Nonporous Particles Research Articles

Layer-by-Layer Assembling and Capsule Formation of Polysaccharide-Based Polyelectrolytes Studied by Whispering Gallery Mode Experiments and Confocal Laser Scanning Microscopy

The layer-by-layer (LbL) assembling of oppositely charged polyelectrolytes was studied using semi-synthetic polysaccharide derivatives, namely the polycations 6-aminoethylamino-6-deoxy cellulose (ADC) and cellulose (2-(ethylamino)ethylcarbamate (CAEC), as well as the polyanion cellulose sulfate (CS). The synthetic polymers poly(allylamine) (PAH) and poly(styrene sulfonate) (PSS) were employed as well for comparison. The stepwise adsorption process was monitored by whispering gallery mode (WGM) experiments and zeta-potential measurements. Distinct differences between synthetic- and polysaccharide-based assemblies were observed in terms of the quantitative adsorption of mass and adsorption kinetics. The LbL-approach was used to prepare µm-sized capsules with the aid of porous and non-porous silica particle templates. The polysaccharide-based capsule showed a switchable permeability that was not observed for the synthetic polymer materials. At ambient pH values of 7, low-molecular dyes could penetrate the capsule wall while no permeation occurred at elevated pH values of 8. Finally, the preparation of protein-loaded LbL-capsules was studied using the combination of CAEC and CS. It was shown that high amounts of protein (streptavidin and ovomucoid) can be encapsulated and that no leaking or disintegration of the cargo macromolecules occurred during the preparation step. Based on this work, potential use in biomedical areas can be concluded, such as the encapsulation of bioactive compounds (e.g., pharmaceutical compounds, antibodies) for drug delivery or sensing purposes.

Application of mesoporous silica particles as an additive for controlling rheological, thermal, and filtration properties of water-based fluids

Mesoporous silica particles (MSP) have received increasing interest for various applications because of their unique features such as controlled pore size, low density, high chemical and thermal stability, and high surface area. In this study, MSP was applied as an additive in water-based drilling fluids (WBMs). The effect of MSP on the rheological, thermal, filtration, and structural properties of WBMs was investigated. The results were compared with those of analogous fluids containing conventional nonporous silica particles (SSP). Rheological assays showed shear-thinning and viscoelastic behavior, which were more noticeable for fluids including MSP. It was observed that low concentrations of MSP (0.25 %wt) can achieve the same rheological properties as the fluids with higher SSP content (up to 0.5 %wt). The rheological properties of SSP-containing fluids were not significantly affected by the presence of NaCl or aging tests. The theoretical Herschel–Bulkley model represents the rheological behavior of WBMs. The MSP-based WBMs exhibited better filtration properties before aging. The microstructures of the WBMs were analyzed using Scanning Electron Microscopy (SEM). A homogeneous distribution of SSP in the WBMs was observed, while particle agglomeration was observed in WBMs containing MSP. In addition, surface interactions were studied to elucidate the interactions between particles and fluid constituents. The surface interaction, assessed through ζ-potential and FTIR analysis, revealed that the binding affinities of BT, PAC, and XGD with MSP were augmented compared to their individual values. Based on the experimental results, MSP constitutes a promising alternative as an additive for the design of WBMs.

