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Phosphotungstic acid (HPW) and silicotungstic acid (HSiW) were tested as homogeneous and as heterogeneous catalysts (after immobilized on different supports as high surface area graphite -HSAG500-, montmorillonite -MMT- and alumina -Al2O3-) for the in situ transesterification of sewage sludge lipids. Both catalysts exhibited similar performance in homogeneous phase, with slightly higher biodiesel yield for HPW. When the different supports were tested with HPW, the maximum yield obtained follow the trend: MMT > HSAG500 > Al2O3, but a greater leaching of the heteropolyacid (HPA) was observed with MMT. Therefore, HSAG500 showed the best results with a good FAMEs profile. The percentage of active phase was optimized from 1 to 40%, reaching the optimum at 10%. A more heterogeneous surface is obtained with larger quantities, also favouring the HPA leaching. The reaction temperature and the use of sonication as pre-treatment were also optimized. The best results were obtained after sonication with HPW-HSAG500 (10%) as catalyst, catalyst/sludge ratio 1:2, MeOH/sludge ratio 33:1, 120 °C and 21 h of reaction time with a maximum biodiesel yield of 31.1 % (FAMEs/lipids). In view of the results obtained HPW supports on HSAG500 offers a novel alternative as heterogeneous acid catalyst for in situ transesterification using sewage sludge as raw material.

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Simultaneous utilization of photogenerated electrons and holes to achieve overall redox reactions is attractive but still far from practical application. The emerging step (S)-scheme mechanism has proven to be an ideal approach to inhibit charge recombination and supply photoinduced charges with highest redox potentials. Herein, a hierarchical phosphotungstic acid (H3PW12O40, HPW)@Znln2S4 (ZISW) heterojunction was prepared through one-pot hydrothermal method for simultaneous hydrogen (H2) evolution and benzyl alcohol upgrading. The fabricated HPW-based heterojunctions indicated much enhanced visible-light absorption, promoted photogenerated charge transfer and inhibited charge recombination, owing to hierarchical architecture based on visible-light responsive Znln2S4 microspheres, and S-scheme charge transfer pathway. The S-scheme mechanism was further verified by free-radical trapping electron spin resonance (ESR) spectra. Moreover, the wettability of composite heterojunction was improved by the modification of hydrophilic HPW, contributing to gaining active hydrogen (H+) from water sustainably. The optimal ZISW-30 heterojunction photocatalyst indicated an enhanced hydrogen evolution rate of 27.59 mmol g-1 h-1 in benzyl alcohol (10 vol. %) solution under full-spectrum irradiation, along with highest benzaldehyde production rate is 8.32 mmol g-1 h-1. This work provides a promising guideline for incorporating HPW into S-scheme heterojunctions to achieve efficient overall redox reactions.

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The imidazo[1,2-a]pyridine moiety is present in drugs with several biological activities. The most direct way of obtaining this nucleus is the Groebke-Blackburn-Bienaymé three-component reaction (GBB-3CR) between aminopyridines, aldehydes, and isocyanides under both Lewis and Brønsted acid catalysis. However, several catalysts for this reaction have major drawbacks such as being expensive, extremely dangerous, strong oxidizing, and even explosive. In this scenario, heteropolyacids emerge as greener and safer alternatives due to their very strong Brønsted acidity. In particular, phosphotungstic acid (HPW) is an economical and green attractive catalyst for being cheap, non-toxic, and is known for its chemical and thermal stability. Herein, we report a straightforward approach to the GBB-3CR using HPW as catalyst in ethanol under microwave (µw) heating. This convenient environmentally benign methodology is broad in scope, provides the heterobicyclic products in high yields (up to 99%), with a low catalyst loading (2 mol %) in only 30 minutes, and allows the successful use of aliphatic aldehydes, substrates not so frequently explored with most usual catalysts for this reaction. Furthermore, the aforementioned advantages make this methodology very attractive and superior to the existing ones.

