Enhanced and copper concentration dependent virucidal effect against SARS-CoV-2 of electrospun poly(vinylidene difluoride) filter materials.

Virucidal filter materials were prepared by electrospinning a solution of 28 wt % poly(vinylidene difluoride) in N,N-dimethylacetamide without and with the addition of 0.25 wt %, 0.75 wt %, 2.0 wt %, or 3.5 wt % Cu(NO3)2 · 2.5H2O as virucidal agent. The fabricated materials had a uniform and defect free fibrous structure and even distribution of copper nanoclusters. X-ray diffraction analysis showed that during the electrospinning process, Cu(NO3)2 · 2.5H2O changed into Cu2(NO3)(OH)3. Electrospun filter materials obtained by electrospinning were essentially macroporous. Smaller pores of copper nanoclusters containing materials resulted in higher particle filtration than those without copper nanoclusters. Electrospun filter material fabricated with the addition of 2.0 wt % and 3.5 wt % of Cu(NO3)2 · 2.5H2O in a spinning solution showed significant virucidal activity, and there was 2.5 ± 0.35 and 3.2 ± 0.30 logarithmic reduction in the concentration of infectious SARS-CoV-2 within 12 h, respectively. The electrospun filter materials were stable as they retained virucidal activity for three months.

Self-cementing properties of oil shale solid heat carrier retorting residue.

Oil shale-type organic-rich sedimentary rocks can be pyrolysed to produce shale oil. The pyrolysis of oil shale using solid heat carrier (SHC) technology is accompanied by large amount of environmentally hazardous solid residue-black ash-which needs to be properly landfilled. Usage of oil shale is growing worldwide, and the employment of large SHC retorts increases the amount of black ash type of waste, but little is known about its physical and chemical properties. The objectives of this research were to study the composition and self-cementing properties of black ash by simulating different disposal strategies in order to find the most appropriate landfilling method. Three disposal methods were simulated in laboratory experiment: hydraulic disposal with and without grain size separation, and dry dumping of moist residue. Black ash exhibited good self-cementing properties with maximum compressive strength values of >6 MPa after 90 days. About 80% of strength was gained in 30 days. However, the coarse fraction (>125 µm) did not exhibit any cementation, thus the hydraulic disposal with grain size separation should be avoided. The study showed that self-cementing properties of black ash are governed by the hydration of secondary calcium silicates (e.g. belite), calcite and hydrocalumite.

Hydrothermal Regeneration of Ammonium as a Basin-Scale Driver of Primary Productivity.

Hydrothermal vents are important targets in the search for life on other planets due to their potential to generate key catalytic surfaces and organic compounds for biogenesis. Less well studied, however, is the role of hydrothermal circulation in maintaining a biosphere beyond its origin. In this study, we explored this question with analyses of organic carbon, nitrogen abundances, and isotopic ratios from the Paleoproterozoic Zaonega Formation (2.0 Ga), NW Russia, which is composed of interbedded sedimentary and mafic igneous rocks. Previous studies have documented mobilization of hydrocarbons, likely associated with magmatic intrusions into unconsolidated sediments. The igneous bodies are extensively hydrothermally altered. Our data reveal strong nitrogen enrichments of up to 0.6 wt % in these altered igneous rocks, suggesting that the hydrothermal fluids carried ammonium concentrations in the millimolar range, which is consistent with some modern hydrothermal vents. Furthermore, large isotopic offsets of ∼10‰ between organic-bound and silicate-bound nitrogen are most parsimoniously explained by partial biological uptake of ammonium from the vent fluid. Our results, therefore, show that hydrothermal activity in ancient marine basins could provide a locally high flux of recycled nitrogen. Hydrothermal nutrient recycling may thus be an important mechanism for maintaining a large biosphere on anoxic worlds.

Design of High Volume CFBC Fly Ash Based Calcium Sulphoaluminate Type Binder in Mixtures with Ordinary Portland Cement.