ASSESSMENT OF SPECIFIC SURFACE AREA AND POROSITY OF SUBSOILS

Soils and subsoils have a complex structure consisting of several elements with different morphology and chemical composition, combining micro-, meso-, and macroporous substructures. Classical approaches, such as Brunauer-Emmett-Teller (BET) or Barrett-Joyner-Halenda (BJH) methods, cannot provide an accurate assessment of morphological characteristics of such solids, nor can do modern sophisticated numerical methods which depend on idealized models of pores that hardly reflect a real morphology of heterogeneous solids in question. The present study describes a way to overcome this difficulty by applying a combination of the αS-plot technique and a modified Remy-Poncelet method. The proposed approach allowed estimating the volumes of the untramicropores, supermicropores and the sum of meso- and macropores as well as the specific surface areas of the solid without ultramicropores and of the solid without all micropores. The former specific surface area is a more reasonable estimate of the area available for layer coverage than the BET specific surface area, and all together these characteristics provide a detail description of solid’s morphology. Subsoil samples excavated from different depths were used as exemplary solids. They mostly consisted of quartz, feldspar, and clay minerals and had different sorts of pores associated with the clay fraction and soil aggregates as well as a relatively large fraction of non-porous sand particles. Relations of the morphological properties with subsoil profile and mineralogical composition are discussed. For citation: Asnin L.D., Samoylov M.S., Pershina M.V., Tselishchev Yu.G., Sliusar N.N. Assessment of specific surface area and porosity of subsoils. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 6. P. 55-64. DOI: 10.6060/ivkkt.20246706.6996.

Leveraging Expertise in Thermal Catalysis to Understand Plasma Catalysis.

Best practices in testing heterogeneous catalysts are translated to plasma-catalytic experiments. Independent determination of plasma-catalytic and plasma-chemical contributions is essential. Non-porous catalyst particles are preferred because active sites inside sub-micron pores cannot contribute. Temperature variation is needed to determine kinetics, despite the complexity of thermal effects in plasma. Rigorous checks on catalyst deactivation and mass balance are needed. Plasma enhanced reversed reactions should be minimized by keeping conversion low and far from thermodynamic equilibrium, preventing underestimation of the rate of forward reaction. In contrast, plasma-catalytic studies often aim at conversions surpassing thermodynamic equilibrium, not obtaining any information on kinetics. Calculation of catalyst activity per active sites (turn-over-frequency) requires also appropriate characterization to determine the number of active sites. The relationship between kinetics and thermodynamics for plasma-catalysis is discussed using endothermic decomposition of CO2 and exothermic synthesis of ammonia from N2 and H2 as examples. Assuming Langmuir-Hinshelwood and Eley-Rideal mechanisms, the effect of excitation of reactant molecules on activation barriers and surface coverages are discussed, influencing reaction rates. The consequences of reversed reactions are considered. Plasma-catalysis with catalysts applied for thermal catalysis at much higher temperature should be avoided, as adsorbed species are bonded too strongly resulting in low rates.

Comparison of superhydrophobic biodegradable PLA films with fluorine-free hexamethyldisilazane grafted silica and mesoporous silica particles

This study reports the surface coating of fluorine-free hexamethyldisilazane (HMDS) on non-porous silica particles (SPs) and mesoporous silica particles (MSPs), with nanopores arranged in the straight channels, and compares the degree of superhydrophobicity by coating them on biodegradable PLA film by gravure process. The particle sizes of SPs and MSPs are 50 nm and 800 nm, and the amount of HMDS grafted onto SPs and MSPs is 0.5% and 9.5%, respectively. The superhydrophobicity of these particles is confirmed by the measurement of water contact angle (WCA) as a function of HMDS concentration for SPs and MSPs from 0 to 1.6 M, respectively. The WCA of HMDS@SPs and HMDS@MSPs grafted with 1.6 M of HMDS is 152° and 151° (WCA of unmodified SPs and MSPs is 13.85° and 27.65°). To apply superhydrophobic PLA film coating, 5 wt% of HMDS@SPs and HMDS@MSPs were mixed with gravure solution and then coated on biodegradable polylactic acid (PLA) film. The results showed that the WCA of PLA film with HMDS@SPs and HMDS@MSPs were 98.40° and 152.31°, respectively. This remarkable difference in WCA is due to the dissociation of HMDS molecules grafted on the surface of SPs and MSPs, which are easily separated by the gravure solvent. For MSPs materials composed of many nanopores, the dissociated HMDS molecules are initially released into the solution but are retained within the nanopores. Therefore, the residual amount of HMDS molecules dissociated by the gravure solution is much higher in HMDS@MSPs than in HMDS@SPs.

