Application of TGA/c-DTA for Distinguishing between Two Forms of Naproxen in Pharmaceutical Preparations.

Naproxen is one of the most used non-steroidal anti-inflammatory drugs (NSAIDs). It is used to treat pain of various origins, inflammation and fever. Pharmaceutical preparations containing naproxen are available with prescription and over-the-counter (OTC). Naproxen in pharmaceutical preparations is used in the form of acid and sodium salt. From the point of view of pharmaceutical analysis, it is crucial to distinguish between these two forms of drugs. There are many costly and laborious methods to do this. Therefore, new, faster, cheaper and, at the same time, simple-to-perform identification methods are sought. In the conducted studies, thermal methods such as thermogravimetry (TGA) supported by calculated differential thermal analysis (c-DTA) were proposed to identify the type of naproxen in commercially available pharmaceutical preparations. In addition, the thermal methods used were compared with pharmacopoeial methods for the identification of compounds, such as high-performance liquid chromatography (HPLC), Fourier-transform infrared spectroscopy (FTIR), UV-Vis spectrophotometry, and a simple colorimetric analyses. In addition, using nabumetone, a close structural analog of naproxen, the specificity of the TGA and c-DTA methods was assessed. Studies have shown that the thermal analyses used are effective and selective in distinguishing the form of naproxen in pharmaceutical preparations. This indicates the potential possibility of using TGA supported by c-DTA as an alternative method.

UV-activated persulfates oxidation of anthraquinone dye: Kinetics and ecotoxicological assessment.

Sulfate radical-based advanced oxidation processes (SR-AOPs) are gaining popularity as a feasible alternative for removing recalcitrant pollutants in an aqueous environment. Persulfates, namely peroxydisulfate (PDS) and peroxymonosulfate (PMS) are the most common sulfate radical donors. Persulfates activation by ultraviolet (UV) irradiation is considered feasible due to the high concentration of radicals produced as well as the lack of catalysts leaching. The research focuses on determining the impact of activated PDS and PMS on the degradation of anthraquinone dye, i.e., Acid Blue 129 (AB129). UV-activated PDS and PMS can quickly degrade the AB129 as well as restrict the formation of by-products. This could explain the reduced ecotoxicity levels of the treated water after degradation, using an aquatic plant (Lemna minor) and a crustacean (Daphnia magna). This, on the other hand, can ensure that the sulfate radical-based processes can be an environmentally friendly technology.

Bioaccumulation of Trace Elements from Aqueous Solutions by Selected Terrestrial Moss Species.

The interrelationship between metal concentrations in mosses and their surroundings prompts research toward examining their accumulation properties, as it is particularly important for their usage in biomonitoring studies that use mosses. In this study, the kinetics of elemental sorption in three moss species (Pleurozium schreberi, Dicranum polysetum, and Sphagnum fallax) were investigated under laboratory conditions. Sorption from metal salt solutions was carried out under static conditions with decreasing elemental concentration. Functional groups responsible for binding metal cations to the internal structures of the mosses were also identified. It was shown that the equilibrium state was reached after about 60 min. Under the conditions of the experiment, in the first 10 min of the process, about 70.4-95.3% of metal ions were sorbed from the solution into the moss gametophytes by P. schreberi (57.1-89.0% by D. polysetum and 54.1-84.5% by S. fallax) with respect to the concentration of this analyte accumulated in the mosses at equilibrium. It can be assumed that the exposure of mosses with little contamination by heavy metals in an urbanized area under active biomonitoring will cause an increase in the concentration of these analytes in proportion to their concentration in atmospheric aerosols. In the case of P. schreberi and D. polysetum, the O-H/N-H band was enormously affected by the adsorption process. On the other hand, FTIR (Fourier transform infrared spectroscopy) analysis of S. fallax after adsorption showed slight changes for most of the bands analyzed. Based on this study, it can be concluded that mosses can be used as, for example, a biomonitor in monitoring of urban ecosystems, but also in the phytoremediation of surface waters.

Cyclodextrin-based strategies for removal of persistent organic pollutants.