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Previous research on covalent organic framework (COF)-based photocatalytic H2O2 synthesis from oxygen reduction focuses more on charge carrier separation but less on the electron utilization efficiency of O2. Herein, we put forward a facile approach to simultaneously promote charge separation and tailor the oxygen reduction pathway by introducing phosphotungstic acid (PTA) into the cationic COF skeleton. Experiments verified that PTA, as an electron transport medium, establishes a fast electron transfer channel from the COF semiconductor conductor band to the substrate O2; meanwhile, the reaction path is optimized by its catalytic cycle for preferable dioxygen capture and reduction in oxygen reduction reaction (ORR) kinetics. The existence of PTA promotes the rate and tendency of converting O2 into •O2- intermediates, which is conducive to boosting the photocatalytic activity and selectivity toward the sequential two-step single-electron ORR. As expected, compared to the pristine TTB-EB, the optimal PTA0.5@TTB-EB achieves a 2.2-fold improvement of visible-light-driven photocatalytic performance with a H2O2 production rate of 897.94 µmol·L-1·h-1 in pure water without using any sacrificial agents. In addition, owing to the robust electrostatic interaction and the confinement effect of porous TTB-EB channels, the PTA@TTB-EB composite possessed favorable stability.

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In this study, we have developed a novel catalyst synthesized by phosphotungstic acid and a gemini quaternary ammonium cation salt. This quaternary ammonium salt not only reduces the interfacial tension between olefins and hydrogen peroxide but also forms a notably stable structure with phosphotungstic acid. Dodecene was successfully epoxidized to epoxy dodecane with a selectivity of 82.9 %. The impact of initial conditions was systematically investigated such as molar ratio, temperature, reaction time, and catalyst dosage on the catalytic performance. Characterization of the catalyst morphology was performed by SEM, TEM and SAXS. Raman spectra, FT-IR and XPS spectra were employed to perform the catalyst transformation during the epoxidation reaction. This catalytic mechanism study could provide the industrial application in the epoxidation of long-chain olefins.

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Micro-computed tomography (microCT) is a common tool for the visualization of the internal composition of organic tissues. Collagen comprises approximately 25-35% of the whole-body protein content in mammals, and the structure and arrangement of collagen fibers contribute significantly to the integrity of tissues. Collagen type I is also frequently used as a key structural component in tissue-engineered and bioprinted tissues. However, the imaging of collagenous tissues is limited by their inherently low X-ray attenuation, which makes them indistinguishable from most other soft tissues. An imaging contrast agent that selectively alters X-ray attenuation is thus essential to properly visualize collagenous tissue using a standard X-ray tube microCT scanner. This review compares various contrast-enhanced techniques reported in the literature for MicroCT visualization of collagen-based tissues. An ideal microCT contrast agent would meet the following criteria: (1) it diffuses through the tissue quickly; (2) it does not deform or impair the object being imaged; and (3) it provides sufficient image contrast for reliable visualization of the orientation of individual fibers within the collagen network. The relative benefits and disadvantages of each method are discussed. Lugol's solution (I3K), phosphotungstic acid (H3PW12O40), mercury(II) chloride (HgCl2), and Wells-Dawson polyoxometalates came closest to fitting the criteria. While none of the contrast agents discussed in the literature met all criteria, each one has advantages to consider in the context of specific lab capabilities and imaging priorities.

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The present research is the first report on the application of Keggin-type phosphotungstic acid/polyvinylidene fluoride membrane. This compound as a simple, cost-effective and novel sorbent was used for the extraction and pre-concentration of two organophosphorus pesticides in real samples in the thin film solid-phase microextraction (TFME) method. TFME as one of the sub-branches of solid phase microextraction resolves the problems of SPME methods, including their limited absorption capacity. These extraction methods have a high surface-to-volume ratio, which improves their sensitivity compared to other geometries. Under optimal conditions, the limit of detections (LODs), the limit of quantifications (LOQs), and relative standard deviation (RSD) of this method varied in the ranges of 0.29-0.31 µg L-1, 0.96-1.0 µg L-1, and 3.9%-6.2%, respectively. This method showed a linear dynamic range (LDR) of 1.0-500 µg L-1 with a coefficient of determination (r2) above 0.9978. This promising method was used to analyze malathion and diazinon.

