Sporopollenin Capsules as Biomimetic Templates for the Synthesis of Hydroxyapatite and ß-TCP.

Pollen grains, with their resilient sporopollenin exine and defined morphologies, have been explored as bio-templates for the synthesis of calcium phosphate minerals, particularly hydroxyapatite (HAp) and ß-tricalcium phosphate (TCP). Various pollen morphologies from different plant species (black alder, dandelion, lamb's quarters, ragweed, and stargazer lily) were evaluated. Pollen grains underwent acid washing to remove allergenic material and facilitate subsequent calcification. Ragweed and lamb's quarter pollen grains were chosen as templates for calcium phosphate salts deposition due to their distinct morphologies. The calcification process yielded well-defined spherical hollow particles. The washing step, intended to reduce the protein content, did not significantly affect the final product; thus, justifying the removal of this low-yield step from the synthesis process. Characterisation techniques, including X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectroscopy, and thermal gravimetric analysis, confirmed the successful calcification of pollen-derived materials, revealing that calcified grains were principally composed of calcium deficient HAp. After calcination, biphasic calcium phosphate composed of HAp and TPC was obtained. This study demonstrated the feasibility of using pollen grains as green and sustainable bio-templates for synthesizing biomaterials with controlled morphology, showcasing their potential in biomedical applications such as drug delivery and bone regeneration.

3D printing of LEGO® like designs with tailored release profiles for treatment of sleep disorder.

3D printed LEGO®-like designs are an attractive approach for the development of compartmental delivery systems due to their potential for dose personalisation through the customisation of drug release profiles. Additive manufacturing technologies such as Fused Deposition Modelling (FDM) are ideal for the printing of structures with complex geometries and various sizes. This study is a paradigm for the fabrication of 3D printed LEGO® -like tablets by altering the design of the modular units and the filament composition for the delivery of different drug substances. By using a combination of placebo and drug loaded compartments comprising of immediate release (hydroxypropyl cellulose) and pH dependant polymers (hypromellose acetate succinate) we were able to customise the release kinetics of melatonin and caffeine that can potentially be used for the treatment of sleep disorders. The LEGO® -like compartments were designed to achieve immediate release of melatonin followed by variable lag times and controlled release of caffeine.

Recent Advances in Electrochemical Sensors for Caffeine Determination.

The determination of target analytes at very low concentrations is important for various fields such as the pharmaceutical industry, environmental protection, and the food industry. Caffeine, as a natural alkaloid, is widely consumed in various beverages and medicines. Apart from the beneficial effects for which it is used, caffeine also has negative effects, and for these reasons it is very important to determine its concentration in different mediums. Among numerous analytical techniques, electrochemical methods with appropriate sensors occupy a special place since they are efficient, fast, and entail relatively easy preparation and measurements. Electrochemical sensors based on carbon materials are very common in this type of research because they are cost-effective, have a wide potential range, and possess relative electrochemical inertness and electrocatalytic activity in various redox reactions. Additionally, these types of sensors could be modified to improve their analytical performances. The data available in the literature on the development and modification of electrochemical sensors for the determination of caffeine are summarized and discussed in this review.

Curcumin and Diclofenac Therapeutic Efficacy Enhancement Applying Transdermal Hydrogel Polymer Films, Based on Carrageenan, Alginate and Poloxamer.

Films based on carrageenan, alginate and poloxamer 407 have been formulated with the main aim to apply prepared formulations in wound healing process. The formulated films were loaded with diclofenac, an anti-inflammatory drug, as well as diclofenac and curcumin, as multipurpose drug, in order to enhance encapsulation and achieve controlled release of these low-bioavailability compounds. The obtained data demonstrated improved drug bioavailability (encapsulation efficiency higher than 90%), with high, cumulative in vitro release percentages (90.10% for diclofenac, 89.85% for curcumin and 95.61% for diclofenac in mixture-incorporated films). The results obtained using theoretical models suggested that curcumin establishes stronger, primarily dispersion interactions with carrier, in comparison with diclofenac. Curcumin and diclofenac-loaded films showed great antibacterial activity against Gram-positive bacteria strains (Bacillus subtilis and Staphylococcus aureus, inhibition zone 16.67 and 13.67 mm, respectively), and in vitro and in vivo studies indicated that curcumin- and diclofenac-incorporated polymer films have great potential, as a new transdermal dressing, to heal wounds, because diclofenac can target the inflammatory phase and reduce pain, whereas curcumin can enhance and promote the wound healing process.

