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Featured Application: This study provides an innovative approach to prevent the migration of carbonate apatite (CAp) granules during implantation. The proposed method combines the setting properties of calcium sulfate hemihydrate (CSH) with CAp granules, enabling their use as a stable, porous scaffold for bone regeneration. Granular bone substitutes are commonly used in dental treatments owing to their adaptability to irregular bone defects. However, granule migration during and after implantation poses a significant challenge, impairing bone regeneration. This study addresses this issue by setting carbonate apatite (CAp) granules using crystal interlocking owing to the bassanite (calcium sulfate hemihydrate (CSH))-to-gypsum (calcium sulfate dihydrate (CSD)) transformation on the granule surface. CAp granules were mixed with CSH slurry (water/CSH ratio of 0.4) at varying CSH/CAp ratios of 0.33, 0.43, 0.54, 0.67, and 0.82. At all of these mixing ratios, needle-shaped CSD crystals formed on the CAp granule surface, and the CSD crystals interlocked with each other; consequently, CAp granules were set. As the CSH/CAp ratio increased from 0.33 to 0.82, the CSD crystal length increased from 6.58 to 6.79 μm, while the setting time decreased from 30.3 to 15.5 min. Although the porosity of the set CAp granules decreased with an increase in the CSH/CAp ratio, the set granules maintained intergranular spaces of 77.3 μm at a CSH/CAp ratio of 0.82 conducive to cellular infiltration. After immersion in saline for six days, the set CAp granules at a CSH/CAp ratio of 0.82 maintained their original shape, demonstrating enhanced stability compared to lower CSH/CAp ratios where partial or complete collapse occurred. The porosity and specific surface area increased to 59.9% and 3.66 m2/g, respectively, and the intergranular spaces increased to 176.4 μm. Therefore, mixing the CAp granules with CSH at a ratio of 0.82 may prevent granule migration during and after implantation. Moreover, the CSD component of the granules is likely to resorb more rapidly than the CAp component in vivo, promoting porosity in the set granules and facilitating efficient bone replacement. [ABSTRACT FROM AUTHOR]

This study presents the synthesis of a CuO-TiO2–saponite ternary nanocomposite via a hydrothermal method, designed to efficiently remove bromocresol green dye. Characterization techniques, including X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy, confirmed significant interactions between metal oxide nanoparticles and the clay mineral matrix. Diffuse reflectance and photoluminescence analyses revealed a narrow band gap and surface defects, such as oxygen vacancies, enhancing the material's photocatalytic properties. Under UV irradiation, the nanocomposite achieved 83% discoloration of bromocresol green dye within 150 min. The inhibitor studies identified hydroxyl and superoxide radicals as key species in the degradation mechanism. This work underscores the potential of clay-mineral-based nanocomposites, where clay minerals function both as structural support and as enhancers of the semiconductor's photocatalytic activity. [ABSTRACT FROM AUTHOR]

The gypsum crystals (CaSO4·2H2O) crystallizes in a low symmetry system (monoclinic) and shows a marked layered structure along with a perfect cleavage parallel to the {010} faces. Owing to its widespread occurrence, as a single or twinned crystal, here the gypsum equilibrium (E.S.) and growth shapes (G.S.) have been re-visited. In making the distinction among E.S. and G.S., in the present work, the basic difference between epitaxy and homo-taxy is clearly evidenced. Gypsum has also been a fruitful occasion to recollect the general rules concerning either contact or penetration twins, for free growing and for twinned crystals nucleating onto pre-existing substrates. Both geometric and crystal growth aspects have been considered as well, by unifying theory and experiments of crystallography and crystal growth through the intervention of β adh , the physical quantity representing the specific adhesion energy between gypsum and other phases. Hence, the adhesion energy allowed us to systematically use the Dupré's formula. In the final part of the paper, peculiar attention has been paid to sediments (or solution growth) where the crystal size is very small, in order to offer a new simple way to afford classical (CNT) and non-classical nucleation (NCNT) theories, both ruling two quantities commonly used in the industrial crystallization: the total induction times ( t i n d t o t a l ) and crystal size distribution (CSD). [ABSTRACT FROM AUTHOR]

Determining the mechanisms of the formation of giant crystals is a challenging subject. Gypsum, calcium sulfate dihydrate (CaSO4·2H2O), is known to form crystals larger than one meter in several locations worldwide. These selenite crystals grow at different temperatures, either in sedimentary or hydrothermal systems. The famous selenite crystals of the geode of Pulpí (Almería, Spain) are known to have grown at a temperature T = 20 ± 5 °C and have been proposed to form in a subaqueous environment by a self-feeding mechanism triggered by anhydrite dissolution and the ripening of microcrystalline gypsum, enhanced by oscillations in temperature. This paper reports the monitored crystallization of gypsum crystals, from anhydrite powder dissolution, inside airtight evaporation-free reactors under oscillating low temperatures (15 °C < T < 25 °C). These crystals are clearly smaller than the ones in the Pulpí mine but exhibit similar habits (i.e., single blocky crystals and twins following the 100 twinning law). The growth rate of gypsum single crystals has been measured to be between 3.8 and 35.3 µm/day. Noteworthy, we document the occurrence of the 100 contact twinning law of gypsum, which is the most widespread twinning law in natural environments but never univocally reported in laboratory experiments. The selection of the 100 contact twinning law has been correlated to the low supersaturation values obtained in the experiment, where the concentration in these long-duration experiments can be safely assumed to be the equilibrium concentration, i.e., 0.3 (at 25 °C) ≤ SI ≤ 0.4 (at 15 °C). We discuss the relevance of our experiment for forming the gypsum crystals of Pulpí in the framework of the geological history of Pulpí mineralization. These laboratory model experiments contribute to a deeper understanding of mineral nucleation and growth processes in natural environments. [ABSTRACT FROM AUTHOR]