Large scale synthesis of mesoporous and nonporous silica submicron particles via polymer‐derived ceramic method

AbstractMesoporous silica particles (MSPs) are highly important in applications like H2 storage, catalysis/biocatalysis, adsorption, separation, and particularly in biomedical applications. The typical methods for producing MSPs are fast self‐assembly, soft and hard templating, and the modified Stöber method. These approaches have drawbacks like high cost, being time‐consuming, and low scale. Herein, as a novel strategy, a polymer‐derived ceramic method for large‐scale production of mesoporous and dense silica submicron particles with high yield and low cost is presented. This method requires commercial silicone resin, polydimethylsiloxane, as the main precursor of silica. However, this technique did not show high control over the size and surface area compared with the typical methods of MSPs synthesis but is definitely a significant step toward the large‐scale synthesis of MSPs.

Origin of Enhancement of Orbital Magnetic Moment in SiO2-Coated Fe3O4 Nanocomposites Studied by X-ray Magnetic Circular Dichroism.

In this study, magnetic Fe3O4 nanoparticles (NPs) were dispersed uniformly by varying the thickness of the SiO2 coating, and their electronic and magnetic properties were investigated. X-ray diffraction confirmed the structural configuration of monophase inverse-spinel Fe3O4 NPs in nanometer size. Scanning electron microscopy revealed the formation of proper nonporous crystallite particles with a clear core-shell structure with silica on the surface of Fe3O4 NPs. The absorption mechanism studied through the zeta potential indicates that SiO2-coated Fe3O4 nanocomposites (SiO2@Fe3O4 NCs) possess electrostatic interactions to control their agglomeration in stabilizing suspensions by providing a protective shield of amorphous SiO2 on the oxide surface. High-resolution transmission electron microscopy images demonstrate a spherical morphology having an average grain diameter of ∼11-17 nm with increasing thickness of SiO2 coating with the addition of a quantitative presence and proportion of elements determined through elemental mapping and electron energy loss spectroscopy studies. Synchrotron-based element-specific soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) techniques have been involved in the bulk-sensitive total fluorescence yield mode to understand the origin of magnetization in SiO2@Fe3O4 NCs. The magnetization hysteresis of Fe3O4 was determined by XMCD. At room temperature, the magnetic coercivity (Hc) is as high as 1 T, which is about 2 times more than the value of the thin film and about 5 times more pronounced than that of NPs. For noninteracting single-domain NPs with the Hc spread from 1 to 3 T, the Stoner-Wohlfarth model provided an intriguing explanation for the hysteresis curve. These curves determine the different components of Fe oxides present in the samples that derive the remnant magnetization involved in each oxidation state of Fe and clarify which Fe component is responsible for the resultant magnetism and magnetocrystalline anisotropy based on noninteracting single-domain particles.

Use graphene coated silica core shell particles to provide rapid, precise, and equivalent chemical composition distribution analysis for polyolefin materials by high temperature thermal gradient interaction chromatography

High temperature thermal gradient interaction chromatography (HT-TGIC) has been widely used to measure chemical composition distribution due to its applicability to separate crystalline and non-crystalline amorphous polyolefin materials. The compatibility of HT-TGIC with various detectors (infrared (IR), light scattering (LS), and viscometer) has also allowed a comprehensive analysis of molecular architecture of polyolefin and recycled plastics. The introduction of an easy-to-fabricate graphene coated onto non-porous silica particles as HT-TGIC column in 2020 showed a superior chromatographic performance over the traditional graphite column. A reduction in peak broadness (∼47 %) under identical experimental conditions was demonstrated in that research. This paper similarly uses a graphene column but with the focus on optimization of experimental parameters (concentration, and thermal cooling and heating rates etc.). Equivalent chemical composition distribution (CCD) data to that obtained by the incumbent graphite column over a wide range of polyolefins products was achieved, in addition to a shortened analysis time from 120 min down to 88 min per sample. The materials studied included semicrystalline linear low-density polyethylene (LLDPE), elastomers, terpolymers, model blends to mimic recycled plastics. The results also suggest that the elimination of substrate pores enable a better HT-TGIC separation. Coupling the ease and reproducibility of the graphene column fabrication process enables long term chromatographic robustness. This not only results in equivalent CCD data compared to the traditional graphite column but also a 27 % reduction in analysis time. These results demonstrate a substantial advancement of technology in the high throughput industrial laboratory setting where fast testing turnaround time is critical. In addition, simple fabrication with commercially available silica particles and graphene nanopowder provides a cost-effective approach to make HT-TGIC columns reproducibly.