Growing concerns on global industrial greenhouse gas emissions have boosted research for developing alternative, less CO2 intensive binders for partial to complete replacement of ordinary Portland cement (OPC) clinker. Unlike slag and pozzolanic siliceous low-Ca class F fly ashes, the Ca- and S-rich class C ashes, particularly these formed in circulating fluidised bed combustion (CFBC) boilers, are typically not considered as viable cementitious materials for blending with or substituting the OPC. We studied the physical, chemical-mineralogical characteristics of the mechanically activated Ca-rich CFBC fly ash pastes and mortars with high volume OPC substitution rates to find potential alternatives for OPC in building materials and composites. Our findings indicate that compressive strength of pastes and mortars made with partial to complete replacement of the mechanically activated CFBC ash to OPC is comparable to OPC concrete, showing compared to OPC pastes reduction in compressive strength only by <10% at 50% and <20% at 75% replacement rates. Our results show that mechanically activated Ca-rich CFBC fly ash can be successfully used as an alternative CSA-cement type binder.

Preparation and characterization of hot-melt extruded polycaprolactone-based filaments intended for 3D-printing of tablets.

Hot-melt extruded (HME) filaments are an essential intermediate product for the three- dimensional (3D) printing of drug delivery systems (DDSs) by the fused deposition modelling (FDM) process. The aim of this study was to design novel polymeric 3D-printable HME filaments loaded with active pharmaceutical ingredients (APIs). The physical solid-state properties, mechanical properties, drug release and short-term storage stability of the filaments and 3D-printed DDSs were studied. Physical powder mixtures of polycaprolactone (PCL), plasticizer and API were manually blended, extruded by a single-screw extruder, and printed by a table-top FDM 3D-printing system. The composition of PCL and arabic gum (ARA) enabled the incorporation of 20%, 30% and 40% (w/w) of indomethacin (IND) and theophylline (THEO) into the HME filaments. The uneven distribution of API throughout the filaments impaired 3D printing. The HME filaments loaded with 20% IND or THEO were selected for the further analysis and printing tests (the ratio of PCL, ARA and IND or THEO was 7:1:2, respectively). The IND filaments were yellowish, mechanically strong and flexible, and they had a uniform filament diameter and smooth outer surface. The filaments containing THEO were smooth and off-white. The 3D-printed tablets fabricated from IND or THEO-loaded filaments showed sustained drug release in vitro. The drug release rate, however, significantly increased by changing the geometry of 3D-printed tablets from a conventional tablet structure to an unorthodox lattice ("honeycomb") structure. Overall, the combination of PCL and ARA provides an interesting novel polymeric carrier system for 3D-printable HME filaments and tablets.

The kaolinite shuttle links the Great Oxidation and Lomagundi events.

The ~2.22-2.06 Ga Lomagundi Event was the longest positive carbon isotope excursion in Earth's history and is commonly interpreted to reflect perturbations in continental weathering and the phosphorous cycle. Previous models have focused on mechanisms of increasing phosphorous solubilization during weathering without focusing on transport to the oceans and its dispersion in seawater. Building from new experimental results, here we report kaolinite readily absorbs phosphorous under acidic freshwater conditions, but quantitatively releases phosphorous under seawater conditions where it becomes bioavailable to phytoplankton. The strong likelihood of high weathering intensities and associated high kaolinite content in post-Great-Oxidation-Event paleosols suggests there would have been enhanced phosphorus shuttling from the continents into marine environments. A kaolinite phosphorous shuttle introduces the potential for nonlinearity in the fluxes of phosphorous to the oceans with increases in chemical weathering intensity.

Electrospun Amphiphilic Nanofibers as Templates for In Situ Preparation of Chloramphenicol-Loaded Liposomes.