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Micro-computed tomography (micro-CT) provides valuable data for studying soft tissue, though it is often affected by sample movement during scans and low contrast in X-ray absorption. This can result in lower image quality and geometric inaccuracies, collectively known as 'artefacts'. To mitigate these issues, samples can be embedded in hydrogels and enriched with heavy metals for contrast enhancement. However, the long-term durability of these enhancements remains largely unexplored. In this study, we examine the effects of two contrast enhancement agents - iodine and phosphotungstic acid (PTA) - and two hydrogels - agarose and Poloxamer 407 - over a 14-day period. We used Drosophila melanogaster as a test model for our investigation. Our findings reveal that PTA and agarose are highly durable, while iodine and poloxamer hydrogel exhibits higher leakage rates. These observations lay the foundation for estimating contrast stabilities in contrast-enhanced micro-CT with hydrogel embedding and serve to inform future research in this field.

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Multiple stains have been historically utilized in electron microscopy to provide proper contrast and superior image quality enabling the discovery of ultrastructures. However, the use of these stains in microbiological viability assessment has been limited. Phosphotungstic acid (PTA) staining is a common negative stain used in scanning electron microscopy (SEM). Here, we investigate the feasibility of a new SEM-PTA assay, aiming to determine both viable and dead microbes. The optimal sample preparation was established by staining bacteria with different PTA concentrations and incubation times. Once the assay conditions were set, we applied the protocol to various samples, evaluating bacterial viability under different conditions, and comparing SEM-PTA results to culture. The five minutes 10% PTA staining exhibited a strong distinction between viable micro-organisms perceived as hypo-dense, and dead micro-organisms displaying intense internal staining which was confirmed by high Tungsten (W) peak on the EDX spectra. SEM-PTA viability count after freezing, freeze-drying, or oxygen exposure, were concordant with culture. To our knowledge, this study is the first contribution towards PTA staining of live and dead bacteria. The SEM-PTA strategy demonstrated the feasibility of a rapid, cost-effective and efficient viability assay, presenting an open-view of the sample, and providing a potentially valuable tool for applications in microbiome investigations and antimicrobial susceptibility testing.

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Herein, we report the synthesis of bimetal-organic frameworks (BMOFs) with both Brønsted and Lewis acidities, in which phosphotungstic acid (PTA) was encapsulated in BMOFs. It is efficient in converting starch to 5-hydroxymethyl-furfural (HMF) in deep eutectic solvents (DESs) such as choline chloride and formic acid. The highest yield of HMF (37.94%) was obtained using P0.5/BMOFs1.0 to catalyze starch in a mixed solvent system comprising DESs and ethyl acetate (EAC) (v/v; 2:3) at 180 °C and a reaction time of 10 min. Employing a DES as a cocatalyst and solvent reduced the use of organic solvents. The catalyst showed adequate reusability, and the HMF yield only decreased by 2.88% after six cycles of reuse compared with that of the initial catalyst. This study demonstrates the application potential of BMOFs in the conversion of biomass to useful molecules with commercial and/or research value.