Water could be considered one of the essential natural resources on our planet. However, water contamination has become virtually ubiquitous during the past decades due to several factors, e.g., world population growth, water use in chemical production, and agriculture. Among contaminants, persistent organic pollutants (POPs) were widely spread during the last few decades and are now present all around the world. POPs are connected with several different illnesses, and therefore the removal of these pollutants from water is a challenge for coming years. Cyclodextrins (CDs) are environmentally friendly and cheap pollutant adsorbents due to their peculiar physicochemical properties. Moreover, CDs are relatively easy to use, and many techniques are reported for their functionalization. In addition, several CD derivatives are known and some of them are commercially available. CDs and CD-functionalized materials could be used for removal of different pollutants by using various methods, e.g., adsorption/extraction, soil washing, and electrokinetic/catalytic processes. This is the first review article that provides an overview of CDs/CD-based materials and their use in the remediation of POPs listed under the Stockholm Convention. The mechanisms of the POPs removal by CDs are also discussed.

Gum Hydrocolloids Reinforced Silver Nanoparticle Sponge for Catalytic Degradation of Water Pollutants.

The accumulation of organic contaminants including dyes in aquatic systems is of significant environmental concern, necessitating the development of affordable and sustainable materials for the treatment/elimination of these hazardous pollutants. Here, a green synthesis strategy has been used to develop a self-assembled gum kondagogu-sodium alginate bioconjugate sponge adorned with silver nanoparticles, for the first time. The properties of the nanocomposite sponge were then analyzed using FTIR, TGA, SEM, and MicroCT. The ensued biobased sponge exhibited hierarchical microstructure, open cellular pores, good shape memory, and mechanical properties. It merges the attributes of an open cellular porous structure with metal nanoparticles and are envisaged to be deployed as a sustainable catalytic system for reducing contaminants in the aqueous environment. This nanocomposite sponge showed enhanced catalytic effectiveness (km values up to 37 min-1 g-1 and 44 min-1 g-1 for methylene blue and 4-nitrophenol, respectively), antibacterial properties, reusability, and biodegradability (65% biodegradation in 28 days).

Effect of heparin treatment on pulmonary embolism and in-hospital death in unvaccinated COVID-19 patients without overt deep vein thrombosis.

BACKGROUND: Pulmonary embolism (PE) without overt deep vein thrombosis (DVT) was common in hospitalized coronavirus-induced disease (COVID)-19 patients and represented a diagnostic, prognostic, and therapeutic challenge. The aim of this study was to analyze the prognostic role of PE on mortality and the preventive effect of heparin on PE and mortality in unvaccinated COVID-19 patients without overt DVT. METHODS: Data from 401 unvaccinated patients (age 68 ± 13 years, 33% females) consecutively admitted to the intensive care unit or the medical ward were included in a retrospective longitudinal study. PE was documented by computed tomography scan and DVT by compressive venous ultrasound. The effect of PE diagnosis and any heparin use on in-hospital death (primary outcome) was analyzed by a classical survival model. The preventive effect of heparin on either PE diagnosis or in-hospital death (secondary outcome) was analyzed by a multi-state model after having reclassified patients who started heparin after PE diagnosis as not treated. RESULTS: Median follow-up time was 8 days (range 1-40 days). PE cumulative incidence and in-hospital mortality were 27% and 20%, respectively. PE was predicted by increased D-dimer levels and COVID-19 severity. Independent predictors of in-hospital death were age (hazards ratio (HR) 1.05, 95% confidence interval (CI) 1.03-1.08, p < 0.001), body mass index (HR 0.93, 95% CI 0.89-0.98, p = 0.004), COVID-19 severity (severe versus mild/moderate HR 3.67, 95% CI 1.30-10.4, p = 0.014, critical versus mild/moderate HR 12.1, 95% CI 4.57-32.2, p < 0.001), active neoplasia (HR 2.58, 95% CI 1.48-4.50, p < 0.001), chronic obstructive pulmonary disease (HR 2.47; 95% CI 1.15-5.27, p = 0.020), respiratory rate (HR 1.06, 95% CI 1.02-1.11, p = 0.008), heart rate (HR 1.03, 95% CI 1.01-1.04, p < 0.001), and any heparin treatment (HR 0.35, 95% CI 0.18-0.67, p = 0.001). In the multi-state model, preventive heparin at prophylactic or intermediate/therapeutic dose, compared with no treatment, reduced PE risk and in-hospital death, but it did not influence mortality of patients with a PE diagnosis. CONCLUSIONS: PE was common during the first waves pandemic in unvaccinated patients, but it was not a negative prognostic factor for in-hospital death. Heparin treatment at any dose prevented mortality independently of PE diagnosis, D-dimer levels, and disease severity.