In response to the need for improvement in the utilization of ammonium-rich solutions after the electrochemical reduction of nitrate (NO3−–RR), this study combined phosphorus-containing wastewater and adopted the electrochemical precipitation method for the preparation of struvite (MAP) to simultaneously recover nitrogen and phosphorus resources. At a current density of 5 mA·cm−2 and an initial solution pH of 7.0, the recovery efficiencies for nitrogen and phosphorus can reach 47.15% and 88.66%, respectively. Under various experimental conditions, the generated struvite (MgNH4PO4·6H2O) exhibits a typical long prismatic structure. In solutions containing nitrate and nitrite, the coexisting ions have no significant effect on the final product, struvite. Finally, the characterization of the precipitate product by X-ray diffraction (XRD) revealed that its main component is struvite, with a high purity reaching 93.24%. Overall, this system can effectively recover ammonium nitrogen from the NO3−–RR solution system after nitrate reduction, with certain application prospects for the recovery of ammonium nitrogen and phosphate. [ABSTRACT FROM AUTHOR]

Water seepage flow can dissolve soluble minerals that exist in rock formations. With the development of the excavated area due to dissolution, the water seepage velocity (discharge) into the dissolved rock will also increase. Therefore, water seepage and dissolution propagation are two interrelated processes. Mosul Dam foundation has experienced these processes since its construction, resulting in karstification in the reservoir and foundation of the dam. The present seepage-dissolution measure to minimize this phenomenon relies on traditional cementitious grouts. However, this measure has not been able to address the issue effectively. Currently, there are a few studies on the chemical remediation of soluble rocks under the influence of high-velocity water flow and water pressure. Therefore, the first part of the current study focuses on the impact of high-velocity water flow and water pressure on the dissolution acceleration of gypsum/anhydrite rocks. In the second part, the waterproof capacity of silica colloidal and its impact on the solubility reduction of the rocks is evaluated. Two distinct laboratory models were designed to simulate rock dissolution in the dam abutments and under the dam. Two sets of experiments were conducted on untreated and silica-treated samples. The experiments were executed on the samples extracted from Fatha Formation outcrop and problematic layers of brecciated gypsum situated at varying depths of the Mosul Dam foundation. The obtained findings reveal that the colloidal silica grout markedly prevents the water seepage impact on the soluble rock and that it can be very useful as an alternative to cement-based grouts. [ABSTRACT FROM AUTHOR]

This study combined inorganic α-hemihydrate gypsum (α-HHG) with organic polyacrylamide (PAM) hydrogel to create a novel α-HHG/PAM composite material. Through this facile composite strategy, this fabricated material exhibited a significantly longer initial setting time and higher mechanical strength compared to α-HHG. The effects of the addition amount and the concentration of PAM precursor solution on the flowability of the α-HHG/PAM composite material slurry, initial setting time, and mechanical properties of the hardened specimens were investigated. The structural characteristics of the composite material were examined using XRD, FE-SEM, and TGA. The results showed that the initial setting time of the α-HHG/PAM composite material was 25.7 min, which is an extension of 127.43% compared to that of α-HHG. The flexural strength and compressive strength of the oven-dried specimens were 23.4 MPa and 58.6 MPa, respectively, representing increases of 34.73% and 84.86% over values for α-HHG. The XRD, FE-SEM, and TGA results all indicated that the hydration of α-HHG in the composite material was incomplete. The incompleteness is caused by the competition between the hydration process of inorganic α-HHG and the gelation process of the acrylamide molecules for water, which hinders some α-HHG from entirely reacting with water. The enhanced mechanical strength of the α-HHG/PAM composite material results from the tight interweaving and integrating of organic and inorganic networks. This study provides a concise and efficient approach to the modification research of hemihydrate gypsum. [ABSTRACT FROM AUTHOR]

This review article delves into the growing recognition of fractal structures in mesoscale phenomena. The article highlights the significance of realistic fractal-like aggregate models and efficient modeling codes for comparing data from diverse experimental findings and computational techniques. Specifically, the article discusses the current state of fractal aggregate modeling, with a focus on particle clusters that possess adjustable fractal dimensions ( D f ). The study emphasizes the suitability of different models for various D f –intervals, taking into account factors such as particle size, fractal prefactor, the polydispersity of structural units, and interaction potential. Through an analysis of existing models, this review aims to identify key similarities and differences and offer insights into future developments in colloidal science and related fields. [ABSTRACT FROM AUTHOR]

The direct incorporation of Sb(V) ions into a polycondensed silsesquioxane network based on heptaisobutyl POSS units (Sb(V)-POSSs) through a corner-capping reaction is reported for the first time in this work. As a reference sample, a completely condensed monomeric Sb(III)-POSS was prepared using a similar synthetic protocol. The chemical properties of both Sb-containing POSSs were investigated with different analytical and spectroscopic techniques. The analyses confirm the success of the corner-capping reaction for both samples and indicate that an Sb(V)-POSS sample is characterized by a heterogenous multimeric arrangement with an irregular organization of POSS cages linked to Sb(V) centers, and has a more complex structure with respect to the well-defined monomeric Sb(III)-POSS. [ABSTRACT FROM AUTHOR]

Considerable efforts are made worldwide to reduce inorganic scale in reverse osmosis plants, boilers and heat exchangers, evaporators, industrial water systems, geothermal power plants and oilfield applications. These include the development of new environmentally friendly antiscalants and the improvement of conventional ones. The present report is dedicated to the unconventional application of spruce wood shavings in combination with polyacrylate (PAA-F1) in a model case of gypsum scale formation. The electrical conductivity of freshly prepared gypsum solutions with a saturation SI = 2.3 and a concentration of 0.05 mol·dm−3 was analyzed over time at 25°C. It is demonstrated that the small amounts of wood shavings (0.1% by mass) alone, after being in contact with CaCl2 and Na2SO4 stock solutions for 15 min, increase the induction time tind by 25 min relative to the blank experiment (tindblank). In the presence of PAA-F1 (0.1 mg·dm−3), the difference Δtind = tind − tindblank constitutes 110 min, whereas the sequential treatment of the stock solutions with the shavings followed by PAA-F1 injection gives Δtind = 205 min. The observed synergism is associated with the selective removal of colloidal Fe(OH)3solid and Al(OH)3solid nanoimpurities from the stock solutions via their sorption to the well-developed surface of wood. Wood shavings therefore represent a very promising and environmentally friendly material that can significantly improve the effectiveness of conventional antiscalants. [ABSTRACT FROM AUTHOR]

