Removing siloxanes and hydrogen sulfide from landfill gases with biochar and activated carbon filters.

Landfill gas (LFG) is formed by microorganisms within a landfill; it can be utilized as a renewable fuel in power plants. Impurities such as hydrogen sulfide and siloxanes can cause significant damage to gas engines and turbines. The aim of this study was to determine the filtration efficiencies of biochar products made of birch and willow to remove hydrogen sulfides, siloxanes, and volatile organic compounds from the gas streams compared to activated carbon. Experiments were conducted on a laboratory scale with model compounds and in a real LFG power plant where microturbines are used to generate power and heat. The biochar filters removed heavier siloxanes effectively in all of the tests. However, the filtration efficiency for volatile siloxane and hydrogen sulfide declined quickly. Biochars are promising filter materials but require further research to improve their performance.

Real-Time On-Site Multielement Analysis of Environmental Waters with a Portable X-ray Fluorescence (pXRF) System.

Strict regulations are in place to control the effluents of mining sites and other industries. Heavy metal contamination of aquatic systems caused by leakages is difficult to mitigate as it takes time to detect and localize the leak. Dynamic sampling would drastically reduce the time to locate leakages and allow faster actions to reduce the impact on the environment. The present study introduces a novel portable multielement water analysis system to simultaneously measure Mn, Ni, Cu, Zn, Pb, and U in water samples from natural sources within 15 min from the sampling. The metals are preconcentrated from a 10 mL water sample into a nanoporous filter based on bisphosphonate-modified thermally carbonized porous silicon. The metals can be conveniently analyzed from the filter with a portable XRF analyzer in field conditions. The system was empirically calibrated for a lake water matrix with neutral pH and low alkaline metal concentration. A strong correlation between the XRF intensities and the ICP-MS results was obtained in a concentration range from 50 to 10 000 µg/L. With a DPO-2000C XRF analyzer, the detection limits were 103, 86, 92, 35, 44, and 43 µg/L for Mn, Ni, Cu, Zn, Pb, and U, respectively. The corresponding values with X-MET8000 Expert Geo were 137, 46, 62, 38, 29, and 54. The system was successfully validated with simulated multielement lake water samples and piloted in field conditions. The system provides an efficient way to monitor metals in environmental waters in cases where quick on-site results are needed.

Colonic Delivery of α-Linolenic Acid by an Advanced Nutrient Delivery System Prolongs Glucagon-Like Peptide-1 Secretion and Inhibits Food Intake in Mice.

SCOPE: Nutrients stimulate the secretion of glucagon-like peptide-1 (GLP-1), an incretin hormone, secreted from enteroendocrine L-cells which decreases food intake. Thus, GLP-1 analogs are approved for the treatment of obesity, yet cost and side effects limit their use. L-cells are mainly localized in the distal ileum and colon, which hinders the utilization of nutrients targeting GLP-1 secretion. This study proposes a controlled delivery system for nutrients, inducing a prolonged endogenous GLP-1 release which results in a decrease food intake. METHODS AND RESULTS: α-Linolenic acid (αLA) was loaded into thermally hydrocarbonized porous silicon (THCPSi) particles. In vitro characterization and in vivo effects of αLA loaded particles on GLP-1 secretion and food intake were studied in mice. A total of 40.4 ± 3.2% of loaded αLA is released from particles into biorelevant buffer over 24 h, and αLA loaded THCPSi significantly increased in vitro GLP-1 secretion. Single-dose orally given αLA loaded mesoporous particles increased plasma active GLP-1 levels at 3 and 4 h and significantly reduced the area under the curve of 24 h food intake in mice. CONCLUSIONS: αLA loaded THCPSi particles could be used to endogenously stimulate sustain gastrointestinal hormone release and reduce food intake.

Biogenic nanoporous silicon carrier improves the efficacy of buparvaquone against resistant visceral leishmaniasis.