Enhanced degradation of sulfamethoxazole by a modified nano zero-valent iron with a ß-cyclodextrin polymer: Mechanism and toxicity evaluation.

Rising concern about emerging and already persisting pollutants in water has urged the scientific community to develop novel remedial techniques. A new group of remediation methods is based on the modification of nanoscale zero-valent iron particles (nZVI), which are well known for treating volatile organic compounds and heavy metals. The properties of nZVI may be further enhanced by modifying their structure or surface using "green" polymers. Herein, nZVI was modified by a ß-cyclodextrin polymer (ß-CDP), which is considered an environmentally safe and inexpensive adsorbent of contaminants. This composite was used for the first time for the degradation of sulfamethoxazole (SMX). Coating by ß-CDP not only enhanced the degradation of SMX (>95%, under 10 min) by the nanoparticles in a wide pH range (3-9) and enabled their efficient reusability (for three cycles) but also made the coated nZVI less toxic to the model bioindicator microalga Raphidocelis subcapitata. Moreover, degradation products of SMX were found to be less toxic to Escherichia coli bacteria and R. subcapitata microalga, contrary to the SMX antibiotic itself, indicating a simple and eco-friendly cleaning process. This research aims to further stimulate and develop novel remedial techniques based on nZVI, and provides a potential application in the degradation of antibiotics in a wide pH range. Moreover, the wealth of available cyclodextrin materials used for surface modification may open a way to discover more efficient and attractive composites for environmental applications.

Effects of Antithrombotic Agents on Ophthalmological Outcomes, Cardiovascular Risk, and Mortality in Hypertensive Patients with Retinal Vein Occlusion: An Exploratory Retrospective Study.

Background and objectives: Because few data are available, the aim of this study is to analyze the effects of antithrombotic agents (ATAs) on visual function and long-term risk of cardiovascular events and mortality in hypertensive patients with retinal vein occlusion (RVO). Materials and methods: Hypertensive patients with RVO were consecutively selected from 2008 to 2012 and followed for a median of 8.7 years. Ophthalmologists evaluated and treated RVO complications, and best-corrected visual acuity (BCVA) was checked at each visit during the first one year of follow-up. Survival analysis was conducted on the rate of the composite endpoint of all-cause deaths or non-fatal cardiovascular events. Results: Retrospectively, we collected data from 80 patients (age 68 ± 12 years, 39 males). Central and branch RVO was present in 41 and 39 patients, respectively, and 56 patients started ATAs (50 antiplatelet drugs, 6 warfarin, and 2 low-molecular weight heparin). Average BCVA of the cohort did not change significantly during one-year of follow-up. The only predictor of BCVA was the baseline BCVA value. There was a reduction in proportion and severity of macular edema and an increase in the cumulative proportion of retinal vein patency reestablishment during the follow-up, independent of treatment. ATAs had no effects on one-year BCVA, intraocular complications, or the composite endpoint rate. Conclusions: In this exploratory study, ATAs had no effect on BCVA during the first one year of follow-up and on the composite endpoint during the long-term follow-up. Further prospective studies need to be conducted with an accurate standardization of the intraocular and antithrombotic treatment to define the positive or negative role of ATAs in hypertensive patients with RVO.

Influence of catalyst zeta potential on the activation of persulfate.