The precipitation of struvite from wastewater is a potential alternative for the recovery of nutrients, especially phosphorus, which is an essential macronutrient for agriculture but can be harmful to the environment when improperly disposed of in water bodies. In addition, struvite has elements of great added value for agricultural activity (P, N, and Mg) and is, therefore, considered a sustainable alternative fertilizer. In its formation process, several intervening physicochemical factors may be responsible for the production yield levels. Optimization processes can help to define and direct the factors that truly matter for precipitation. In this context, a sequential design of experiments (DOE) methodology was applied to select and optimize the main struvite precipitation factors in wastewater. Initially, a screening was performed with eight factors with the aid of Plackett–Burman design, and the factors with a real influence on the process were identified. Then, a Doehlert design was used for optimization by applying the response surface methodology and the desirability function. The results were used to identify the optimal points of the pH (10.2), N/P ratio (≥4), and initial phosphorus concentration (183.5 mg/L); these values had a greater effect on phosphorus recovery and the production of struvite, which was confirmed through thermochemical analysis of the decomposition of its structure by differential scanning calorimeter—glass transition temperature (DSC-TG) and phase identification by X-ray diffraction (XRD). The determination of the best synthesis conditions is an enormous contribution to the control of the process because these conditions lead to better yields and higher levels of phosphorus recovery. [ABSTRACT FROM AUTHOR]

The mechanism of the nonclassical crystallization pathway of calcium sulfate dihydrate (gypsum) with calcium sulfate hemihydrate (bassanite) as a precursor has been considered in many studies. However, studies on the crystallization of gypsum in natural environments have rarely been reported, especially with regard to natural estuaries, which are one of the most important precipitation environments for calcium sulfate. Here, surface sediments (0–5 cm) of Lingding Bay of the Pearl River Estuary in China were sampled and analyzed. X-ray powder diffraction (XRD) analysis showed that calcium sulfate in the surface sediments mainly existed in the form of gypsum. In high-resolution transmission electron microscopy (HR-TEM) analysis, calcium sulfate nanoparticles were observed in the surface sediments. These particles mainly included spherical calcium sulfate nanoparticles (diameter ranging from 10–50 nm) and bassanite nanorod clusters (sizes ranging from 30 nm × 150 nm to 100 nm × 650 nm), and their main elements included O, S and Ca, with small amounts of N, Si, Na and Mg. The bassanite nanorods self-assembled into aggregates primarily co-oriented along the c axis (i.e., [001] direction). In epitaxial growth into larger bassanite nanorods (100 nm × 650 nm), the crystal form of gypsum could be observed. Based on the observations and analyses, we proposed that the crystallization of gypsum in surface sediments of the natural estuary environment could occur through the nonclassical crystallization pathway. In this pathway, bassanite nanoparticles and nanorods appear as precursors (nanoscale precursors), grow via self-assembly, and are finally transformed into gypsum. This work provided evidence supporting and enhancing the understanding of the crystallization pathway of calcium sulfate phases in the natural estuary environment. Furthermore, the interactions between calcium sulfate nanoparticles and the natural estuary environment were examined. [ABSTRACT FROM AUTHOR]

Polycationic polypeptides prompt the polycondensation of inorganic oxides, most notably of silica. Hen egg-white lysozyme is a small polycationic protein that is quite conveniently used to this end. The fate of the protein after the completion of the polycondensation reaction is still a matter of debate. We have recently proven that lysozyme strongly interacts with silica. In this study, we use spin-label-based EPR spectroscopy to investigate whether the protein shows an orientational preference with respect to the silica surface within the composite. We find that a large share of the protein behaves as when it is adsorbed on pre-formed silica, albeit with a more marked preference for orientations that point the patches with higher surface charge density toward the material. In addition, a part of the protein shows a less-defined behavior. With this study, we provide additional information on the nature of the protein-material interactions in this class of bioinspired solids. [ABSTRACT FROM AUTHOR]

Deposits of calcium sulfate scale on the surfaces of industrial equipment in distillation facilities, reverse osmosis desalination plants, in oil and gas industries lead to significant clogging of pipes and membranes and to a serious increase in production costs. For the mitigation of scale formation, the wide spectrum of antiscalants is applied. The present work is dedicated to the study of calcium sulfate deposition from supersaturated aqueous solutions in the presence of polyacrylic antiscalant with fluorescent marker (naphthalimide fragment) PAA-F1, which provides traceability of the scale inhibitor and a better understanding of its efficacy. A paradoxical phenomenon is being described here. Antiscalant causes a change in the crystal phase from bassanite to gypsum, significantly reduces the amount of deposit, but does not reveal the presence of its molecules either at the kink, step, or at selected edge sites of deposited crystals. Contrary to the predictions of the theory, it either stays in the aqueous phase, or forms its own separate phase Ca-PAA-F1. It is demonstrated that the antiscalant does not block the surfaces of calcium sulfate nuclei or crystal surfaces, but rather the foreign particles of nanodust with particle sizes around 1 nm, naturally occurring in any aqueous solution. As a result, the number of calcium nucleation sites is reduced, and the rate of scale formation decreases without any apparent antiscalant–scale interaction. On the grounds of the current experiment, the substoichiometric effect of scale inhibition obtained an alternative, quite stoichiometric explanation. [ABSTRACT FROM AUTHOR]

Equipment scaling leads to reduced production efficiency in a wide range of industrial applications worldwide. Various antiscaling agents are currently commonly used to mitigate this problem. However, irrespective of their long and successful application in water treatment technologies, little is known about the mechanisms of scale inhibition, particularly the localization of scale inhibitors on scale deposits. The lack of such knowledge is a limiting factor in the development of applications for antiscalants. Meanwhile, fluorescent fragments integrated into scale inhibitor molecules have provided a successful solution to the problem. The focus of this study is, therefore, on the synthesis and investigation of a novel fluorescent antiscalant: (2-(6-morpholino-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)yl)ethylazanediyl)bis(methylenephosphonic acid) (ADMP-F) which is an analog of the commercial antiscalant: aminotris(methylenephosphonic acid) (ATMP). ADMP-F has been found to effectively control the precipitation of CaCO3 and CaSO4 in solution and is a promising tracer for organophosphonate scale inhibitors. ADMP-F was compared with two other fluorescent antiscalants—polyacrylate (PAA-F1) and bisphosphonate (HEDP-F)—and was found to be highly effective: PAA-F1 > ADMP-F >> HEDP-F (CaCO3) and PAA-F1 > ADMP-F > HEDP-F (CaSO4·2H2O). The visualization of the antiscalants on the deposits provides unique information on their location and reveals differences in the "antiscalant-deposit" interactions for scale inhibitors of different natures. For these reasons, a number of important refinements to the mechanisms of scale inhibition are proposed. [ABSTRACT FROM AUTHOR]