pH-Responsive Hydrogel Beads Based on Alginate, κ-Carrageenan and Poloxamer for Enhanced Curcumin, Natural Bioactive Compound, Encapsulation and Controlled Release Efficiency.

Polyphenolic compounds are used for treating various diseases due to their antioxidant and anticancer properties. However, utilization of hydrophobic compounds is limited due to their low bioavailability. In order to achieve a greater application of hydrophobic bioactive compounds, hydrogel beads based on biopolymers can be used as carriers for their enhanced incorporation and controlled delivery. In this study, beads based on the biopolymers-κ-carrageenan, sodium alginate and poloxamer 407 were prepared for encapsulation of curcumin. The prepared beads were characterized using IR, SEM, TGA and DSC. The curcumin encapsulation efficiency in the developed beads was 95.74 ± 2.24%. The release kinetics of the curcumin was monitored in systems that simulate the oral delivery (pH 1.2 and 7.4) of curcumin. The drug release profiles of the prepared beads with curcumin indicated that the curcumin release was significantly increased compared with the dissolution of curcumin itself. The cumulative release of curcumin from the beads was achieved within 24 h, with a final release rate of 12.07% (gastric fluid) as well as 81.93% (intestinal fluid). Both the in vitro and in vivo studies showed that new hydrogel beads based on carbohydrates and poloxamer improved curcumin's bioavailability, and they can be used as powerful carriers for the oral delivery of different hydrophobic nutraceuticals.

Electrochemical determination of L-tryptophan in food samples on graphite electrode prepared from waste batteries.

One of the goals of this research was to develop an electrochemical sensor that had the ability to determine the target analyte and was both cheap and non-toxic. Another goal was to influence the reduction of electronic waste. In accordance with these, a graphite rod from zinc-carbon batteries was used to prepare an electrochemical sensor for the determination of L-tryptophan in Britton-Robinson buffer solution. Two electrochemical methods were used in the experimental research, differential pulse voltammetry and cyclic voltammetry. The effect of different parameters, including the pH value of supporting solution, scan rate, as well as the concentration of L-tryptophan on the current response, was studied. The pH value of Britton-Robinson buffer influenced the intensity of L-tryptophan oxidation peak, as well as the peak potential. The intensity of the current response was the highest at pH 4.0, while the peak potential value became lower as the pH increased, indicating that protons also participated in the redox reaction. Based on the obtained data, electrochemical oxidation of L-tryptophan at the graphite electrode was irreversible, two electron/two proton reaction. In addition, it was observed that the oxidation peak increased as the scan rate increased. According to the obtained electrochemical data, it was suggested that the oxidation of L-tryptophan was mixed controlled by adsorption and diffusion. The linear correlation between oxidation peak and L-tryptophan concentration was investigated in the range 5.0-150.0 µM and the obtained values of limit of detection and limit of quantification were 1.73 µM and 5.78 µM, respectively. Also, the prepared electrochemical sensor was successful in determination of target analyte in milk and apple juice samples.

Continuous Manufacture and Scale-Up of Theophylline-Nicotinamide Cocrystals.

The aim of the study was the manufacturing and scale-up of theophylline-nicotinamide (THL-NIC) pharmaceutical cocrystals processed by hot-melt extrusion (HME). The barrel temperature profile, feed rate and screw speed were found to be the critical processing parameters with a residence time of approximately 47 s for the scaled-up batches. Physicochemical characterization using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and X-ray diffraction of bulk and extruded materials revealed the formation of high purity cocrystals (98.6%). The quality of THL-NIC remained unchanged under accelerated stability conditions.