Visceral leishmaniasis is a vector-borne protozoan infection that is fatal if untreated. There is no vaccination against the disease, and the current chemotherapeutic agents are ineffective due to increased resistance and severe side effects. Buparvaquone is a potential drug against the leishmaniases, but it is highly hydrophobic resulting in poor bioavailability and low therapeutic efficacy. Herein, we loaded the drug into silicon nanoparticles produced from barley husk, which is an agricultural residue and widely available. The buparvaquone-loaded nanoparticles were several times more selective to kill the intracellular parasites being non-toxic to macrophages compared to the pure buparvaquone and other conventionally used anti-leishmanial agents. Furthermore, the in vivo results revealed that the intraperitoneally injected buparvaquone-loaded nanoparticles suppressed the parasite burden close to 100%. By contrast, pure buparvaquone suppressed the burden only by 50% with corresponding doses. As the conclusion, the biogenic silicon nanoparticles are promising carriers to significantly improve the therapeutic efficacy and selectivity of buparvaquone against resistant visceral leishmaniasis opening a new avenue for low-cost treatment against this neglected tropical disease threatening especially the poor people in developing nations.

Low-Load Metal-Assisted Catalytic Etching Produces Scalable Porosity in Si Powders.

The recently discovered low-load metal-assisted catalytic etching (LL-MACE) creates nanostructured Si with controllable and variable characteristics that distinguish this technique from the conventional high-load variant. LL-MACE employs 150 times less metal catalyst and produces porous Si instead of Si nanowires. In this work, we demonstrate that some of the features of LL-MACE cannot be explained by the present understanding of MACE. With mechanistic insight derived from extensive experimentation, it is demonstrated that (1) the method allows the use of not only Ag, Pd, Pt, and Au as metal catalysts but also Cu and (2) judicious combinations of process parameters such as the type of metal, Si doping levels, and etching temperatures facilitate control over yield (0.065-88%), pore size (3-100 nm), specific surface area (20-310 m2·g-1), and specific pore volume (0.05-1.05 cm3·g-1). The porous structure of the product depends on the space-charge layer, which is controlled by the Si doping and the chemical identity of the deposited metal. The porous structure was also dependent on the dynamic structure of the deposited metal. A distinctive comet-like structure of metal nanoparticles was observed after etching with Cu, Ag, Pd, and, in some cases, Pt; this structure consisted of 10-50 nm main particles surrounded by smaller (<5 nm) nanoparticles. With good scalability and precise control of structural properties, LL-MACE facilitates Si applications in photovoltaics, energy storage, biomedicine, and water purification.

Controlling the Nature of Etched Si Nanostructures: High- versus Low-Load Metal-Assisted Catalytic Etching (MACE) of Si Powders.

Metal-assisted catalytic etching (MACE) involving Ag deposited on Si particles has been reported as a facile method for the production of Si nanowires (Si NWs). We show that the structure of Si particles subjected to MACE changes dramatically in response to changing the loading of the Ag catalyst. The use of acetic acid as a surfactant and controlled injection of AgNO3(aq) enhanced Ag deposition. The use of acetic acid and controlled injection of H2O2 not only facilitated optimization of the etching step but also allowed us to identify a previously unobserved etching regime that we denote as low-load MACE (LL-MACE). Material produced by LL-MACE exhibits dramatically different yield and structural characteristics as compared to conventionally produced material. We demonstrate the production of Si NWs as well as mesoporous Si nanoparticles from an inexpensive metallurgical-grade Si powder. High loading of Ag (HL-MACE) generates parallel etch track pores created by the correlated motion of Ag nanoparticles. The uniform size distribution (predominantly 70-100 nm) of the Ag nanoparticles is generated dynamically during etching. The walls of these etch track pores are cleaved readily by ultrasonic agitation to form Si NWs. Low loading of Ag (LL-MACE) creates 10-50 nm Ag nanoparticles that etch in an uncorrelated (randomly directed) fashion to generate a bimodal distribution of mesoporosity peaking at ∼4 and 13-21 nm. The use of a syringe pump to deliver the oxidant (H2O2) and Ag+ is essential for increased product uniformity and yield. Different process temperatures and grades of Si produced significantly different pore size distributions. These results facilitate the production of Si NWs and mesoporous nanoparticles with high yield, low cost, and controlled properties that are suitable for applications in, e.g., lithium-ion batteries, drug delivery, as well as biomedical imaging and contrast enhancement.

Inorganic mesoporous particles for controlled α-linolenic acid delivery to stimulate GLP-1 secretion in vitro.