Silica particles convert thiol-containing molecules to disulfides

Synthetic amorphous silica is a common food additive and a popular cosmetic ingredient. Mesoporous silica particles are also widely studied for their potential use in drug delivery and imaging applications because of their unique properties, such as tunable pore sizes, large surfaces areas, and assumed biocompatibility. Such a nanomaterial, when consisting of pure silicon dioxide, is generally considered to be chemically inert, but in this study, we showed that oxidation yields for different compounds were facilitated by simply incubating aqueous solutions with pure silica particles. Three thiol-containing molecules, L-cysteine, glutathione, and D-penicillamine, were studied separately, and it was found that more than 95% of oxidation happened after incubating any of these compounds with mesoporous silica particles in the dark for a day at room temperature. Oxidation increased over incubation time, and more oxidation was found for particles having larger surface areas. For nonporous silica particles at submicron ranges, yields of oxidation were different based on the structures of molecules, correlating with steric hindrance while accessing surfaces. We propose that the silyloxy radical (SiO•) on silica surfaces is what facilitates oxidation. Density functional theory calculations were conducted for total energy changes for reactions between different aqueous species and silicon dioxide surfaces. These calculations identified two most plausible pathways of the lowest energy to generate SiO• radicals from water radical cations H2O•+ and hydroxyl radicals •OH, previously known to exist at water interfaces.

3D printed porous particle and its geotechnical properties

The study of effects of particle breakage on the mechanical properties of soil composed of porous particles is challenging due to the heterogeneity of the shape and inner void structure of individual particles, even for an identical soil sample, which imparts a compound effect on the mechanical properties. Advancements in three-dimensional (3D) printing technique have enabled the replication of objects with the same shape but different inner structures. This study investigated the feasibility of replicating porous and non-porous particles with the same particle shape characteristics, such as form, waviness, and texture, using 3D printing technique. The particle shape characteristics were evaluated using image analysis. Single particle crushing and triaxial compression tests were conducted to characterize the mechanical properties of the 3D printed and porous volcanic soil particles. It is observed that the mechanical response in the single particle crushing test varies for volcanic soil, which may be attributed to the heterogeneity in the shape and porosity of the particles. However, for each type of 3D printed particle, the response has a high repeatability and varies based on particle porosity. Furthermore, the effects of porosity on the shear response are demonstrated through triaxial tests on 3D printed particles of different porosities. It is noted that although a quantitative comparison is not possible, a qualitative similarity is observed in the response of the 3D printed porous particles with natural porous volcanic soil. Thus, insights into the mechanical response of porous particles can be gained using 3D printed particles.

Drug-Eluting Porous Embolic Microspheres for Trans-Arterial Delivery of Dual Synergistic Anticancer Therapy for the Treatment of Liver Cancer.

Blockage of blood supply while administering chemotherapy to tumors, using trans-arterial chemoembolization (TACE), is the most common treatment for intermediate and advanced-stage unresectable Hepatocellular carcinoma (HCC). However, HCC is characterized by a poor prognosis and high recurrence rates (≈30%), partly due to a hypoxic pro-angiogenic and pro-cancerous microenvironment. This study investigates how modifying tissue stress while improving drug exposure in target organs may maximize the therapeutic outcomes. Porous degradable polymeric microspheres (MS) are designed to obtain a gradual occlusion of the hepatic artery that nourishes the liver, while enabling efficient drug perfusion to the tumor site. The fabricated porous MS are introduced intrahepatically and designed to release a combination therapy of Doxorubicin (DOX) and Tirapazamine (TPZ), which is a hypoxia-activated prodrug. Liver cancer cell lines that are treated with the combination therapy under hypoxia reveal a synergic anti-proliferation effect. An orthotopic liver cancer model, based on N1-S1 hepatoma in rats, is used for the efficacy, biodistribution, and safety studies. Porous DOX-TPZ MS are very effective in suppressing tumor growth in rats, and induction tissue necrosis is associated with high intratumor drug concentrations. Porous particles without drugs show some advantages over nonporous particles, suggesting that morphology may affect the treatment outcomes.