Niclosamide is an FDA-approved anthelmintic that is being studied in clinical trials as a chemotherapeutic and broad-spectrum antiviral. Additionally, several other applications are currently in the preclinical stage. Unfortunately, niclosamide is a poorly water soluble molecule, with reduced oral bioavailability, which hinders its use for new indications. Moreover, niclosamide is a poor glass former; in other words, the molecule has a high tendency to recrystallize, and it is virtually impossible to generate a stable amorphous solid employing the neat molecule. Previously, our group reported the development of an amorphous solid dispersion (ASD) of niclosamide (niclosamide ASD) that generates nanoparticles during its dissolution, not only increasing niclosamide's apparent solubility from 6.6 ± 0.4 to 481.7 ± 22.2 µg/mL in fasted state simulated intestinal fluid (FaSSIF) but also its oral bioavailability 2.6-fold in Sprague–Dawley rats after being administered as a suspension. Nevertheless, niclosamide ASD undergoes recrystallization in acidic media, and an enteric oral dosage form is needed for its translation into the clinic. In this work, we further characterized the nanoparticles that generated during the dissolution of the niclosamide ASD. Cryogenic transmission electron microscopy (Cryo-TEM) and wide-angle X-ray scattering (WAXS) revealed that the nanoparticles were amorphous and had a particle size of ~150 nm. The oral dosage forms of niclosamide ASD were formulated using commercial enteric capsules (Capsuline® and EudracapTM) and as enteric-coated tablets. The enteric dosage forms were tested using pH-shift dissolution and acid-uptake tests, using the USP type II dissolution apparatus and the disintegration apparatus, respectively. The capsules exhibited a higher percentage of weight gain, and visual rupture of the Capsuline capsules was observed. Eudracap capsules protected the formulation from the acidic media, but polymer gelling and the formation of a nondispersible plug were noted during dissolution testing. In contrast, enteric-coated tablets protected the formulation from acid ingress and maintained the performance of niclosamide ASD granules during dissolution in FaSSIF media. These enteric-coated tablets were administered to beagle dogs at a niclosamide dose of 75 mg/kg, resulting in plasma concentrations of niclosamide higher than those reported in the literature using solubilized niclosamide at a higher dose (i.e., 100 mg/kg). In summary, an enteric oral dosage form of niclosamide ASD was formulated without hindering the generation of nanoparticles while maintaining the increase in the niclosamide's apparent solubility. The enteric-coated tablets successfully increased the niclosamide plasma levels in dogs when compared to a niclosamide solution prepared using organic solvents. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of novel luminescent amorphous POSS-based polysilsesquioxanes (PSQs) with Tb3+ and Eu3+ ions directly integrated in the polysilsesquioxane matrix is presented. Two different Tb3+/Eu3+ molar ratios were applied, with the aim of disclosing the relationships between the nature and loading of the ions and the luminescence properties. Particular attention was given to the investigation of site geometry and hydration state of the metal centers in the inorganic framework, and of the effect of the Tb3+ → Eu3+ energy transfer on the overall optical properties of the co-doped materials. The obtained materials were characterized by high photostability and colors of the emitted light ranging from orange to deep red, as a function of both the Tb3+/Eu3+ molar ratio and the chosen excitation wavelength. A good energy transfer was observed, with higher efficiency displayed when donor/sensitizer concentration was lower than the acceptor/activator concentration. The easiness of preparation and the possibility to finely tune the photoluminescence properties make these materials valid candidates for several applications, including bioimaging, sensors, ratiometric luminescence-based thermometers, and optical components in inorganic or hybrid light-emitting devices. [ABSTRACT FROM AUTHOR]

The nanosheet-seeding growth (NSG) technique is an interesting synthesis method for preparing two-dimensional (2D) materials by employing ultrathin nanosheets as templates. In this work, the synthesis of 2D TiO2 nanoplates using Ti0.87O2 nanosheets via the NSG process is thoroughly studied to achieve a better understanding of this process. The influence of various synthesis conditions on the morphology and phase composition has been carefully examined. The study of synthesis time reveals that the TiO2 grows in the Stranski–Krastanov mode on the templates and the growth follows second-order kinetics. It is also found that the concentration of precursors and the synthesis time are the effective parameters in controlling the thickness of TiO2 nanoplates. The phase of the sample changes from anatase TiO2 to NH4TiOF3 and the morphology changes from flake to disk with the increase in the precursor concentration. The synthesis temperature has a large influence on the morphology and thickness of the sample but has little effect on the phase composition. However, the synthesis temperature changes the color of the sample, and a high temperature enlarges the light absorption range of the sample. [ABSTRACT FROM AUTHOR]

Acute febrile illness (AFI) is a morbid condition with a sudden onset of fever with at least seven days of evolution, where no signs or symptoms related to an apparent infection have been identified. In Latin America, a high proportion of disease is typically due to malaria and arboviruses. However, among the infectious etiologies, tick-borne diseases (TBDs) should also be considered, especially in areas where people come into direct contact with these arthropods. This study aims to describe the etiology and epidemiology related to tick-borne agents in patients with AFI and the tick's natural infection by agents of TBD in the rural tropical Magdalena Medio region in Colombia, and explore the factors associated with the presence of Coxiella burnetii infection. We conduct a cohort study enrolling 271 patients with AFI to detect the bacteria of the genera Anaplasma, Ehrlichia, Coxiella, Rickettsia, Borrelia, and Francisella through molecular techniques, and additionally evaluate the presence of IgG antibodies with commercially available kits. We also conduct tick collection in the patient's households or workplaces for the molecular screening of the same bacterial genera. Seropositivity to IgG antibodies was obtained for all the bacteria analyzed, with Francisella being the most common at 39.5% (107/271), followed by R. rickettsii at 31.4% (85/271), Ehrlichia at 26.9% (73/271), R. typhi at 15.5% (42/271), Anaplasma at 14.4% (39/271), and Borrelia at 6.6% (18/271). However, these bacteria were not detected by the molecular techniques used. Coxiella burnetii infection was detected in 39.5% of the patients: 49.5% only by phase I and II IgG antibodies, 33.6% only by real-time PCR, and 16.8% had a concordant positive result for both techniques. A total of 191 adult ticks, 111 females and 80 males, were collected and identified as Rhipicephalus sanguineus s.l. and Rhipicephalus microplus. In the 169 adult ticks in which natural infection was evaluated, Ehrlichia spp. was detected in 21.3% (36/169), Coxiella spp. in 11.8% (20/169), and Anaplasma spp. in 4.7% (8/169). In conclusion, we identified the prior exposition to Francisella, Anaplasma, Ehrlichia, Rickettsia, Borrelia, and Coxiella in patients through serological tests. We also detected the infection of C. burnetii using molecular techniques. In the ticks, we identified bacteria of the genera Coxiella, Anaplasma, and Ehrlichia. These results suggest the importance of these zoonotic agents as possible causes of AFI in this region. [ABSTRACT FROM AUTHOR]