Novel treatment methods for obesity are urgently needed due to the increasing global severity of the problem. Gastrointestinal hormones, such as GLP-1 and PYY, are secreted by the enteroendocrine cells, playing a critical role in regulating food intake. Digested nutrients trigger the secretion of these hormones, which have a very short half-life. α-Linolenic acid (αLA) has been shown to stimulate GLP-1 secretion, however, chemical instability and fast uptake in the small intestine hinder its use in body weight management. We developed a novel delivery system based on inorganic mesoporous particles for αLA to increase secretion of gastrointestinal peptides. αLA was loaded to thermally hydrocarbonized porous silicon particles (THCPSi). 47.9 ±â€¯3.84% and 30.7 ±â€¯2.86% of αLA was released during 6 h from 3.0% and 9.2% loading degree (w/w) samples in vitro, respectively. Native αLA (50 µM) significantly increased GLP-1 secretion from enteroendocrine STC-1 and GLUTag cell lines. αLA loaded THCPSi significantly and dose dependently stimulated GLP-1 secretion from STC-1 cells, whereas empty particles did not. We demonstrated in vitro that THCPSi particles have the potential to be used as a controlled delivery system for nutrients such as αLA, increasing GLP-1 secretion. Our results justify further in vivo investigations.

Mesoporous systems for poorly soluble drugs - recent trends.

When poor aqueous solubility of active pharmaceutical ingredients is encountered during a drug formulation process, the toolbox typically utilized contains pharmaceutical salts, co-crystals, solid dispersions, cyclodextrins, lipids, liposomes and nanocrystals etc. Especially in the pharmaceutical industry, the option which confers the greatest benefit with the lowest risk is usually chosen. Several factors affect the final decision, but new technologies should also be considered especially if they can address several issues at the same time. Mesoporous inorganic systems are emerging technologies which can be utilized for improving the dissolution of poorly soluble drugs. The number of the scientific papers in this field is steadily increasing and the focus of the studies is moving away from in vitro to in vivo experiments with the first human trial already completed. Meanwhile, several start-up companies focusing on mesoporous carriers have been established. Therefore, it is conceivable that the first commercial products will find their way to pharmacies during the next 5-10 years. The present review surveys recent progress in research on mesoporous materials as carriers of poorly soluble drugs. We will concentrate on the research published since our previous review published in 2012 [10.1016/j.ijpharm.2012.09.008] up to the present day.

Cytotoxicity assessment of porous silicon microparticles for ocular drug delivery.

Porous silicon (PSi) is a promising material for the delivery and sustained release of therapeutic molecules in various tissues. Due to the constant rinsing of cornea by tear solution as well as the short half-life of intravitreal drugs, the eye is an attractive target for controlled drug delivery systems, such as PSi microparticles. Inherent barriers ensure that PSi particles are retained in the eye, releasing drugs at the desired speed until they slowly break down into harmless silicic acid. Here, we have examined the in vitro cytotoxicity of positively and negatively charged thermally oxidized (TOPSi) and thermally carbonized (TCPSi) porous silicon microparticles on human corneal epithelial (HCE) and retinal pigment epithelial (ARPE-19) cells. In addition to ocular assessment under an inverted microscope, cellular viability was evaluated using the CellTiter Blue™, CellTiter Fluor™, and lactate dehydrogenase (LDH) assays. CellTiter Fluor proved to be a suitable assay but due to non-specific and interfering responses, neither CellTiter Blue nor LDH assays should be used when evaluating PSi particles. Our results suggest that the toxicity of PSi particles is concentration-dependent, but at least at concentrations less than 200µg/ml, both positively and negatively charged PSi particles are well tolerated by human corneal and retinal epithelial cells and therefore applicable for delivering drug molecules into ocular tissues.

Novel delivery systems for improving the clinical use of peptides.