The hydration of phospholipids, electrospun into polymeric nanofibers and used as templates for liposome formation, offers pharmaceutical advantages as it avoids the storage of liposomes as aqueous dispersions. The objective of the present study was to electrospin and characterize amphiphilic nanofibers as templates for the preparation of antibiotic-loaded liposomes and compare this method with the conventional film-hydration method followed by extrusion. The comparison was based on particle size, encapsulation efficiency and drug-release behavior. Chloramphenicol (CAM) was used at different concentrations as a model antibacterial drug. Phosphatidylcoline (PC) with polyvinylpyrrolidone (PVP), using ethanol as a solvent, was found to be successful in fabricating the amphiphilic composite drug-loaded nanofibers as well as liposomes with both methods. The characterization of the nanofiber templates revealed that fiber diameter did not affect the liposome size. According to the optical microscopy results, the immediate hydration of phospholipids deposited on the amphiphilic nanofibers occurred within a few seconds, resulting in the formation of liposomes in water dispersions. The liposomes appeared to aggregate more readily in the concentrated than in the diluted solutions. The drug encapsulation efficiency for the fiber-hydrated liposomes varied between 14.9 and 28.1% and, for film-hydrated liposomes, between 22.0 and 77.1%, depending on the CAM concentrations and additional extrusion steps. The nanofiber hydration method was faster, as less steps were required for the in-situ liposome preparation than in the film-hydration method. The liposomes obtained using nanofiber hydration were smaller and more homogeneous than the conventional liposomes, but less drug was encapsulated.

Long-term mineral transformation of Ca-rich oil shale ash waste.

Power generation and other industries using solid fossil fuels like coal, lignite, oil shale and peat are responsible for producing large quantities of solid residues that are often chemically reactive and/or unstable and are disposed in holding ponds and deposition sites. Stability and long-term behaviour of such deposits are typically studied in short-term laboratory experiments that cannot describe nor predict long-term changes taking place in these materials. Here, we study long-term (>40 years) transformations, in highly alkaline conditions, of the Ca-rich ash deposit in Estonia composed of oil shale processing residues from the Eesti power plant. Detailed mineralogical, chemical and micromorphological analyses using X-ray diffraction, X-ray fluorescence, 29Si nuclear magnetic resonance, scanning electron microscopy and other methods were applied in order to identify the composition of the waste with a focus on formation and transformation of semicrystalline phases in the deposit. The results show progressive formation of calcium-silicate-hydrate (C-S-H) type phase at the expense of silicate minerals and amorphous glass phases with increasing depth and age of the sediments, from about 25% in the upper part of the depository to over 60% in the oldest-deepest part. This demonstrates that over time the high alkalinity of the ash is responsible for initiating natural alkali-activation. The formation of C-S-H-type phases increases the mechanical strength of the sediment and ensures long-term stability of waste deposits. These findings may encourage the use of these ashes in binder or other construction material production or as construction aggregates.

Hydrated calcareous oil-shale ash as potential filter media for phosphorus removal in constructed wetlands.

The P-retention in hydrated calcareous ash sediment from oil-shale burning thermal power plants in Estonia was studied. Batch experiments indicate good (up to 65 mg P g(-1)) P-binding capacity of the hydrated oil-shale ash sediment, with a removal effectiveness of 67-85%. The high phosphorus sorption potential of hydrated oil-shale ash is considered to be due to the high content of reactive Ca-minerals, of which ettringite Ca6Al2(SO4)3(OH)12.26H2O and portlandite Ca(OH)2 are the most important. The equilibrium dissolution of ettringite provides free calcium ions that act as stable nuclei for phosphate precipitation. The precipitation mechanism of phosphorus removal in hydrated ash plateau sediment is suggested by Ca-phosphate formation in batch experiments at different P-loadings. Treatment with a P-containing solution causes partial-to-complete dissolution of ettringite and portlandite, and precipitation of Ca-carbonate and Ca-phosphate phases, which was confirmed by X-ray diffraction (XRD) and scanning electron microscope (SEM)-EDS studies. Thus, the hydrated oil-shale ash sediment can be considered as a potential filtration material for P removal in constructed wetlands for wastewater treatment.