Crystal nucleation determining the formation and assembly pathway of first organic materials is the central science of various scientific disciplines such as chemical, geochemical, biological, and synthetic materials. However, our current understanding of the molecular mechanisms of nucleation remains limited. Over the past decades, the advancements of new experimental and computational techniques have renewed numerous interests in detailed molecular mechanisms of crystal nucleation, especially structure evolution and solution chemistry. These efforts bifurcate into two categories: (modified) classical nucleation theory (CNT) and non-classical nucleation mechanisms. In this review, we briefly introduce the two nucleation mechanisms and summarize current molecular understandings of crystal nucleation that are specifically applied in polymorphic crystallization systems of small organic molecules. Many important aspects of crystal nucleation including molecular association, solvation, aromatic interactions, and hierarchy in intermolecular interactions were examined and discussed for a series of organic molecular systems. The new understandings relating to molecular self-assembly in nucleating systems have suggested more complex multiple nucleation pathways that are associated with the formation and evolution of molecular aggregates in solution. [ABSTRACT FROM AUTHOR]

In this study, novel lanthanide-containing double-decker polyhedral oligomeric silsesquioxanes (POSS) were prepared by combining the partially condensed TetraSilanolPhenyl POSS with terbium (Tb3+) and europium (Eu3+) ions. This open-cage POSS possesses four diametrically opposite silanol groups that are able to coordinate, under mild conditions, different luminescent ions through a simple corner-capping method. The two metal-containing POSS functionalized with Tb3+ and with an equimolar combination of Tb3+ and Eu3+ show a completely condensed structure with different luminescent properties. Their emission features depend on the chemical nature of the metal ions incorporated in the framework. An improved stokes shift was detected in the bimetallic compound containing both the Tb3+ and Eu3+ ions, promoted by the occurrence of a Tb3+→Eu3+ energy transfer mechanism. These characteristics identify this metal-functionalized silica platform as a potential candidate for the development of novel luminescent devices. [ABSTRACT FROM AUTHOR]

The goal of this study was to describe the variation in hospital-based diagnostic care activities for patients with symptomatology suspect for breast cancer in The Netherlands. Two cohorts were included: the 'benign' cohort (30,334 women suspected of, but without breast cancer) and the 'malignant' cohort (2236 breast cancer patients). Hospital-based financial data was combined with tumor data (malignant cohort) from The Netherlands Cancer Registry. Patterns within diagnostic pathways were analyzed. Factors influencing the number of visits and number of diagnostic care activities until diagnosis were identified in the malignant cohort with multivariable Cox and Poisson regression models. Compared to patients with benign diagnosis, patients with malignant disease received their diagnosis less frequently in one day, after an equal average number of hospital visits and higher average number of diagnostic activities. Factors increasing the number of diagnostic care activities were the following: lower age and higher cM-and cN-stages. Factors increasing the number of days until (malignant) diagnosis were as follows: higher BIRADS-score, screen-detected and higher cN-and cT-stages. Hospital of diagnosis influenced both number of activities and days to diagnosis. The diagnostic care pathway of patients with malignant disease required more time and diagnostic activities than benign disease and depends on hospital, tumor and patient characteristics. [ABSTRACT FROM AUTHOR]

During the last couple of decades, the rapidly advancing field of nanotechnology has produced a wide palette of nanomaterials, most of which are considered as “synthetic” and, among the wider public, are often met with a certain suspicion. Despite the technological sophistication behind many of these materials, “nano” does not always equate with “artificial”. Indeed, nature itself is an excellent nanotechnologist. It provides us with a range of fine particles, from inorganic ash, soot, sulfur and mineral particles found in the air or in wells, to sulfur and selenium nanoparticles produced by many bacteria and yeasts. These nanomaterials are entirely natural, and, not surprisingly, there is a growing interest in the development of natural nanoproducts, for instance in the emerging fields of phyto- and phyco-nanotechnology. This review will highlight some of the most recent—and sometimes unexpected—advances in this exciting and diverse field of research and development. Naturally occurring nanomaterials, artificially produced nanomaterials of natural products as well as naturally occurring or produced nanomaterials of natural products all show their own, particular chemical and physical properties, biological activities and promise for applications, especially in the fields of medicine, nutrition, cosmetics and agriculture. In the future, such natural nanoparticles will not only stimulate research and add a greener outlook to a traditionally high-tech field, they will also provide solutions—pardon—suspensions for a range of problems. Here, we may anticipate specific biogenic factories, valuable new materials based on waste, the effective removal of contaminants as part of nano-bioremediation, and the conversion of poorly soluble substances and materials to biologically available forms for practical uses. [ABSTRACT FROM AUTHOR]

Synchrotron-based small-and wide-angle X-ray scattering (SAXS/WAXS) was used to examine in situ the precipitation of gypsum (CaSO4·2H2O) from solution. We determined the role of (I) supersaturation, (II) temperature and (III) additives (Mg2+ and citric acid) on the precipitation mechanism and rate of gypsum. Detailed analysis of the SAXS data showed that for all tested supersaturations and temperatures the same nucleation pathway was maintained, i.e., formation of primary particles that aggregate and transform/re-organize into gypsum. In the presence of Mg2+ more primary particle are formed compared to the pure experiment, but the onset of their transformation/reorganization was slowed down. Citrate reduces the formation of primary particles resulting in a longer induction time of gypsum formation. Based on theWAXS data we determined that the precipitation rate of gypsum increased 5-fold from 4 to 40 °C, which results in an effective activation energy of ∼30 kJ·mol-1. Mg2+ reduces the precipitation rate of gypsum by more than half, most likely by blocking the attachment sites of the growth units, while citric acid only weakly hampers the growth of gypsum by lowering the effective supersaturation. In short, our results show that the nucleation mechanism is independent of the solution conditions and that Mg2+ and citric acid influence differently the nucleation pathway and growth kinetics of gypsum. These insights are key for further improving our ability to control the crystallization process of calcium sulphate. [ABSTRACT FROM AUTHOR]