Peptides have long been recognized as a promising group of therapeutic substances to treat various diseases. Delivery systems for peptides have been under development since the discovery of insulin for the treatment of diabetes. The challenge of using peptides as drugs arises from their poor bioavailability resulting from the low permeability of biological membranes and their instability. Currently, subcutaneous injection is clinically the most common administration route for peptides. This route is cost-effective and suitable for self-administration, and the development of appropriate dosing equipment has made performing the repeated injections relatively easy; however, only few clinical subcutaneous peptide delivery systems provide sustained peptide release. As a result, frequent injections are needed, which may cause discomfort and additional risks resulting from a poor administration technique. Controlled peptide delivery systems, able to provide required therapeutic plasma concentrations over an extended period, are needed to increase peptide safety and patient compliancy. In this review, we summarize the current peptidergic drugs, future developments, and parenteral peptide delivery systems. Special emphasis is given to porous silicon, a novel material in peptide delivery. Biodegradable and biocompatible porous silicon possesses some unique properties, such as the ability to carry exceptional high peptide payloads and to modify peptide release extensively. We have successfully developed porous silicon as a carrier material for improved parenteral peptide delivery. Nanotechnology, with its different delivery systems, will enable better use of peptides in several therapeutic applications in the near future.

Systematic in vitro and in vivo study on porous silicon to improve the oral bioavailability of celecoxib.

Mesoporous materials are promising candidates for improving dissolution rate of poorly water-soluble drugs in vitro and their bioavailability in vivo. In the present study, sixteen batches of celecoxib-loaded PSi particles with pore sizes ranging from 17 to 58 nm and celecoxib content from 5 to 36 w-% were prepared and a detailed physicochemical characterization of the drug was performed by several methods. Interaction between co-culture of Caco-2/HT29-MTX cells and unloaded PSi particles was tested in toxicity assays, and increased toxicity for particles with large pore size was observed. Dissolution rate of celecoxib was improved in vitro by lowering the drug loading degree which hindered the recrystallization of celecoxib on the external surface of the particles. The fastest permeation of loaded celecoxib through the co-culture monolayer as well as the highest bioavailability in rats was observed with the particles with small pore size and low loading degree. New insights were obtained on how various parameters of the mesoporous delivery system affect the state of the drug inside the pores and its release in vitro and in vivo.

Improved stability and biocompatibility of nanostructured silicon drug carrier for intravenous administration.

Nanotechnology has attracted considerable interest in the field of biomedicine, where various nanoparticles (NPs) have been introduced as efficient drug carrier systems. Mesoporous silicon (PSi) is one of the most promising materials in this field due to its low toxicity, good biodegradability, high surface area, tunable pore size and controllable surface functionality. However, recognition by the reticuloendothelial system and particle agglomeration hinder the use of PSi for intravenous applications. The present paper describes a dual-PEGylation method, where two PEG molecules with different sizes (0.5 and 2 kDa) were grafted simultaneously in a single process onto thermally oxidized PSi NPs to form a high-density PEG coating with both brush-like and mushroom-like conformation. The material was characterized in detail and the effects of the dual-PEGylation on cell viability, protein adsorption and macrophage uptakes were evaluated. The results show that dual-PEGylation improves the colloidal stability of the NPs in salt solutions, prolongs their half-lives, and minimizes both protein adsorption and macrophage uptake. Therefore, these new dual-PEGylated PSi NPs are potential candidates for intravenous applications.

Nanocarriers and the delivered drug: effect interference due to intravenous administration.

Intravenously administered nanocarriers are widely studied to improve the delivery of various therapeutic agents. However, recent in vivo studies have demonstrated that intravenously administered nanocarriers that do not contain any drug may affect cardiovascular function. Here we provide an example where the drug and the nanocarrier both affect the same cardiovascular parameters following intravenous administration. The peptide ghrelin antagonist (GhA) increases arterial pressure, while thermally hydrocarbonized porous silicon nanoparticles (THCPSi) transiently decrease it, as assessed with radiotelemetry in conscious rats. As a result, intravenous administration of GhA-loaded THCPSi nanoparticles partially antagonized GhA activity: arterial pressure was not increased. When the cardiovascular effects of GhA were blocked with atenolol pretreatment, GhA-loaded nanoparticles reduced arterial pressure to similar extent as drug-free nanoparticles. These data indicate that the biological activity of a drug delivered within a nanocarrier may be obscured by the biological responses induced by the nanocarrier itself.

Injected nanoparticles: the combination of experimental systems to assess cardiovascular adverse effects.