Air-drying is sufficient pre-treatment for in situ visualization of microbes on minerals with scanning electron microscopy.

Scanning electron microscopy (SEM) is a powerful tool for observing microbe-mineral interactions in situ. Despite its wide usage in geomicrobiology there is no consensus on how the samples should be handled before visualizing in SEM. We compared response of artificial laboratory-grown bacterial community and natural in situ microbes on terrestrial basalt to different sample pre-treatment methods with the aim to preserve microbe-mineral interaction interface. Air-drying was the only method that maintained the location of loosely attached bacteria on a mineral surface, whereas chemical fixation and drying dislocated the cells. On the contrary, chemical fixation preserved the cellular morphology while air-drying caused the collapse of most of the laboratory-grown cells. Natural microbial communities on dry terrestrial basalt were composed of desiccation resistant microbes which remained attached to the surface and partially maintained their morphology regardless of the sample pre-treatment method. None of the tested methods allowed visualization of microbe-mineral interface in a biofilm. We suggest air-drying as a main sample pre-treatment method for visualizing microbes on mineral surfaces when loss of morphology is secondary to potentially dislocated cells and to potential chemical changes in the sample caused by the chemical fixation reagents.

Authigenesis of biomorphic apatite particles from Benguela upwelling zone sediments off Namibia: The role of organic matter in sedimentary apatite nucleation and growth.

Sedimentary phosphorites comprise a major phosphorus (P) ore, yet their formation remains poorly understood. Extant polyphosphate-metabolizing bacterial communities are known to act as bacterial phosphate-pumps, leading to episodically high dissolved phosphate concentrations in pore waters of organic-rich sediment. These conditions can promote the precipitation of amorphous precursor phases that are quickly converted to apatite-usually in carbonate fluorapatite form [Ca10 (PO4 ,CO3 )6 F2-3 ]. To assess the mechanisms underpinning the nucleation and growth of sedimentary apatite, we sampled P-rich sediments from the Namibian shelf, a modern environment where phosphogenesis presently occurs. The P-rich fraction of the topmost centimetres of sediment mainly consists of pellets about 50-400 µm in size, which in turn are comprised of micron-sized apatite particles that are often arranged into radial structures with diameters ranging from 2 to 4 µm, and morphologies that range from rod-shapes to dumbbells to spheres that resemble laboratory-grown fluorapatite-gelatin nanocomposites known from double-diffusion experiments in organic matrices. The nucleation and growth of authigenic apatite on the Namibian shelf is likely analogous to these laboratory-produced precipitates, where organic macromolecules play a central role in apatite nucleation and growth. The high density of apatite nucleation sites within the pellets (>109 particles per cm3 ) suggests precipitation at high pore water phosphate concentrations that have been reported from the Namibian shelf and may be attributed to microbial phosphate pumping. The intimate association of organic material with the apatite could suggest a possible role of biological substrata, such as exopolymeric substances (EPS), in the nucleation of apatite precursors. Importantly, we do not observe any evidence that the apatite particles are actual phosphatized microbes, contradicting some earlier studies. Nevertheless, these results further evidence the potential importance of microbially derived (extracellular) organic matter as a template for phosphatic mineral nucleation in both recent and ancient phosphorites.

Ratiometric in vivo auditioning of targeted silver nanoparticles.

