxicity, and optimal mechanical properties. These films are therefore a promising option for offering women a means of self-protection against the sexual transmission of HIV.

Mucoadhesive Vaginal Discs based on Cyclodextrin and Surfactants for the Controlled Release of Antiretroviral Drugs to Prevent the Sexual Transmission of HIV.

The strategies for developing vaginal microbicides to protect women against human immunodeficiency virus (HIV) sexual transmission are constantly changing. Although the initial dosage forms required daily administration to offer effective protection, the trend then moved towards sustained-release dosage forms that require less frequency of administration in order to improve women's compliance with the treatment. Nevertheless, another possible strategy is to design on-demand products that can be used in a coitally-dependent manner and only need to be administered immediately before intercourse to offer protection. Vaginal discs based on freeze-dried hydroxypropylmethyl cellulose gels have been developed for this purpose, containing two surfactants, i.e., sodium dodecyl sulphate and polysorbate 60, alone or in combination with 2-hydroxypropyl-ß-cyclodextrin, to achieve a formulation capable of incorporating both hydrophilic and lipophilic drugs. Several studies have been carried out to evaluate how the inclusion of these substances modifies the structure of gels (viscosity and consistency studies) and the porosimetry of the freeze-dried discs (scanning electron microscopy micrographs, mechanical properties, swelling behaviour). The drug release and mucoadhesive properties of the discs have also been evaluated with a view to their clinical application. The systems combining sodium dodecyl sulphate and 2-hydroxypropyl-ß-cyclodextrin were found to be adequate for the vaginal administration of both Tenofovir and Dapivirine and also offer excellent mucoadhesion to vaginal tissue; these discs could therefore be an interesting option for a coitally-dependent administration to protect women against HIV transmission.

Vaginal Polyelectrolyte Layer-by-Layer Films Based on Chitosan Derivatives and Eudragit® S100 for pH Responsive Release of Tenofovir.

Women are still at high risk of contracting the human immunodeficiency virus (HIV) virus due to the lack of protection methods under their control, especially in sub-Saharan countries. Polyelectrolyte multilayer smart vaginal films based on chitosan derivatives (chitosan lactate, chitosan tartate, and chitosan citrate) and Eudragit® S100 were developed for the pH-sensitive release of Tenofovir. Films were characterized through texture analysis and scanning electron microscopy (SEM). Swelling and drug release studies were carried out in simulated vaginal fluid and a mixture of simulated vaginal and seminal fluids. Ex vivo mucoadhesion was evaluated in bovine vaginal mucosa. SEM micrographs revealed the formation of multilayer films. According to texture analysis, chitosan citrate was the most flexible compared to chitosan tartrate and lactate. The swelling studies showed a moderate water uptake (<300% in all cases), leading to the sustained release of Tenofovir in simulated vaginal fluid (up to 120 h), which was accelerated in the simulated fluid mixture (4-6 h). The films had high mucoadhesion in bovine vaginal mucosa. The multilayer films formed by a mixture of chitosan citrate and Eudragit® S100 proved to be the most promising, with zero toxicity, excellent mechanical properties, moderate swelling (<100%), high mucoadhesion capacity, and Tenofovir release of 120 h and 4 h in vaginal fluid and the simulated fluid mixture respectively.

Carbon-GO Composites with Preferential Water versus Ethanol Uptake.

The elimination of small amounts of water from alcohols is by no means a trivial issue in many practical applications like, for instance, the dehumidification of biocombustibles. The use of carbonaceous materials as sorbents has been far less explored than that of other materials because their hydrophobic character has typically limited their water uptake. Herein, we designed a synthetic process based on the use of eutectic mixtures that allowed the homogeneous dispersion of graphene oxide (GO) in the liquid containing the carbon precursor, e.g., furfuryl alcohol. Thus, after polymerization and a subsequent carbonization process, we were able to obtain porous carbon-GO composites where the combination of pore diameter and surface hydrophilicity provided a remarkable capacity for water uptake but extremely low methanol and ethanol uptake along the entire range of relative pressures evaluated in this work. Both the neat water uptake and the uptake difference between water and either methanol or ethanol of our carbon-GO composites were similar or eventually better than the uptake previously reported for other materials, also exhibiting preferential water-to-alcohol adsorption, e.g., porous coordination polymers, metal-organic frameworks, polyoxometalates, and covalent two-dimensional nanosheets embedded in a polymer matrix. Moreover, water versus alcohol uptake was particularly remarkable at low partial pressures in our carbon-GO composites.

Chitosan-Based Mucoadhesive Vaginal Tablets for Controlled Release of the Anti-HIV Drug Tenofovir.

Vaginal microbicides have the potential to give women at high risk of contracting HIV the option of self-protection by preventing the sexual transmission of the virus. In this paper, mucoadhesive vaginal tablets based on chitosan, alone and in combination with pectin and locust bean gum, were developed for the sustained release of tenofovir (an antiretroviral drug). The formulations were placed in simulant vaginal fluid (SVF) to swell, and Hg porosity and SEM microscopy were used for the microstructural characterization of the swelling witnesses. The results show that the association of pectin and chitosan generated polyelectrolyte complexes and produced a robust system able to maintain its structure during the swelling process, when small pores are formed. Drug release and bovine vaginal mucoadhesion studies were performed in SVF showing that tenofovir-controlled dissolution profiles and adhesion to the mucosa were conditioned by the swelling processes of the polymer/s in each formulation. Tablets based on chitosan/pectin have the most homogeneous tenofovir dissolution profiles and last up to 96 h, remaining attached to the vaginal mucosa for the same period. These formulations can therefore be considered a good option for the self-protection of women from the sexual transmission of HIV.

Application of a glass fertilizer in sustainable tomato plant crops.

BACKGROUND: Glass frits with a P2 O5 /K2 O ratio equal to 0.65 and different concentrations of SiO2 (6.5-56.0 wt%), CaO (0-5.1 wt%) and Al2 O3 (0-14.6 wt%) have been prepared and analysed as potential glass fertilizers (GF). RESULTS: P2 O5 and K2 O were leached primarily within the first 5 days but the total amount was dependent on the SiO2 /Al2 O3 ratio of the glass frit. Sustained P2 O5 and K2 O leaching for more than 40 days could be obtained if the glass frit contained more than 7% Al2 O3 . A final glass frit composition (29% SiO2 , 5% CaO, 7% Al2 O3 , 30% P2 O5 , 25% K2 O) was selected and used in an experimental tomato crop of 1 ha area, where one half was fertilized with an NPK conventional fertilizer and the other half with the GF fertilizer. CONCLUSION: After harvesting the tomato crops, the GF fertilizer was found to result in a higher yield than the NPK conventional fertilizer: 59980 kg and 74 360 kg for NKP and GF, respectively. The general characteristics of the harvested tomato fruits and leaves were similar in the two cases and the differences fell within statistical error. No differences in any of the soil characteristics were detected as a result of the use of GF. © 2018 Society of Chemical Industry.