Overview of Erasmus+ NETCHEM project: ICT networking for overcoming technical and social barriers in instrumental analytical chemistry education.

The paper briefly presents goals, activities, challenges, and outcomes of the NETCHEM project ( http://www.netchem.ac.rs/ ) that was co-funded by the Erasmus+ Program of European Union (573885-EPP-1-2016-1-RS-EPPKA2- CBHE-JP). The project has been started in October 2016 and with extension lasted until April 2020. Western Balkan region has been targeted by upgrading capacities for education and research in environmental and food analysis in cooperation with partners from France, the UK, and Czech Republic. NETCHEM platform providing Web Accessed Remote Instrumental Analytical Laboratories (WARIAL) network, Database service and Open education system was created in order to improve the cooperation, educational, and research capacities of Higher Education Institutions involved, but also targeting whether audience not only from academic domain but from industry as well. The NETCHEM platform is free for access to public; thus, the external users to NETCHEM consortium can not only see its content but also actively participate, enter Database and WARIAL network, and upload their own educational/research material.

Corrosion Behavior of Titanium in Simulated Body Solutions with the Addition of Biomolecules.

Titanium is one of the most used biomaterials for different applications. The aim of this study is to investigate the influence of adenine, thymine, and l-histidine as important biomolecules in the human body on the corrosion behavior of titanium in simulated body solutions. Open circuit measurements, potentiodynamic measurements, electrochemical impedance spectroscopy measurements, and quantum chemical calculations were employed during the investigation. All electrochemical methods used revealed that the investigated biomolecules provide better corrosion resistance to titanium in artificial body solutions. The increase in corrosion resistance is a result of the formation of a stable protective film on the metal surface. Also, quantum chemical calculations are in compliance with electrochemical test results and indicate that adenine, thymine, and l-histidine may act as corrosion inhibitors in the investigated solutions.

Influence of 5-Chlorobenzotriazole on Inhibition of Copper Corrosion in Acid Rain Solution.

This paper aims to examine the efficiency of 5-chlorobenzotriazole (5Cl-BTA) as a copper corrosion inhibitor in acidic rain solutions with a pH value of 2.42 by the electrochemical polarization method. 5-Chlorobenzotriazole acts similar to a mixed type inhibitor, according to the potentiodynamic polarization measurements. Results obtained in this research suggest that 5Cl-BTA is a good inhibitor; it decreases anodic and cathodic reaction rates, and the highest inhibition efficiency was 91.2%. The inhibitory effect of 5-chlorobenzotriazole is explained by the formation of the layer on the copper surface. Stability of the protective layer increased with inhibitor concentration. Scanning electron microscopy and energy-dispersive analysis of X-rays analysis confirmed that on the electrode surface, a protective layer was formed. Adsorption of 5Cl-BTA obeys the Langmuir adsorption isotherm. 5Cl-BTA showed good inhibitory characteristics even when the Cl- ions were present in examined solutions.

Elucidation of the Controlled-Release Behavior of Metoprolol Succinate from Directly Compressed Xanthan Gum/Chitosan Polymers: Computational and Experimental Studies.

The development and evaluation of a controlled-release (CR) pharmaceutical solid dosage form comprising xanthan gum (XG), low molecular weight chitosan (LCS), and metoprolol succinate (MS) are reported. The research is, partly, based upon the utilization of computational tools: in this case, molecular dynamics simulations (MDs) and the response surface method (RSM) in order to underpin the design/prediction and to minimize the experimental work required to achieve the desired pharmaceutical outcomes. The capability of the system to control the release of MS was studied as a function of LCS (% w/w) and total polymer (LCS and xanthan gum (XG)) to drug ratio (P/D) at different tablet tensile strengths. MDs trajectories, obtained by using different ratios of XG/LCS as well as XG and high molecular weight chitosan (HCS), showed that the driving force for the interaction between XG and LCS is electrostatic in nature, the most favorable complex is formed when LCS is used at 15% (w/w) and, importantly, the interaction between XG and LCS is more favorable than that between XG and HCS. RSM outputs revealed that the release of the drug from the LCS/XG matrix is highly dependent on both the % LCS and the P/D ratio and that the required CR effect can be achieved when using weight fractions of LCS ≤ 20% and P/D ratios ≥2.6:1. Results obtained from in vitro drug release and swelling studies on the prepared tablets showed that using LCS at the weight fractions suggested by MDs and RSM data plays a major role in overcoming the high sensitivity of the controlled drug release effect of XG on ionic strength and pH changes of the dissolution media. In addition, it was found that polymer relaxation is the major contributor to the release of MS from LCS/XG tablets. Using Raman spectroscopy, MS was shown to be localized more in the core of the tablets at the initial stages of dissolution due to film formation between LCS and XG on the tablet surface, which prevents excess water penetration into the matrix. In the later stages of the dissolution process, the film starts to dissolve/erode, allowing full tablet hydration and a uniform drug distribution in the swollen tablet.