Attaching affinity ligands to nanoparticles (NPs) increases selectivity for targeting cells and tissues, and can result in improved sensitivity and reduced off-target toxicity in diagnostic and therapeutic systems. The decision over key features - NP size, shape, coating strategies and targeting ligands for clinical translation is often hampered by a lack of quantitative in vivo NP homing assays. Sensitive, internally controlled assays are needed which allow for quantitative comparisons (auditions) among various formulations of targeted NPs. We recently reported the development of peptide-functionalized, isotopically-barcoded silver NPs (AgNPs) for ultrasensitive studies centered on measuring relative ratios of NP internalization into cultured cells. Here we evaluated the application of this technology for NP homing studies in live mice using peptides with previously described tissue tropism; one peptide that favors vascular beds of the normal lungs (RPARPAR; receptor neuropilin-1, or NRP-1) and another that is selective for central nervous system vessels (CAGALCY). Equimolar mixtures of the peptide-targeted Ag107-NPs and Ag109 control particles were mixed and injected intravenously. Distribution profiles of Ag107 and Ag109 in tissue extracts were determined simultaneously through inductively coupled plasma mass spectrometry (ICP-MS). Compared to non-targeted particles up to ∼9-fold increased lung accumulation was seen for RPARPAR-OH AgNPs (but not for AgNPs functionalized with RPARPAR-NH2, which does not bind to NRP-1). Similarly, AgNPs functionalized with the brain-homing CAGALCY peptide were overrepresented in brain extracts. Spatial distribution (mapping) analysis by laser ablation ICP-MS (LA-ICP-MS) was used to determine the ratio Ag107/Ag109 in tissue cryosections. The mapping demonstrated preferential accumulation of the RPARPAR-AgNPs in the perivascular areas around pulmonary veins, and CAGALCY AgNPs accumulated in discrete areas of the brain (e.g. in the vessels of cerebellar fibrillary tracts). Based on these results, the internally controlled ratiometric AgNP system is suitable for quantitative studies of the effect of targeting ligands on NP biodistribution, at average tissue concentration and distribution at the microscopic level. The platform might be particularly relevant for target sites with high local variability in uptake, such as tumors.

Suberin fatty acids isolated from outer birch bark improve moisture barrier properties of cellulose ether films intended for tablet coatings.

We showed that the addition of suberin fatty acids (SFAs) even at small concentrations significantly improves the water vapor barrier properties of hydroxypropyl methylcellulose (HPMC) films. SFAs were isolated from the outer birch bark using extractive hydrolysis. The effects of SFAs on the film formation of aqueous HPMC were investigated with free films plasticized with polyethylene glycol (PEG 400). Special attention was paid on the physical solid-state, moisture barrier and mechanical stress-strain properties of films intended for tablet film coatings. Topography and surface morphology, glass transition temperature (Tg), tensile strength, Young's modulus, and water vapor permeation (WVP) of films were studied. The addition of SFAs lowered the Tg of films suggesting partial enhancement in film plasticization. The WVP of films decreased with increasing SFAs concentration up to 15% (calculated as a % w/w from a polymer weight). The WVP value for a non-suberized reference film and suberized film plasticized with PEG 400 was 2.13×10(-6) and 0.69[×10(-6) g/(mm(2)×h)×mm/Pa], respectively. The addition of SFAs impaired the mechanical stress-strain properties of HPMC films by reducing the deformation capacity of film. In conclusion, the film properties and performance of aqueous HPMC can be modified by including SFAs in the films.

Electrospun nanofibers as a potential controlled-release solid dispersion system for poorly water-soluble drugs.

Electrospinning was introduced as a novel technique for preparing controlled-release (CR) amorphous solid dispersions (SD) and polymeric nanofibers of a poorly water-soluble drug. Piroxicam (PRX) was used as a low-dose poorly-soluble drug and hydroxypropyl methylcellulose (HPMC) as an amorphous-state stabilising carrier polymer in nanofibers. Raman spectroscopy, X-ray powder diffraction (XPRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were used in the physical characterisation of the CR-SD nanofibers. Special attention was paid on the effects of a polymer and solvent system on the solid-state properties and physical stability of nanofibers. The average dry diameter of the electrospun CR-SD nanofibers ranged from 400 to 600 nm (SEM). PRX existed in amorphous form in the nanofibers immediately after fabrication and after a short-term (3-month) aging at low temperature (6-8 °C/0% RH) and ambient room temperature (22 °C/0% RH). At higher temperature and humidity (30 °C/85% RH), however, amorphous PRX in the nanofibers tended to slowly recrystallise to PRX form III. The electrospun CR-SD nanofibers exhibited a short lag-time, the absence of initial burst release and zero-order linear CR dissolution kinetics. In conclusion, electrospinning can be used to fabricate supersaturating CR-SD nanofibers of PRX and HPMC, and to stabilise the amorphous state of PRX.