There are three groups of scientists dominating the search for the origin of life: the organic chemists (the Soup), the molecular biologists (RNA world), and the inorganic chemists (metabolism and transient-state metal ions), all of which have experimental adjuncts. It is time for Clays and the Origin of Life to have its experimental adjunct. The clay data coming from Mars and carbonaceous chondrites have necessitated a review of the role that clays played in the origin of life on Earth. The data from Mars have suggested that Fe-clays such as nontronite, ferrous saponites, and several other clays were formed on early Mars when it had sufficient water. This raised the question of the possible role that these clays may have played in the origin of life on Mars. This has put clays front and center in the studies on the origin of life not only on Mars but also here on Earth. One of the major questions is: What was the catalytic role of Fe-clays in the origin and development of metabolism here on Earth? First, there is the recent finding of a chiral amino acid (isovaline) that formed on the surface of a clay mineral on several carbonaceous chondrites. This points to the formation of amino acids on the surface of clay minerals on carbonaceous chondrites from simpler molecules, e.g., CO2, NH3, and HCN. Additionally, there is the catalytic role of small organic molecules, such as dicarboxylic acids and amino acids found on carbonaceous chondrites, in the formation of Fe-clays themselves. Amino acids and nucleotides adsorb on clay surfaces on Earth and subsequently polymerize. All of these observations and more must be subjected to strict experimental analysis. This review provides an overview of what has happened and is now happening in the experimental clay world related to the origin of life. The emphasis is on smectite-group clay minerals, such as montmorillonite and nontronite. [ABSTRACT FROM AUTHOR]

Methyl-modified, cobalt-doped silica (Co/MSiO2) materials were synthesized by sol-gel technique calcined in N2 atmospheres, and membranes were made thereof by coating method. The effects of Co/Si molar ratio (nCo) on the physical-chemical constructions of Co/MSiO2 materials and microstructures of Co/MSiO2 membranes were systematically investigated. The gas permeance performance and hydrothermal stability of Co/MSiO2 membranes were also tested. The results show that the cobalt element in Co/MSiO2 material calcined at 400 °C exists not only as Si–O–Co bond but also as Co3O4 and CoO crystals. The introduction of metallic cobalt and methyl can enlarge the total pore volume and average pore size of the SiO2 membrane. The activation energy (Ea) values of H2, CO2, and N2 for Co/MSiO2 membranes are less than those for MSiO2 membranes. When operating at a pressure difference of 0.2 MPa and 200 °C compared with MSiO2 membrane, the permeances of H2, CO2, and N2 for Co/MSiO2 membrane with nCo = 0.08 increased by 1.17, 0.70, and 0.83 times, respectively, and the perm-selectivities of H2/CO2 and H2/N2 increased by 27.66% and 18.53%, respectively. After being steamed and thermally regenerated, the change of H2 permeance and H2 perm-selectivities for Co/MSiO2 membrane is much smaller than those for MSiO2 membrane. [ABSTRACT FROM AUTHOR]

Simple Summary: Q fever is a zoonotic disease with significant public health implications. Sheep are one of the main reservoirs for this disease, whereas abortion is the primary clinical outcome. Q fever is endemic in many countries, including Saudi Arabia. Flock management practices play a significant role in the spread of Q fever infection among flocks. However, information on flock management factors associated with Q fever seropositivity in Saudi Arabia is very scarce. The results obtained from 50 flocks identified three protective factors (lambing pen, change bedding after removing aborted materials, and isolation of aborted ewes) and two risk factors (infestation with ticks and history of Q fever) were associated with Q fever seropositivity. Q fever is a zoonotic disease caused by Coxiella burnetii (C. burnetii), an intracellular, Gram-negative bacterium that infects humans and domestic ruminants. Information on flock management factors associated with Q fever seropositivity in Saudi Arabia is very scarce. Therefore, the objective of this study was to identify the animal and flock management factors associated with Q fever seropositivity. For the assessment of risk factors, a case-control study was carried out. Cases (n = 25) were flocks that had recent abortions within the previous two weeks and were PCR positive for C. burnetii. Control flocks (n = 25) had no history of recent abortion and were PCR negative for C. burnetii. A questionnaire was developed to collect information about the flock management risk factors possibly associated with Q fever exposure in sheep. A total of 2437 sheep serum samples, collected from infected (n = 1610, 10–150 samples/flock) and non-infected (n = 827, 10–65 samples/flock) flocks, were tested for C. burnetii antibodies using a commercial ELISA kit between May 2018 and April 2019. In addition, 521 samples, including 50 aborted materials, 173 vaginal swabs, 134 faecal, and 164 milk samples, were collected for PCR testing. Infected flocks were 100% seropositive (within-flock seroprevalence ranging between 13.8% and 60%) and 100% PCR positive (with animal shedders of C. burnetii through aborted materials and/or vaginal fluids, feces, and milk). However, in non-infected control flocks, 28% were seropositive (within-flock seroprevalence ranging between 6.7% and 20%) and none had C. burnetii shedders. Epidemiological data were analyzed using mixed-effect logistic regression with a random effect for the flock. The results identified three protective factors: flocks with a lambing pen (odds ratio (OR): 0.46; 95% CI: 0.28–0.76), change bedding after removing aborted materials (OR: 0.42; 95% CI: 0.23–0.76), and flocks that isolated aborted ewes (OR: 0.41; 95% CI: 0.25–0.67), as well as two risk factors: flocks infested with ticks (OR: 2.78; 95% CI: 1.65–4.70) and flocks with a history of Q fever (OR: 3.03; 95% CI: 1.42–6.50). These results could be used to improve sheep flock biosecurity measures to prevent the introduction and reduce exposure of sheep and humans to Q fever infection. [ABSTRACT FROM AUTHOR]