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Background and aims: Atherosclerotic plaque rupture in the carotid artery can cause small emboli to travel to cerebral arteries, causing blockages and preventing blood flow leading to stroke. Contrast enhanced micro computed tomography (CEµCT) using a novel stain, phosphotungstic acid (PTA) can provide insights into the microstructure of the vessel wall and atherosclerotic plaque, and hence their likelihood to rupture. Furthermore, it has been suggested that collagen content and orientation can be related to mechanical integrity. This study aims to build on existing literature and establish a robust and reproducible staining and imaging technique to non-destructively quantify the collagen content within arteries and plaques as an alternative to routine histology. Methods: Porcine carotid arteries and human atherosclerotic plaques were stained with a concentration of 1% PTA staining solution and imaged using MicroCT to establish the in situ architecture of the tissue and measure collagen content. A histological assessment of the collagen content was also performed from picrosirius red (PSR) staining. Results: PTA stained arterial samples highlight the reproducibility of the PTA staining and MicroCT imaging technique used with a quantitative analysis showing a positive correlation between the collagen content measured from CEµCT and histology. Furthermore, collagen-rich areas can be clearly visualised in both the vessel wall and atherosclerotic plaque. 3D reconstruction was also performed showing that different layers of the vessel wall and various atherosclerotic plaque components can be differentiated using Hounsfield Unit (HU) values. Conclusion: The work presented here is unique as it offers a quantitative method of segmenting the vessel wall into its individual components and non-destructively quantifying the collagen content within these tissues, whilst also delivering a visual representation of the fibrous structure using a single contrast agent.

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Purpose: Even though current techniques provide two-dimensional (2D) imaging of the mouse mammary gland, they fail to achieve high-resolution three-dimensional (3D) reconstruction and quantification. The objective of this study is to establish and evaluate quantitative visualization of the mouse mammary epithelium through microcomputed tomography (microCT) using phosphotungstic acid (PTA) as a contrast agent. Approach: Ex vivo microCT scan images of the mouse mammary glands were obtained following staining by PTA, whereas for quantification we adapted volumetric parameters that are used for assessing trabecular bone morphometry and can be structurally applicable in the mammary ductal system. The proposed method was validated in distinct developmental stages and upon short-term treatment with synthetic progesterone, using the carmine alum staining for comparison. Results: We demonstrate a simple PTA staining procedure that allows high contrast 3D imaging of mammary glands and quantitation of mammary duct structures using microCT. We validated the proposed method in distinct developmental stages, such as at puberty, adult mice, pregnancy as well as upon progesterone treatment. Compared with carmine alum staining, the microCT analysis provided higher resolution 2D and 3D images of the mammary gland morphology, with lower background that enabled the detection of subtle changes. Conclusions: This work is the first study that employs PTA-enhanced microCT for 3D imaging and volumetric analysis of mouse mammary glands. Our results establish PTA-enhanced microCT as a useful tool for comparative studies of the mouse mammary gland morphology that can apply in mutant mice and for the preclinical evaluation of pharmaceuticals in breast cancer models.

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Composite chitosan/phosphotungstic acid (CS/PTA) with the addition of TiO2 and Al2O3 particles were synthesized to be used as proton exchange membranes in direct methanol fuel cells (DMFCs). The influence of fillers was assessed through X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, liquid uptake, ion exchange capacity and methanol permeability measurements. The addition of TiO2 particles into proton exchange membranes led to an increase in crystallinity and a decrease in liquid uptake and methanol permeability with respect to pristine CS/PTA membranes, whilst the effect of the introduction of Al2O3 particles on the characteristics of membranes is almost the opposite. Membranes were successfully tested as proton conductors in a single module DMFC of 1 cm2 as active area, operating at 50 °C fed with 2 M methanol aqueous solution at the anode and oxygen at the cathode. Highest performance was reached by using a membrane with TiO2 (5 wt.%) particles, i.e., a power density of 40 mW cm-2, almost doubling the performance reached by using pristine CS/PTA membrane (i.e., 24 mW cm-2).

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Tetracyclines are refractory pollutants that cause persistent harm to the environment and human health. Therefore, it is urgently necessary to develop methods to promote the efficient degradation and conversion of tetracyclines in wastewater. This report proposes a photobiocatalytic synergistic system involving the coupling of GeO2/Zn-doped phosphotungstic acid hydrate/TiO2 (GeO2/Zn-HPW/TiO2)-loaded photocatalytic optical hollow fibers (POHFs) and an algal-bacterial biofilm. The GeO2/Zn-HPW/TiO2 photocatalyst exhibits a broad absorption edge extending to 1000 nm, as well as high-efficiency photoelectric conversion and electron transfer, which allow the GeO2/Zn-HPW/TiO2-coated POHFs to provide high light intensity to promote biofilm growth. The resulting high photocatalytic activity rapidly and stably reduces the toxicity and increases the biodegradability of tetracycline-containing wastewater. The biofilm enriched with Salinarimonas, Coelastrella sp., and Rhizobium, maintains its activity for the rapid photocatalytic degradation and biotransformation of intermediates to generate the O2 required for photocatalysis. Overall, the synergistic photocatalytic biofilm system developed herein provides an effective and efficient approach for the rapid degradation and conversion of water containing high concentrations of tetracycline.