When nanocarriers are used for drug delivery they can often achieve superior therapeutic outcomes over standard drug formulations. However, concerns about their adverse effects are growing due to the association between exposure to certain nanosized particles and cardiovascular events. Here we examine the impact of intravenously injected drug-free nanocarriers on the cardiovasculature at both the systemic and organ levels. We combine in vivo and in vitro methods to enable monitoring of hemodynamic parameters in conscious rats, assessments of the function of the vessels after sub-chronic systemic exposure to nanocarriers and evaluation of the direct effect of nanocarriers on vascular tone. We demonstrate that nanocarriers can decrease blood pressure and increase heart rate in vivo via various mechanisms. Depending on the type, nanocarriers induce the dilation of the resistance arteries and/or change the responses induced by vasoconstrictor or vasodilator drugs. No direct correlation between physicochemical properties and cardiovascular effects of nanoparticles was observed. The proposed combination of methods empowers the studies of cardiovascular adverse effects of the nanocarriers.

Mesoporous systems for poorly soluble drugs.

Utilization of inorganic mesoporous materials in formulations of poorly water-soluble drugs to enhance their dissolution and permeation behavior is a rapidly growing area in pharmaceutical materials research. The benefits of mesoporous materials in drug delivery applications stem from their large surface area and pore volume. These properties enable the materials to accommodate large amounts of payload molecules, protect them from premature degradation, and promote controlled and fast release. As carriers with various morphologies and chemical surface properties can be produced, these materials may even promote adsorption from the gastrointestinal tract to the systemic circulation. The main concern regarding their clinical applications is still the safety aspect even though most of them have been reported to be safely excreted, and a rather extensive toxicity screening has already been conducted with the most frequently studied mesoporous materials. In addition, the production of the materials on a large scale and at a reasonable cost may be a challenge when considering the utilization of the materials in industrial processes. However, if mesoporous materials could be employed in the industrial crystallization processes to produce hybrid materials with poorly soluble compounds, and hence to enhance their oral bioavailability, this might open new avenues for the pharmaceutical industry to employ nanotechnology in their processes.

Development of porous silicon nanocarriers for parenteral peptide delivery.

Porous silicon (PSi) is receiving growing attention in biomedical research, for example, in drug and peptide delivery. Inspired by several advantages of PSi, herein, thermally oxidized (TOPSi, hydrophilic), undecylenic acid-treated thermally hydrocarbonized (UnTHCPSi, moderately hydrophilic), and thermally hydrocarbonized (THCPSi, hydrophobic) PSi nanocarriers are investigated for sustained subcutaneous (sc) and intravenous (iv) peptide delivery. The route of administration is shown to affect drastically peptide YY3-36 (PYY3-36) release from the PSi nanocarriers in mice. Subcutaneous nanocarriers are demonstrated to be capable to sustain PYY3-36 delivery over 4 days, with the high absolute bioavailability values of PYY3-36. The pharmacokinetic parameters of PYY3-36 are presented to be similar between the sc PSi nanocarriers despite surface chemistry. In contrast, iv-delivered PSi nanocarriers display significant differences between the surface types. Overall, these results demonstrate the feasibility of PSi nanocarriers for the sustained sc delivery of peptides.

Surface chemistry, reactivity, and pore structure of porous silicon oxidized by various methods.

Oxidation is the most commonly used method of passivating porous silicon (PSi) surfaces against unwanted reactions with guest molecules and temporal changes during storage or use. In the present study, several oxidation methods were compared in order to find optimal methods able to generate inert surfaces free of reactive hydrides but would cause minimal changes in the pore structure of PSi. The studied methods included thermal oxidations, liquid-phase oxidations, annealings, and their combinations. The surface-oxidized samples were studied by Fourier transform infrared spectroscopy, isothermal titration microcalorimetry, nitrogen sorption, ellipsometry, X-ray diffraction, electron paramagnetic resonance spectroscopy, and scanning electron microscopy imaging. Treatment at high temperature was found to have two advantages. First, it enables the generation of surfaces free of hydrides, which is not possible at low temperatures in a liquid or a gas phase. Second, it allows the silicon framework to partially accommodate a volume expansion because of oxidation, whereas at low temperature the volume expansion significantly consumes the free pore volume. The most promising methods were further optimized to minimize the negative effects on the pore structure. Simple thermal oxidation at 700 °C was found to be an effective oxidation method although it causes a large decrease in the pore volume. A novel combination of thermal oxidation, annealing, and liquid-phase oxidation was also effective and caused a smaller decrease in the pore volume with no significant change in the pore diameter but was more complicated to perform. Both methods produced surfaces that were not found to react with a model drug cinnarizine in isothermal titration microcalorimetry experiments. The study enables a reasonable choice of oxidation method for PSi applications.