Electrochemical and DFT studies of brass corrosion inhibition in 3% NaCl in the presence of environmentally friendly compounds.

The effects of adenine, salicylaldoxime and 4(5)-methylimidazole on brass corrosion in NaCl were investigated. The investigation comprised electrochemical techniques, scanning electron microscopy and quantum chemical calculation. The results obtained by polarization measurements show that the examined compounds successfully inhibited the corrosion of brass. Additionally, the quantum mechanical calculations indicate that there is a correlation between energy gap and inhibition efficiency. Moreover, the inhibition mechanism includes the adsorption of the inhibitor on active sites on the electrode surface, which was confirmed by SEM-EDS analysis of the brass.

A Direct Compression Matrix Made from Xanthan Gum and Low Molecular Weight Chitosan Designed to Improve Compressibility in Controlled Release Tablets.

The subject of our research is the optimization of direct compression (DC), controlled release drug matrices comprising chitosan/xanthan gum. The foregoing is considered from two main perspectives; the use of low molecular weight chitosan (LCS) with xanthan gum (XG) and the determination of important attributes for direct compression of the mixtures of the two polymers. Powder flow, deformation behaviour, and work of compression parameters were used to characterize powder and tableting properties. Compression pressure and LCS content within the matrix were investigated for their influence on the crushing strength of the tablets produced. Response surface methodology (RSM) was applied to determine the optimum parameters required for DC of the matrices investigated. Results confirm the positive contribution of LCS in enhancing powder compressibility and crushing strength of the resultant compacts. Compactibility of the XG/LCS mixtures was found to be more sensitive to applied compression pressure than LCS content. LCS can be added at concentrations as low as 15% w/w to achieve hard compacts, as indicated by the RSM results. The introduction of the plasticity factor, using LCS, to the fragmenting material XG was the main reason for the high volume reduction and reduced porosity of the polymer mixture. Combinations of XG with other commonly utilized polymers in controlled release studies such as glucosamine, hydroxypropyl methylcellulose (HPMC), Na alginate (ALG), guar gum, lactose and high molecular weight (HMW) chitosan were also used; all the foregoing polymers failed to reduce the matrix porosity beyond a certain compression pressure. Application of the LCS/XG mixture, at its optimum composition, for the controlled release of two model drugs (metoprolol succinate and dyphylline) was examined. The XG/LCS matrix at 15% w/w LCS content was found to control the release of metoprolol succinate and dyphylline. The former preparation confirmed the strong influence of compression pressure on changing the drug release profile. The latter preparation showed the ability of XG/LCS to extend the drug release at a fixed rate for 12 h of dissolution time after which the release became slightly slower.

Ibuprofen as a corrosion inhibitor for copper in synthetic acid rain solution.

It is known that if unused drugs are improperly disposed, they can pollute the environment. Furthermore, researchers are still trying to find an environmentally friendly corrosion inhibitor. These factors lead to the possible application of unused pharmaceutical compounds as corrosion inhibitors. The feasibility of an anti-inflammatory, analgesic and antipyretic drug, ibuprofen, was evaluated as a potential copper corrosion inhibitor in synthetic acid rain solution. This investigation was performed by applying electrochemical and weight loss measurements and quantum chemical calculations. The results obtained by these techniques revealed the ability of ibuprofen to protect copper from corrosion. The inhibition efficiency of ibuprofen rises with increase in its concentration and can reach a value of 97.3%. The results of surface analysis of treated coupons by scanning electron microscopy and theoretical calculations are consistent with the experimental results.