The effect of the zeta potential of nano zero-valent iron (nZVI) and carbocatalyst on the activation of persulfate was investigated. The oxidation experiments were performed on three different compounds, with variously modified nZVI and three distinct carbocatalysts. From the obtained results, an evident linear correlation between nanoparticles' zeta potential and reaction rate constants of these three compounds oxidation may be observed. This phenomenon is not mechanism-specific and occurs for the radical and non-radical processes. The present work indicates the critical influence of the surface charge of nZVI and carbocatalysts on the persulfate catalytic activation.

Surface modification of zero-valent iron nanoparticles with ß-cyclodextrin for 4-nitrophenol conversion.

Environmental pollution causes irreversible damage to ecosystems and their structure. Therefore, the development of novel remedial techniques is a must for an effective response to emerging contaminants and those already persisting in the environment. The nanosized zero-valent iron (nZVI) is considered as an important nanostructure for the degradation of toxic compounds. Furthermore, the degradative potential of nZVI may be improved by surface modification. In this work nZVI was functionalized with ß-cyclodextrin (ß-CD), which is considered to be an environmentally-friendly and cheap adsorbent for toxic pollutants. Such a 'green' improvement not only enhances the activity of nZVI but also enables the conversion of 4-nitrophenol to 4-aminophenol, which under standard conditions is persistent and does not significantly react with bare nZVI. This research may help to find a solution to treat persistent organic pollutants (POPs) in aqueous environment.

A Polymeric Composite Material (rGO/PANI) for Acid Blue 129 Adsorption.

Over the years, polyaniline (PANI) has received enormous attention due to its unique properties. Herein, it was chosen to develop a new polymeric composite material: reduced graphene oxide/polyaniline (rGO/PANI). The composite was prepared by a simple and cost-effective fabrication method of formation by mixing and sonication in various conditions. The obtained materials were characterized and identified using various techniques such as scanning electron microscopy (SEM), Raman and ATR-FTIR spectroscopy, and X-ray diffraction (XRD). The objective of the paper was to confirm its applicability for the removal of contaminants from water. Water could be contaminated by various types of pollutants, e.g., inorganics, heavy metals, and many other industrial compounds, including dyes. We confirmed that the Acid Blue 129 dyes can be substantially removed through adsorption on prepared rGO/PANI. The adsorption kinetic data were modeled using the pseudo-first-order and pseudo-second-order models and the adsorption isotherm model was identified.

Synthesis of Ag nanoparticles by a chitosan-poly(3-hydroxybutyrate) polymer conjugate and their superb catalytic activity.

This work describes an eco-friendly and sustainable technique for the synthesis of silver nanoparticles (nAg), where chitosan-poly(3-hydroxybutyrate) polymer conjugate (Chit-PHB) acts as a reducing and stabilizing material. The ensuing nanoparticles show an exceptional catalytic activity in the reduction of 4-nitrophenol to 4-aminophenol. nAg were characterized by several techniques, i.e. SEM and TEM-EDX, to confirm their production, size and morphology. Furthermore, infrared spectroscopy analysis proved the presence of a Chit-PHB coating on the nAg. The excellent catalytic properties of the nAg-Chit-PHB was discernible when the activity parameter (κc) normalized by the specific surface area (SSA) of the nanoparticles was taken into consideration; normalization of κc by the SSA is a vital parameter for the assessment of the accessibility to the surface area of particles. Herein synthesized Ag nanoparticles, as far as we know, exhibited the fastest reaction kinetics of 4-nitrophenol reduction compared to the silver nanoparticles reported in the literature.

The Use of a Biopolymer Conjugate for an Eco-Friendly One-Pot Synthesis of Palladium-Platinum Alloys.