Rapid Indomethacin Release from Porous Pectin Particles as a Colon-Targeted Drug Delivery System.

The conventional pectin delivery systems in the colon are often impaired by a slow release rate. Nanostructured particles, especially porous ones, have gained popularity as drug delivery systems owing to their high mass transfer efficiency. In this research, porous pectin particles were synthesized as drug carriers (using indomethacin as a model drug) via template-assisted spray drying. Specific surface areas of the porous pectin particles have been improved by up to 203 m2 g-1 compared with nonporous particles (1 m2 g-1). The porous structure shortened the diffusion path and improved the release rate of drug molecules. Additionally, the predominant drug release mechanism from porous pectin particles is Fickian diffusion, which is different from the combination of erosion and diffusion mechanism observed for nonporous particles. As a result, these porous drug-loaded pectin particles demonstrated rapid drug release rates of up to three times faster than nonporous particles. Control of the release rate could be achieved by changing the porous structure of the particles. This strategy is an efficient means to synthesize porous particles allowing rapid drug release into the colonic target.

Absorption and escape kinetics of spherical biomolecules from fully porous particles utilized in size exclusion chromatography

The increasing demand for the characterization of large biomolecules such as monoclonal antibodies, double-stranded deoxyribonucleic acid (dsDNA), and virus-like particles (VLPs) is raising fundamental questions pertaining to their absorption (ingress) and escape (egress) kinetics from fully porous particles. The exact expression of their concentration profiles is derived as a function of time and radial position across a single sub-3 μm Bridge-Ethylene-Hybrid (BEHTM) Particle present in size exclusion chromatography (SEC) columns. The boundary condition at the external surface area of the particle is a rectangular concentration profile mimicking the passage of the chromatographic zone. Four different BEH Particles were considered in the calculations depending on the molecular size of the analyte: 2.0 μm 100 Å BEH Particles for small molecules, 2.0 μm 200 Å BEH Particles for monoclonal antibodies, 2.0 μm 300 Å BEH Particles for dsDNA (100 base pairs), and 2.5 μm 900 Å BEH Particles for virus-like particles (VLPs).The calculated concentration profiles of small molecules and monoclonal antibodies confirm that all BEH Particles present in the column reach quasi-instantaneously thermodynamic equilibrium with the bulk mobile phase during the passage of the chromatographic band. This is no longer the case for larger biomolecules such as dsDNA or VLPs, especially when the SEC particle is located near the column inlet and for high velocities. The kinetics of biomolecule egress is slower than its kinetics of ingress leading to pronounced peak tailing. The mean concentration of the largest biomolecules in the SEC particles remains always smaller than the maximum bulk concentration. This persistent and transient intra-particle diffusion regime has direct implications on the theoretical expressions of the observed retention factors and plate heights. Classical theories of chromatography assume uniform spatial distribution of the analyte in the particle volume: this hypothesis is not verified for the largest biomolecules. These results imply that non-porous particles or monolithic structures are the most promising stationary phases for the separation and purification of the largest biomolecules in life science.