Effect of isotonic solutions and peptide adsorption on zeta potential of porous silicon nanoparticle drug delivery formulations.

Recently, highly promising results considering the use of porous silicon (PSi) nanoparticles as a controlled and targeted drug delivery system have been published. Drugs are typically loaded into PSi nanoparticles by electrostatic interactions, and the drug-loaded nanoparticles are then administered parenterally in isotonic solutions. Zeta potential has an important role in drug adsorption and overall physical stability of nanosuspensions. In the present study, we used zeta potential measurements to study the impact of the formulation components to the nanosuspension stability. The impact of medium was studied by measuring isoelectric points (IEP) and zeta potentials in isotonic media. The role of drug adsorption was demonstrated with gastrointestinal peptides GLP-1(7-37) and PYY (3-36) and the selection of isotonic additive was demonstrated with peptide-loaded PSi nanoparticles. The results show the notable effect of isotonic solutions and peptide adsorption on zeta potential of PSi nanosuspensions. As a rule of thumb, the sugars (sucrose, dextrose and mannitol) seem to be good media for negatively charged peptide-loaded particles and weak acids (citric- and lactic acid) for positively charged particles. Nevertheless, perhaps the most important rule can be given for isotonic salt solutions which all are very poor media when the stability of nanosuspension is considered.

Freezing tolerance and low molecular weight cryoprotectants in an invasive parasitic fly, the deer ked (Lipoptena cervi).

Insect cold hardiness is often mediated by low molecular weight cryoprotectants, such as sugars, polyols, and amino acids (AA). While many free-living northern insects must cope with extended periods of freezing ambient temperatures (Ta), the ectoparasitic deer ked Lipoptena cervi imago can encounter subfreezing Ta only during a short autumnal period between hatching and host location. Subsequently, it benefits from the body temperature of the cervid host for survival in winter. This study investigated the cold tolerance of the species by determining its lower lethal temperature (100% mortality, LLT100) during faster and slower cold acclimation, by determining the supercooling point (SCP) and by measuring the concentrations of potential low molecular weight cryoprotectants. The LLT100 of the deer ked was approximately -16 ° C, which would enable it to survive freezing nighttime Ta not only in its current area of distribution but also further north. The SCP was -7.8 ° C, clearly higher than the LLT100 , indicating that the deer ked displays freezing tolerance. The concentrations of free AA, especially nonessential AA, were higher in the cold-acclimated deer keds similar to several other insects. The concentrations of proline increased together with γ-aminobutyrate, arginine, asparagine, cystine, glutamate, glutamine, hydroxylysine, sarcosine, serine, and taurine. AA could be hypothesized to act as cryoprotectants by, e.g., protecting enzymes and lipid membranes from damage caused by cold.

Nanostructured porous silicon microparticles enable sustained peptide (Melanotan II) delivery.

Peptide molecules can improve the treatment of a number of pathological conditions, but due to their physicochemical properties, their delivery is very challenging. The study aim was to determine whether nanostructured porous silicon could sustain the release and prolong the duration of action of a model peptide Melanotan II (MTII). Thermally hydrocarbonized nanoporous silicon (THCPSi) microparticles (38-53 µm) were loaded with MTII. The pore diameter, volume, specific surface area and loading degree of the microparticles were analyzed, and the peptide release was evaluated in vitro. The effects of MTII on heart rate and water consumption were investigated in vivo after subcutaneous administration of the MTII loaded microparticles. A peptide loading degree of 15% w/w was obtained. In vitro studies (PBS, pH 7.4, 37 °C) indicated sustained release of MTII from the THCPSi microparticles. In vivo, MTII loaded THCPSi induced an increase in the heart rate 2 h later than MTII solution, and the effect lasted 1 h longer. In addition, MTII loaded THCPSi changed the water consumption after 150 min, when the immediate effect of MTII solution was already diminished. The present study demonstrates that MTII loading into nanosized PSi pore structure enables sustained delivery of an active peptide.