Raising health and environmental concerns over the nanoparticles synthesized from hazardous chemicals have urged researchers to focus on safer, environmentally friendlier and cheaper alternatives as well as prompted the development of green synthesis. Apart from many advantages, green synthesis is often not selective enough (among other issues) to create shape-specific nanoparticle structures. Herein, we have used a biopolymer conjugate and Pd and Pt precursors to prepare sustainable bimetallic nanoparticles with various morphology types. The nanoparticles were synthesized by a novel green approach using a bio-conjugate of chitosan and polyhydroxybutyrate (Cs-PHB). The bio-conjugate plays the simultaneous roles of a reducing and a capping agent, which was confirmed by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and energy dispersive X-ray spectrometry (EDS) analysis, proving the presence of a Cs-PHB layer on the surface of the prepared nanoparticles. The EDS profile also revealed the elemental structure of these nanoparticles and confirmed the formation of a Pd/Pt alloy. TEM morphological analysis showed the formation of star-like, octahedron or decahedron Pd/Pt nanoparticles, depending on the synthesis conditions. The bimetallic Pd/Pt nanoparticles synthesized with various Pd/Pt molar ratios were successfully applied for the catalytic reduction of 4-nitrophenol to 4-aminophenol by borohydride. The calculated κc values (ratio of kapp to the concentration of the catalyst) revealed that the decahedron nanoparticles (size of 15 ± 4 nm), synthesized at the molar ratio of 2:1 (Pd/Pt), temperature of 130 °C, 10 g/L of Cs-PHB conjugate and time of 30 min, exhibited excellent catalytic activity compared to other bimetallic nanoparticles reported in the literature.

Gum Kondagogu/Reduced Graphene Oxide Framed Platinum Nanoparticles and Their Catalytic Role.

This study investigates an environmentally benign approach to generate platinum nanoparticles (Pt NP) supported on the reduced graphene oxide (RGO) by non-edible gum waste of gum kondagogu (GK). The reaction adheres to the green chemistry approach by using an aqueous medium and a nontoxic natural reductant-GK-whose abundant hydroxyl groups facilitate in the reduction process of platinum salt and helps as well in the homogenous distribution of ensued Pt NP on RGO sheets. Scanning Electron Microscopy (SEM) confirmed the formation of kondagogu gum/reduced graphene oxide framed spherical platinum nanoparticles (RGO-Pt) with an average particle size of 3.3 ± 0.6 nm, as affirmed by Transmission Electron Microscopy (TEM). X-ray Diffraction (XRD) results indicated that the Pt NPs formed are crystalline with a face-centered cubic structure, while morphological analysis by XRD and Raman spectroscopy revealed a simultaneous reduction of GO and Pt. The hydrogenation of 4-nitrophenol could be accomplished in the superior catalytic performance of RGO-Pt. The current strategy emphasizes a simple, fast and environmentally benign technique to generate low-cost gum waste supported nanoparticles with a commendable catalytic activity that can be exploited in environmental applications.

Chemical oxidation and reduction of hexachlorocyclohexanes: A review.

Lindane (γ-hexachlorocyclohexane) and its isomers (HCH) are some of the most common and most easily detected organochlorine pesticides in the environment. The widespread distribution of lindane is due to its use as an insecticide, accompanied by its persistence and bioaccumulation, whereas HCH were disposed of as waste in unmanaged landfills. Unfortunately, certain HCH (especially the most reactive ones: γ- and α-HCH) are harmful to the central nervous system and to reproductive and endocrine systems, therefore development of suitable remediation methods is needed to remove them from contaminated soil and water. This paper provides a short history of the use of lindane and a description of the properties of HCH, as well as their determination methods. The main focus of the paper, however, is a review of oxidative and reductive treatment methods. Although these methods of HCH remediation are popular, there are no review papers summarising their principles, history, advantages and disadvantages. Furthermore, recent advances in the chemical treatment of HCH are discussed and risks concerning these processes are given.

A new method for assessment of the sludge disintegration degree with the use of differential centrifugal sedimentation.

A novel method for assessing the disintegration degree (DD) of waste activated sludge (WAS) with the use of differential centrifugal sedimentation method (DCS) was shown herein. The method was validated for a WAS sample at four levels of disintegration in the range of 14.4-82.6% corresponding to the median particle size range of 8.5-1.6 µm. From the several sludge disintegration methods used (i.e. microwave, alkalization, ultrasounds and peroxydisulfate activated by ultrasounds), the activated peroxydisulfate disintegration resulted in the greatest DD 83% and the smallest median particle size of WAS. Particle size distribution of pretreated sludge, measured by DCS, was in a negative correlation with the DD, determined from soluble chemical oxygen demand (SCOD; determination coefficient of 0.995). Based on the obtained results, it may be concluded that the DCS analysis can approximate the WAS disintegration degree.