Calcium sulfate (CaSO4) is one of the most common evaporites found in the earth's crust. It can be found as four main variations: gypsum (CaSO4∙2H2O), bassanite (CaSO4∙0.5H2O), soluble anhydrite, and insoluble anhydrite (CaSO4), being the key difference the hydration state of the sulfate mineral. Naica giant crystals' growth starts from a supersaturated solution in a delicate thermodynamic balance close to equilibrium, where gypsum can form nanocrystals able to grow up to 11–12 m long. The growth rates are reported to be as slow as (1.4 ± 0.2) × 10−5 nm/s, taking thousands of years to form crystals with a unique smoothness and diaphaneity, which may or may not include solid or liquid inclusions. Conservation efforts can be traced back to other gypsum structures found prior to Naica's. Furthermore, in the last two decades, several authors have explored the unique requirements in which these crystals grow, the characterization of their environment and microclimatic conditions, and the prediction of deterioration scenarios. We present a state-of-the-art review on the mentioned topics. Beyond the findings on the origin, in this work we present the current state and the foreseeable future of these astounding crystals. [ABSTRACT FROM AUTHOR]

The present study investigates the gradual replacement of Ca2+ with Mg2+ ions in brushite (CaHPO4·2H2O). To date, this approach has not been systematically explored and may prove beneficial for the production of Ca1−xMgxHPO4·nH2O materials with tailored properties which are suitable for environmental and medical applications. For their production, solutions of sodium dihydrogen orthophosphate dehydrate, NaH2PO4·2H2O, calcium nitrate tetrahydrate, Ca(NO3)2·4H2O, magnesium nitrate hexahydrate, Mg(NO3)2·6H2O and ammonium hydroxide solution, NH4OH, were used. At low Mg/Ca molar ratios (up to 0.25) in the starting solution, partial replacement of Ca with Mg takes place (Mg doping) but no struvite is produced as discrete phase. When the Mg/Ca molar ratio increases gradually to 1.5, in addition to Mg-doped brushite, struvite, NH4MgPO4·6H2O, precipitates. The microstructure of the materials produced for different degrees of Ca replacement with Mg has been analyzed in depth with the use of powdered XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy), thermogravimetric (TG) analysis and SEM (scanning electron microscopy). The results of this study prove that the Mg/Ca ratio in the starting solution can be monitored in such a way that materials with tailored composition are obtained. [ABSTRACT FROM AUTHOR]

Saponite is a trioctahedral 2:1 smectite with the ideal composition MxMg3AlxSi4−xO10(OH,F)2.nH2O (M = interlayer cation). Both the success of the saponite synthesis and the determination of its applications depends on robust knowledge of the structure and composition of saponite. Among the routine characterization techniques, spectroscopic methods are the most common. This review, thus, provides an overview of various spectroscopic methods to characterize natural and synthetic saponites with focus on the extensive work by one of the authors (JTK). The Infrared (IR) and Raman spectra of natural and synthetic saponites are discussed in detail including the assignment of the observed bands. The crystallization of saponite is discussed based on the changes in the IR and Raman spectra and a possible crystallization model is provided. Infrared emission spectroscopy has been used to study the thermal changes of saponite in situ including the dehydration and (partial) dehydroxylation up to 750 °C. 27Al and 29Si magic-angle-spinning nuclear magnetic resonance spectroscopy is discussed (as well as 11B and 71Ga for B- and Ga-Si substitution) with respect to, in particular, Al(IV)/Al(VI) and Si/Al(IV) ratios. X-ray photoelectron spectroscopy provides chemical information as well as some information related to the local environments of the different elements in the saponite structure as reflected by their binding energies. [ABSTRACT FROM AUTHOR]

The primary nucleation mechanism of the gypsum in a bulk aqueous medium was identified as a heterogeneous one for 0.05 and 0.03 mol·L−1 CaSO4·2H2O solutions and 25 °C. By means of a particle counter and dynamic light scattering (DLS) technique, solid nano/microimpurities were found, and controlled in stock brines for gypsum supersaturated solutions preparation. It is demonstrated that the common procedure of reagent grade 0.10 mol·L‒1 CaCl2 and Na2SO4 aqueous solutions filtration via 200 nm membranes is capable to reduce the foreign solid microimpurities content (size > 100 nm) from 106 to 103 units in 1 mL, but fails to affect the more numerous nanofraction (size < 100 nm). Thus, the gypsum nucleation takes place in presence of a significant amount of "nano/microcodust" templates, and has a heterogenous character. The induction time, measured by conductivity for the similar supersaturation levels, reveals a well detectable dependence on nano/microdust concentent: an increasing background particle concentration substantially decreases the induction period at a constant saturation state and temperature, and thus increases the nucleation rate. Therefore, the gypsum nucleation reaction starts tentatively through the fast heterogeneous formation of well-defined, primary nuclei via [Ca2+], [SO42‒], and [CaSO4]o species sorption on the surface of "nano/microdust" particles. Thus, the "nano/microdust", naturally occurring in any high purity chemical, plays a key role in sparingly soluble salts nucleation in the bulk aqueous medium. [ABSTRACT FROM AUTHOR]

Clay minerals surfaces potentially play a role in prebiotic synthesis through adsorption of organic monomers that give rise to highly concentrated systems; facilitate condensation and polymerization reactions, protection of early biomolecules from hydrolysis and photolysis, and surface-templating for specific adsorption and synthesis of organic molecules. This review presents processes of clay formation using saponite as a model clay mineral, since it has been shown to catalyze organic reactions, is easy to synthesize in large and pure form, and has tunable properties. In particular, a method involving urea is presented as a reasonable analog of natural processes. The method involves a two-step process: (1) formation of the precursor aluminosilicate gel and (2) hydrolysis of a divalent metal (Mg, Ni, Co, and Zn) by the slow release of ammonia from urea decomposition. The aluminosilicate gels in the first step forms a 4-fold-coordinated Al3+ similar to what is found in nature such as in volcanic glass. The use of urea, a compound figuring in many prebiotic model reactions, circumvents the formation of undesirable brucite, Mg(OH)2, in the final product, by slowly releasing ammonia thereby controlling the hydrolysis of magnesium. In addition, the substitution of B and Ga for Si and Al in saponite is also described. The saponite products from this urea-assisted synthesis were tested as catalysts for several organic reactions, including Friedel–Crafts alkylation, cracking, and isomerization reactions. [ABSTRACT FROM AUTHOR]