Glassy state molecular mobility and its relationship to the physico-mechanical properties of plasticized hydroxypropyl methylcellulose (HPMC) films.

Changes in tensile properties and the glass transition temperature (Tg) of plasticized polymer films are typically attributed to molecular mobility, often with no empirical data to support such an assertion. Herein solvent cast HPMC films containing varying amounts of PEG, as the plasticizer, were used to assess the dependence of tensile properties and the Tg on glassy state molecular mobility. Molecular mobility (molecular relaxation time and temperature) parameters were determined by Thermally Stimulated Current Spectroscopy (TSC). The tensile properties and Tg of the HPMC films were determined by texture analysis and DSC, respectively. Molecular mobilities detected by TSC were cooperative and occurred at temperatures (Tg') well below (113 to 127 °C) the bulk Tg. The relaxation times (τ) were 71 ±â€¯1, 46 ±â€¯1, 42 ±â€¯1, 36 ±â€¯1 and 29 ±â€¯1 s for HPMC films containing 0, 6, 8, 11 and 17% (w/w) PEG, respectively. The Tg and glassy state molecular mobility were found to be intimately linked and demonstrated a linear dependence. While tensile strength was found to be linearly related to molecular relaxation time, tensile elongation and elastic modulus exhibited a non-linear dependence on molecular mobility. The data presented in this work demonstrates the complex nature of the relationship between plasticizer content, molecular mobility, Tg and tensile properties for plasticized polymeric films. It highlights the fact that the dependence of the bulk physico-mechanical properties on glassy state molecular mobility, differ greatly. Therefore, empirical characterization of molecular mobility is important to fully understand and predict the thermo-mechanical behavior of plasticized polymer films. This work demonstrates the unique capability of TSC to provide key information relating to molecular mobility and its influence on the bulk properties of materials. Data generated using TSC could prove useful for stability and performance ranking, in addition to the ability to predict materials behavior using data generated at or below typical storage conditions in the pharmaceutical, food, and polymer industries.

A novel micro-photogrammetric instrument for visualizing in 3D small objects applied to the quantitative study of the dissolution behavior of a pharmaceutical dosage form.

The work presented here proposes an innovative approach to 3D chemical mapping of solid formulations by microphotogrammetry. We present details of a novel microphotogrammetry apparatus and the first results for the application of photogrammetry to the dissolution analysis of solid pharmaceutical dosage forms. Unlike other forms of optical imaging, microphotogrammetry allows a true 3D model to be constructed that includes direct observation of the sides of the sample rather than only top-down topographic imaging. Volume and structural changes are assessed quantitatively and related to chemical analysis by high performance liquid chromatography. The recently introduced method of chemical identification by dissolution analysis, or chemical imaging by dissolution analysis, is employed for the first time to obtain tomographic images of the dissolution process.

Can emollients of similar composition be assumed to be therapeutically equivalent: a comparison of skin occlusivity and emulsion microstructure.