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Tramadol is an analgesic drug that is mainly excreted in the urine. The entry of Tramadol into water samples causes their biological contamination. Therefore, three catalysts such as bismuth ferrite, cobalt-doped bismuth ferrite, and a magnetized Keggin type of polyoxometalate (α-Fe2O3@phosphotungstic acid), were synthesized as photocatalysts to degrade Tramadol in water samples. The morphology and properties of the prepared photocatalysts were evaluated using several techniques. Effects of several factors, including tramadol concentration, pH, hydrogen peroxide concentration, and photocatalyst amount, were studied and optimized by a design experiment procedure based on Box-Behnken design for reducing the number of experiments and cost and investigating the interactions between factors in the photocatalytic degradation process of Tramadol. These factors were optimized for each prepared photocatalyst individually. Under the optimum conditions, the percentages of tramadol degradation and kinetics of the degradation process were evaluated in the presence of each photocatalyst. The tramadol degradation percentages using bismuth ferrite, cobalt-doped bismuth ferrite, and α-Fe2O3 @phosphotungstic acid were 81.10% for 120 min, 90.63% for 80 min, and 91.32% for 80 min, respectively. The rate constants of tramadol degradation were 0.0145, 0.0329, and 0.0312 min-1 for bismuth ferrite, cobalt-doped bismuth ferrite, and α-Fe2O3 @phosphotungstic acid, respectively. The results indicated the highest percentage of tramadol degradation and rate of the degradation process were obtained using α-Fe2O3 @phosphotungstic acid and cobalt-doped bismuth ferrite, respectively.

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We tried to prevent nonspecific nuclear staining (NS-NS) of picrosirius red (PSR) staining by treating the specimens with one of the heteropoly acids phosphotungstic acid (PTA). We analyzed a total of 35 cases of non-cancerous liver tissue for fibrosis and NS-NS under PSR-alone, phosphomolybdic acid (PMA)-pretreated PSR (PMA + PSR), or PTA-pretreated PSR (PTA + PSR) condition. In addition, we analyzed the photosensitivity of PMA or PTA single stain specimens. PTA + PSR significantly suppressed NS-NS compared with PSR. The color of the specimens did not change into blue by 30 times the exposure to whole slide scanner (WSS) light. The PTA + PSR condition showed the highest correlation with the Ishak score (pathological evaluation of liver fibrosis) compared with other conditions. Furthermore, Sirius Red-positive percentage (SRP%) in PSR was increased in the NS-NS observed cases. SRP% in PMA + PSR was significantly affected by WSS light exposure time. Moreover, the deposition of non-polarized PSR-stained substances (NP-PSR+S) clinging to the collagen fibers potentially explains why SRP% seemed bigger under PSR than PTA + PSR. Our protocol enabled us to analyze the whole slide image of PSR staining by high magnification, which would contribute to the accurate analysis of collagen amount in the tissue sections.

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Phosphotungstic acid covered with CeO2 hollow nanospheres (CeO2@PTA HNSs) has been successfully prepared by a simple method, serving as highly efficient nanozymes for ascorbic acid (AA) colorimetric sensing. In virtue of the unique hollow nanostructures, oxide defects and synergic effects of CeO2 and PTA, the proposed CeO2@PTA HNSs present remarkable intrinsic oxidase-like activity and help capture electrons from 3,3',5,5'-tetramethylbenzidine (TMB). Due to the reducibility of AA, a promising colorimetric sensing platform based on CeO2@PTA HNSs has been constructed for quantitative analysis of AA. The present colorimetric detection exhibits a low limit of detection, good selectivity and stability, as well as reliability in orange juice and milk. This work provides a simple surface defect engineering to prepare high-performance oxidase mimics in the application of colorimetric biosensing.