Simple Preparation Method of Silica Core–Shell Spheres for HPLC in Undergraduate Chemistry

High-performance liquid chromatography (HPLC) experiments are an important part of the undergraduate analytical instrumentation laboratory courses and usually use commercial C18 silica-packed reversed-phase columns. In this experiment, a simple method of preparing SiO2 core–shell packed columns was developed to enable students to master the whole process of HPLC experiment from stationary phase preparation and column packing to separation experiments, just as they do for gas chromatography. Nonporous SiO2 particles with a particle size of approximately 2.2 μm were prepared by a three-step dilution reaction using the sol–gel method. The product yield was 92.1%. Monodisperse and spherical SiO2 core–shell particles (SiO2@dSiO2) with a particle size of about 2.4 μm were prepared by a one-step hydrothermal method using the prepared SiO2 spheres as the core. The product yield was 83.3%. The prepared SiO2@dSiO2 particles were derivatized with n-octadecyldimethylchlorosilane and then packed into a stainless steel chromatography column. A high column efficiency of 83,188 theoretical plates per meter was obtained for fluorene in reversed-phase mode for the separation of a mixture of polycyclic aromatic hydrocarbons. The column efficiency obtained with this method is the same as that of a commercial column packed with fully porous particles of the same particle size. The SiO2 core–shell stationary phase preparation method developed in this experiment has the advantages of simple process, high yield, and good repeatability. The experiment can be designed to be completed over a period of 1–3 weeks. Inorganic material synthesis is another important aspect of this experiment.

Effect of monodisperse mesoporous bioactive glass spheres (MBGs) on the mechanical properties and bioactivity of dental composites

Secondary caries is one of the main reasons for the failure of dental resin composites, and adding bioactive fillers such as bioactive glass and amorphous calcium phosphate to the resin composites has been proved to be an effective solution for this problem. In the present study, we investigated the effect of monodisperse mesoporous bioactive glass spheres (MBGs) we prepared on the mechanical properties and bioactivity of dental resins. The results revealed that compared with traditional bioactive glass (BG), MBGs fillers significantly enhanced the mechanical properties of the dental resin composites, whether they were added alone or as functional fillers together with nonporous silica particles. The dental resins filled with bimodal fillers (mass ratio of MBGs: nonporous silica = 10:50, total filler loading 60 wt%) exhibited the best mechanical performance. Their flexural strength was 37.66% higher than the samples with BG at the same filling proportion. Furthermore, the prepared MBGs possessed excellent monodispersity and sufficient apatite formation performance, and the biocompatibility of the composites were also improved by MBGs fillers. These suggest the potential use of the prepared MBGs as multifunctional fillers for the improvement of the performance of dental resins.

Influence of the nanostructural characteristics of inorganic fillers on the physical properties of resin cements.

Light-curing resin cements, each comprising one of five different inorganic fillers (non-porous and porous spherical SiO2 particles, irregularly shaped glass and ZrO2 particles, and porous ZrO2 spheres), monomers, and polymerization initiators were prepared to determine the effect of filler morphology on the adhesive strength of the resin cement. The strength of adhesion to a computer-aided design/computer-aided manufacturing (CAD/CAM) resin block was investigated mechanically by measuring the tensile bond strength, flexural strength, and elastic modulus. The resin cement containing sub-micron porous ZrO2 spheres had significantly higher tensile bond strength than the other resin cements. The resin cement containing the porous ZrO2 spheres had markedly lower flexural strength and elastic modulus values than the resin cements containing SiO2 and glass fillers.

Reliable Surface Area Assessment of Wet and Dry Nonporous and Nanoporous Particles: Nuclear Magnetic Resonance Relaxometry and Gas Physisorption

The reliable assessment of surface area is extremely important for many applications, e.g., catalysis, separation, and energy storage/conversion. Within this context, major progress has been made concerning the textural characterization of porous materials in the gas/dry state, e.g., gas physisorption and mercury porosimetry. However, these methods are not sufficient for the characterization of wet materials utilized in liquid-phase processes. For this, the application of nuclear magnetic resonance (NMR) relaxometry has been considered, but a systematic and rigorous assessment of the applicability of NMR relaxometry for reliable surface and pore size characterization of nanoporous materials is missing. Hence, we present a systematic study in which we assess the applicability of NMR relaxometry for reliable surface area assessment utilizing for the first time true surface area benchmark data based on argon 87 K adsorption on nonporous particles (silica and carbon black) coupled with the development of an advanced methodology including the investigation of the choice of the probe molecule and the effect of its accessibility to the pore network. Our results show that the method provides a fast (a few minutes per measurement) and reliable surface area of silica and carbon black model materials immersed in a liquid phase. In addition, our work clearly demonstrates the potential of NMR relaxometry for the targeted surface area assessment of defined pore classes (here ultramicropores) and suggests a new methodology for the characterization of pore entrances (pore window size). Furthermore, we investigate the effect of wettability and suggest that NMR relaxometry could be developed into a unique tool for assessing the wetting characteristics of adsorbate phases on pore surfaces. This fundamental study can be considered a first major step in enabling NMR relaxometry for reliable surface area assessment for wet materials, particularly relevant for materials used in processes occurring in a liquid phase.