INTRODUCTION: Emollient therapy is the mainstay for treating skin conditions such as atopic dermatitis and psoriasis. New emollients have been introduced recently and are assumed to be therapeutically interchangeable with the innovator products because, superficially, they appear to have similar compositions. This study compares a) the ex vivo human skin occlusion performance and b) the visual and microscopic properties of Isomol gel (IMG) and Doublebase gel (DBG). MATERIALS AND METHODS: Occlusion was measured gravimetrically by reduction in cumulative 48-hour evaporative weight loss from ex vivo human skin samples following single applications of the two test emollients and Vaseline®. Skin samples from a single donor were mounted in Franz diffusion cells and then the emollients were spread over the skin surface with an applied dose of approximately 2 mg/cm2. The assemblies (four replicates per treatment) were then accurately weighed at baseline (T0) and again after 5-, 24-, and 48-hour postapplication. The quality of the two emollient gel formulations was compared by visual examination of their film-forming characteristics and by microstructural examination using environmental scanning electron microscopy (ESEM). RESULTS: Occlusivity of the DBG emollient gel formulation was comparable with Vaseline and substantially better than IMG, with the DBG-treated skin samples losing less than half as much weight as the IMG-treated skin samples over 48 hours and at a much slower rate during the first 5 hours. The film-forming characteristics and microstructure of the gels were also very different. Whereas DBG maintained a smooth, uniform film over 24 hours, the IMG formulation phase-separated. ESEM results showed that the DBG emulsion has a stable structural matrix with uniform oil droplets, whereas for IMG the emulsion system is inhomogeneous with the oil phase coalescing into larger irregular shaped rafts. CONCLUSIONS: We have demonstrated substantial performance differences between two prescribed emollient gels.

Effect of Protonation State and N-Acetylation of Chitosan on Its Interaction with Xanthan Gum: A Molecular Dynamics Simulation Study.

Hydrophilic matrices composed of chitosan (CS) and xanthan gum (XG) complexes are of pharmaceutical interest in relation to drug delivery due to their ability to control the release of active ingredients. Molecular dynamics simulations (MDs) have been performed in order to obtain information pertaining to the effect of the state of protonation and degree of N-acetylation (DA) on the molecular conformation of chitosan and its ability to interact with xanthan gum in aqueous solutions. The conformational flexibility of CS was found to be highly dependent on its state of protonation. Upon complexation with XG, a substantial restriction in free rotation around the glycosidic bond was noticed in protonated CS dimers regardless of their DA, whereas deprotonated molecules preserved their free mobility. Calculated values for the free energy of binding between CS and XG revealed the dominant contribution of electrostatic forces on the formation of complexes and that the most stable complexes were formed when CS was at least half-protonated and the DA was ≤50%. The results obtained provide an insight into the main factors governing the interaction between CS and XG, such that they can be manipulated accordingly to produce complexes with the desired controlled-release effect.

Removal of cationic pollutants from water by xanthated corn cob: optimization, kinetics, thermodynamics, and prediction of purification process.

The removal of Cr(III) ions and methylene blue (MB) from aqueous solutions by xanthated corn cob (xCC) in batch conditions was investigated. The sorption capacity of xCC strongly depended of the pH, and increase when the pH rises. The kinetics was well fitted by pseudo-second-order and Chrastil's model. Sorption of Cr(III) ions and MB on xCC was rapid during the first 20 min of contact time and, thereafter, the biosorption rate decrease gradually until reaching equilibrium. The maximum sorption capacity of 17.13 and 83.89 mg g-1 for Cr(III) ions and MB, respectively, was obtained at 40 °C, pH 5, and sorbent dose 4 g dm-3 for removal of Cr(III) ions and 1 g dm-3 for removal of MB. The prediction of purification process was successfully carried out, and the verification of theoretically calculated amounts of sorbent was confirmed by using packed-bed column laboratory system with recirculation of the aqueous phase. The wastewater from chrome plating industry was successfully purified, i.e., after 40 min concentration of Cr(III) ions was decreased lower than 0.1 mg dm-3. Also, removal of MB from the river water was successfully carried out and after 40 min, removal efficiency was about 94%.

Chemical Imaging by Dissolution Analysis: Localized Kinetics of Dissolution Behavior to Provide Two-Dimensional Chemical Mapping and Tomographic Imaging on a Nanoscale.

A new approach to achieving chemical mapping on a nanoscale is described that can provide 2D and tomographic images of surface and near-surface structure. The method comprises dissolving material from the surface of the sample by applying a series of aliquots of solvent, then analyzing their contents after removing them; in between exposures, the surface is imaged with atomic force microscopy. This technique relies on being able to compensate for any drift between images by use of software. It was applied to a blend of two polymers, PMMA and PS. The analytical data identified the material that was dissolved, and the topography images enabled the location of the various materials to be determined by analyzing local dissolution kinetics. The prospects for generalizing the approach are discussed.