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Keggin-type phosphotungstic acid (HPW) supported on imidazolyl-activated carbon (AC-COIMI-HPW) catalysts was prepared, which was used to catalyze the oxidation of benzyl alcohol with aqueous H2O2. In the presence of AC-COIMI-HPW, the benzyl alcohol conversion of 90.2% with 91.8% selectivity of benzaldehyde was obtained at 90°C for 6 h in an acetonitrile aqueous solution. The catalyst exhibited an outstanding performance for the oxidation of various benzyl alcohols and aliphatic alcohols. In addition, the catalyst could be easily recovered and reused five times without significant deactivation. The characterization results showed that HPW was chemically bonded on the surface of the carbon material through an ionic bond. It is proposed that the combination of the imidazole cation with the HPW anion could not only tune the redox catalytic properties of the PW anion but also enhance the compatibility of the catalyst in the reaction medium, thereby improving the catalytic performance.

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This work presents the development of a cost-effective electric-stimulus-responsive bending actuator based on a sulfonated polyvinyl chloride (SPVC)-phosphotungstic acid (PTA) ionic polymer-metal composite (IPMC), using a simple solution-casting method followed by chemical reduction of platinum (Pt) ions as an electrode. The characterizations of the prepared IPMC were performed using Fourier-transform infrared (FTIR) spectroscopy, Scanning electron microscopy (SEM), X-ray diffraction (XRD) techniques, Thermogravimetric analysis (TGA), and Energy-dispersive X-ray (EDX) analysis. Excellent ion-exchange capacity (IEC) and proton conductivity (PC), with values of ca. 1.98 meq·g-1 and ca. 1.6 mS·cm-1, respectively, were observed. The water uptake (WU) and water loss (WL) capacities of the IPMC membranes were measured at 25 °C, and found to have maxima of ca. 48% for 10 h, and ca. 36% at 6 V DC for almost 9 min, respectively. To analyze the actuation performance of the developed membrane, tip displacement and actuation force measurements were conducted. Tip displacement was found to be ca. 15.1 mm, whereas bending actuation was found to be 0.242 mN at 4 V DC. The moderate water loss, good proton conductivity (PC), high thermal stability, and good electrochemical properties of the developed IPMC membrane actuator position it as a cost-effective alternative to highly expensive conventional perfluorinated polymer-based actuators.

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BACKGROUND: 5-Hydroxymethylfurfural (5-HMF) is a high value-added platform compound which can be obtained by dehydration of hexose under acidic conditions. OBJECTIVE: In this paper, a novel impregnation strategy for the molecular sieves (ZSM-5) as carrier and phosphotungstic acid (TPA) as active ingredient is proposed, the influence of the fructose dehydration process were studied and eco-friendliness, low-cost 5-hydroxymethylfurfural (5-HMF) was successfully obtained. METHOD: The structure surface area, pore size, acidity and microstructure of solid acid catalysts were investigated by XRD, BET, NH3-TPD and SEM. The influences of reaction temperature, reaction time, catalyst dosage on the yield of 5-hydroxymethylfurfural (5-HFM) were investigated. RESULTS: The results showed that TPA/ZSM-5 (mass ratio 20:10) has good dispersion and catalytic activity, fructose dosage 5 g, reaction temperature 140 °C, reaction time 2 h, catalyst dosage 0.5 g, and the yield of 5-hydroxymethylfurfural was 80.75% and after five times use the yield of 5-HMF remained above 75%. CONCLUSION: The novel solid acid TPA/ZSM-5 catalyst exhibited good catalytic activity and stability for the fructose dehydration to produce 5-HMF.

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