Soluplus graft copolymer: potential novel carrier polymer in electrospinning of nanofibrous drug delivery systems for wound therapy.

Electrospinning is an effective method in preparing polymeric nanofibrous drug delivery systems (DDSs) for topical wound healing and skin burn therapy applications. The aim of the present study was to investigate a new synthetic graft copolymer (Soluplus) as a hydrophilic carrier polymer in electrospinning of nanofibrous DDSs. Soluplus (polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (PCL-PVAc-PEG)) was applied in the nonwoven nanomats loaded with piroxicam (PRX) as a poorly water-soluble drug. Raman spectroscopy, X-ray powder diffraction, differential scanning calorimetry, and scanning electron microscopy (SEM) were used in the physical characterization of nanofibrous DDSs. According to the SEM results, the drug-loaded PCL-PVAc-PEG nanofibers were circular in cross-section with an average diameter ranging from 500 nm up to 2 µm. Electrospinning stabilized the amorphous state of PRX. In addition, consistent and sustained-release profile was achieved with the present nanofibrous DDSs at the physiologically relevant temperature and pH applicable in wound healing therapy. In conclusion, electrospinning can be used to prepare nanofibrous DDSs of PCL-PVAc-PEG graft copolymer (Soluplus) and to stabilize the amorphous state of a poorly water-soluble PRX. The use of this synthetic graft copolymer can open new options to formulate nanofibrous DDSs for wound healing.

Solid-state properties of softwood lignin and cellulose isolated by a new acid precipitation method.

Solid-state and powder properties of softwood lignin and cellulose prepared by a new catalytic oxidation and acid precipitation method were characterized and compared with the commercial softwood and hardwood lignin and cellulose products. Catalytic pre-treated softwood lignin (CPSL) and cellulose (CPSC) were isolated from pine wood (Pinus sylvestris). CPSL with nearly micronized-scale particle size showed excellent powder flow and densification behavior due to the round shape and electrically minimum charged surface characteristics of particles. CPSL and the reference lignin studied were amorphous solids while CPSC exhibited a typical crystal lattice for cellulose I. In conclusion, physicochemical material properties of lignin and cellulose can be modified for biomedical and pharmaceutical applications with the present catalytic oxidation and acid precipitation method.

Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments.

Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years.

Phosphorus removal using Ca-rich hydrated oil shale ash as filter material--the effect of different phosphorus loadings and wastewater compositions.

We studied the phosphorus (P) binding capacity of Ca-rich alkaline filter material - hydrated oil shale ash (i.e. hydrated ash) in two onsite pilot-scale experiments (with subsurface flow filters) in Estonia: one using pre-treated municipal wastewater with total phosphorus (TP) concentration of 0.13-17.0 mg L(-1) over a period of 6 months, another using pre-treated landfill leachate (median TP 3.4 mg L(-1)) for a total of 12 months. The results show efficient P removal (median removal of phosphates 99%) in horizontal flow (HF) filters at both sites regardless of variable concentrations of several inhibitors. The P removal efficiency of the hydrated ash increases with increasing P loading, suggesting direct precipitation of Ca-phosphate phases rather than an adsorption mechanism. Changes in the composition of the hydrated ash suggest a significant increase in P concentration in all filters (e.g. from 489.5 mg kg(-1) in initial ash to 664.9 mg kg(-1) in the HF filter after one year in operation), whereas almost all TP was removed from the inflow leachate (R(2) = 0.99). Efficiency was high throughout the experiments (median outflow from HF hydrated ash filters 0.05-0.50 mg L(-1)), and P accumulation did not show any signs of saturation.