Production of electrospun nanofibers based on graphene oxide/gum Arabic.

Over the last few years, the electrospinning technique has attracted significant attention for the production of novel nanofibrous materials. At the same time, the use of graphene oxide and the natural products extracted from plants and/or trees have become very popular in various fields of science. In this work, a new method for the production of nanofibers based on a combination of Gum Arabic (GA), as a natural tree gum exudate, PVA, as an environmentally-friendly stabilizer, and graphene oxide (GO) has been developed and characterized. SEM analysis showed fundamental differences on the surface of bare nanofibers with and without GO, and also significantly smaller fiber diameters in the case of the presence of GO (fibers <100 nm present). Raman spectroscopy confirmed and TGA analysis approximated the content of GO in the nanofibers. Adsorption of methylene blue on the produced nanofibrous membrane was about 50% higher in the presence of GO, which opens the possibility to use GO/GA/PVA fibers in several applications, for example for the removal of dyes.

Oxidative stress is activated by free fatty acids in cultured human hepatocytes.

BACKGROUND: Nonalcoholic fatty liver disease (NAFLD) is strongly associated to oxidative stress, metabolic syndrome, and cardiovascular risk. Hepatocytes overloaded with fatty acids (FA) could generate substances that interfere with endothelial function, providing a potential explanation for this association. We have investigated the response of cultured human hepatoblastoma cells (Hep-G2) that were exposed to FA by measuring markers of oxidative stress and thrombosis and expression of the insulin receptor. METHODS: Hep-G2 cells were conditioned with a mixture of FA with or without N-acetyl-L-cysteine (NAC), glutathione (GSH), or adiponectin (ADN). After 7 days, we measured intracellular GSH (iGSH), nitric oxide (NO), malondialdehyde (MDA), and tissue plasminogen inhibitor-1 (PAI-1). Real-time polymerase chain reaction (PCR) was used to determine gene expression of inducible nitric oxide synthase (iNOS) and insulin receptor (INS-R). RESULTS: Exposure to FA decreased iGSH and NO levels in Hep-G2 cells and increased MDA and PAI-1 production. Gene expression of iNOS and INS-R in Hep-G2 cells was decreased by exposure to FA. Co-incubation with NAC and GSH prevented the change of iNOS mRNA levels, but not of INS-R; co-incubation with ADN restored the gene expression of INS-R, but not of i-NOS. ADN prevented also the FA-induced increase in MDA in cultured human endothelial cells. CONCLUSION: Exposure to FA activates oxidative stress and production of prothrombotic markers and decreases expression of insulin receptors in cultured human hepatocytes. These effects of FA are partially prevented by ADN and might contribute to the increased cardiovascular risk in patients with NAFLD and metabolic syndrome.

[PUFA in patients with ischemic cardiopathy]. / I PUFA n-3 nel paziente con cardiopatia ischemica.

n-3 Poliunsaturated Fatty Acids (PUFA) are essential; foods rich in n-3 are fat fish and some vegetal oil. PUFA are precursors of Eicosanoids, involved in the processes of inflammation, thrombosis and immunity. Firstly, observational studies measured reduction of cardiovascular disease (CVD) incidence with greater PUFA dietary intake. Experimental studies discovered antiahrrhytmic, antiatherogenic, antiaggregating and antiinflammatory properties. Retrospective analysis found lower incidence of sudden death (SD) in fish consumers. Randomized, prospective trials after myocardial infarction showed, in people either eating fish or receiving an n-3 PUFA supplement, a reduction of SD, explained by specific effect on membrane ion channels. The lack of results on atherothrombosis do not match with most experimental results, and should better be evaluated in absence of aspirin therapy. Low evidence supports use of n-3 PUFA in angina or revascularization procedures. Recent observations denote positive effect on endothelial function of large and resistance arteries. Actually evidence-based medicine suggest: improve of fish consumption for primary prevention of CVD; n-3 PUFA supplementation for hypertrigliceridemia and secondary prevention of SD after myocardial infarction, which is also cost-effectiveness.