Solving the delivery of Lactococcus lactis: Improved survival and storage stability through the bioencapsulation with different carriers

Probiotics are live microorganisms that confer beneficial effects on the health of the host if administered in adequate amounts (106 CFU viable microorganisms/g of food). As the most frequent route of administration of these microorganisms is oral, the number of them that remains viable through the gastrointestinal tract decreases substantially. Thus, in this research work, we developed a series of alginate-based microparticles using different adjuvants such as methylcellulose, carboxymethylcellulose, chitosan, carbopol, β-cyclodextrin, starch, carrageenan, and Eudragit® RS 100 as carriers for improving the survival of Lactococcus lactis. The alginate-based formulations exhibited very good drug encapsulation efficiency, up to 90%. Release studies from selected microparticles revealed that almost 100% of bacteria were in solution at 30min. By scanning electron microscopy, irregular nonporous particles with a size between 200 and 500µm were seen. In particular, microparticles formulated with alginate-carboxymethylcellulose and alginate-methylcellulose exhibited the best protection for the bacterial cells against both simulated gastric juice and simulated intestinal juice. In addition, those microparticulate systems were able to maintain the viability of the encapsulated bacteria in large numbers for at least 24weeks. Thus, the present study confirmed that these alginate-based microparticles are a valuable approach for keeping the viability and storage stability of L. lactis.

Determination of the kinetic parameters of leaching from experimental data using the non-porous shrinking particle model: Effect of error propagation

All alternatives of the non-porous shrinking particle model (NSPM) referred to in the literature were reviewed and critically compared – they differ especially in their ability to reflect the role of three crucial model parameters: the order of reaction, liquid/solid ratio and activity coefficient of the leaching reagent. A procedure to calculate an experimental error related to the methodology of laboratory leaching tests (including the effect of different ore-particle size) has been proposed. Error propagation in the process of determination of the apparent order of reaction and activation energy from experimental data was analysed in detail, to estimate the systematic error of the simulation model developed. The simulation models tested were validated using the experimental data for the reaction system MgO-HCl-H2O. Based on the results obtained, some recommendations for an effective practical use of the NSPM have been suggested.

SiO2 nanospheres as surfactant and template in aqueous dispersion polymerizations yielding highly nanoporous resin particles

HypothesisHigh nitrogen containing resins such as poly(melamine-co-formaldehyde) (PMF) are known for their very good adsorption properties. Until now, using an ecofriendly hard-templating approach with SiO2 nanospheres in water for synthesis, only yielded either highly porous particles with diameters up to 1 µm or non-porous particles with diameters above 1 µm. Small particles cannot be used as fixed bed adsorbents in columns because of the very high pressure occurring. ExperimentsTo yield particles with high porosity and larger diameters for the use as fixed bed adsorbent, we investigated the influence of several synthesis parameters on porosity and particle morphology. FindingsFrom all variations, we proposed a mechanism for the complex interplay between the PMF prepolymer and resin species with SiO2 nanoparticles acting both as Pickering-like surfactant and template particle. With this knowledge we were able to produce a suitable column material with high specific surface area up to 260 m2/g. We then proved the application of this material for aqueous dichromate adsorption in batch, yielding a maximum capacity of 138 mg/g with recyclability. In column experiments, the contamination of 5 mg/L dichromate in water was reduced to drinking water safe levels for an influent volume equal to over 160 bed volumes.