We have explored an efficient strategy to enhance the overall photocatalytic performances of layered perovskites by increasing the density of hydroxyl group by protonation. The experimental procedure consisted of the slow replacement of interlayer Rb+ cation of RbLaTa2O7 Dion-Jacobson (DJ) perovskite by H+ via acid treatment. Two layered perovskites synthesized by mild (1200 °C for 18 h) and harsh (950 and 1200 °C, for 36 h) annealing treatment routes were used as starting materials. The successful intercalation of proton into D-J interlayer galleries was confirmed by FTIR spectroscopy, thermal analyses, ion chromatography and XPS results. In addition, the ion-exchange route was effective to enlarge the specific surface area, thus enhancing the supply of photocharges able to participate in redox processes involved in the degradation of organic pollutants. HLaTa_01 protonated layered perovskite is reported as a efficient photocatalyst for photomineralization of trichloroethylene (TCE) to Cl− and CO2 under simulated solar light. The enhanced activity is attributed to combined beneficial roles played by the increased specific surface area and high density of hydroxyl groups, leading to an efficiency of TCE mineralization of 68% moles after 5 h of irradiation. [ABSTRACT FROM AUTHOR]

Gypsum scaling in reverse osmosis (RO) desalination process is studied in presence of a novel fluorescent 1,8-naphthalimide-tagged polyacrylate (PAA-F1) by fluorescent microscopy, scanning electron microscopy (SEM), dynamic light scattering (DLS) and a particle counter technique. A comparison of PAA-F1 with a previously reported fluorescent bisphosphonate HEDP-F revealed a better PAA-F1 efficacy, and a similar behavior of polyacrylate and bisphosphonate inhibitors under the same RO experimental conditions. Despite expectations, PAA-F1 does not interact with gypsum. For both reagents, it is found that scaling takes place in the bulk retentate phase via heterogeneous nucleation step. The background "nanodust" plays a key role as a gypsum nucleation center. Contrary to popular belief, an antiscalant interacts with "nanodust" particles, isolating them from calcium and sulfate ions sorption. Therefore, the number of gypsum nucleation centers is reduced, and in turn, the overall scaling rate is diminished. It is also shown that, the scale formation scenario changes from the bulk medium, in the beginning, to the sediment crystals growth on the membrane surface, at the end of the desalination process. It is demonstrated that the fluorescent-tagged antiscalants may become very powerful tools in membrane scaling inhibition studies. [ABSTRACT FROM AUTHOR]

The first detection of gypsum (CaSO4·2H2O) by the Mars Science Laboratory (MSL) rover Curiosity in the Gale Crater, Mars created a profound impact on planetary science and exploration. The unique capability of plasma spectroscopy, which involves in situ elemental analysis in extraterrestrial environments, suggests the presence of water in the red planet based on phase characterization and provides a clue to Martian paleoclimate. The key to gypsum as an ideal paleoclimate proxy lies in its textural variants and terrestrial gypsum samples from varied locations and textural types have been analyzed with laser-induced breakdown spectroscopy (LIBS) in this study. Petrographic, sub-microscopic, and powder X-ray diffraction characterizations confirm the presence of gypsum (hydrated calcium sulphate; CaSO4·2H2O), bassanite (semi-hydrated calcium sulphate; CaSO4·½H2O), and anhydrite (anhydrous calcium sulphate; CaSO4), along with accessory phases (quartz and jarosite). The principal component analysis of LIBS spectra from texturally varied gypsums can be differentiated from one another due to the chemical variability in their elemental concentrations. The concentration of gypsum is determined from the partial least-square regressions model. The rapid characterization of gypsum samples with LIBS is expected to work well in extraterrestrial environments. [ABSTRACT FROM AUTHOR]

Organosilica membranes are a type of novel materials derived from organoalkoxysilane precursors. These membranes have tunable networks, functional properties and excellent hydrothermal stability that allow them to maintain high levels of separation performance for extend periods of time in either a gas-phase with steam or a liquid-phase under high temperature. These attributes make them outperform pure silica membranes. In this review, types of precursors, preparation method, and synthesis factors for the construction of organosilica membranes are covered. The effects that these factors exert on characteristics and performance of these membranes are also discussed. The incorporation of metals, alkoxysilanes, or other functional materials into organosilica membranes is an effective and simple way to improve their hydrothermal stability and achieve preferable chemical properties. These hybrid organosilica membranes have demonstrated effective performance in gas and liquid-phase separation. [ABSTRACT FROM AUTHOR]

The controlled crystallisation of struvite (MgNH4PO4∙6H2O) is a viable means for the recovery and recycling of phosphorus (P) from municipal and industrial wastewaters. However, an efficient implementation of this recovery method in water treatment systems requires a fundamental understanding of struvite crystallisation mechanisms, including the behavior and effect of metal contaminants during struvite precipitation. Here, we studied the crystallisation pathways of struvite from aqueous solutions using a combination of ex situ and in situ time-resolved synthesis and characterization techniques, including synchrotron-based small- and wide-angle X-ray scattering (SAXS/WAXS) and cryogenic transmission electron microscopy (cryo-TEM). Struvite syntheses were performed both in the pure Mg-NH4-PO4 system as well as in the presence of cobalt (Co), which, among other metals, is typically present in waste streams targeted for P-recovery. Our results show that in the pure system and at Co concentrations < 0.5 mM, struvite crystals nucleate and grow directly from solution, much in accordance with the classical notion of crystal formation. In contrast, at Co concentrations ≥ 1 mM, crystallisation was preceded by the transient formation of an amorphous nanoparticulate phosphate phase. Depending on the aqueous Co/P ratio, this amorphous precursor was found to transform into either (i) Co-bearing struvite (at Co/P < 0.3) or (ii) cobalt phosphate octahydrate (at Co/P > 0.3). These amorphous-to-crystalline transformations were accompanied by a marked colour change from blue to pink, indicating a change in Co2+ coordination in the formed solid from tetrahedral to octahedral. Our findings have implications for the recovery of nutrients and metals during struvite crystallisation and contribute to the ongoing general discussion about the mechanisms of crystal formation. [ABSTRACT FROM AUTHOR]

Structural characteristics of hydrolysates formed from the aqueous Ti-, Zr-, and Ti, Zr-pillaring solutions prepared from inorganic precursors (TiCl4 and ZrOCl2), was investigated and compared with that of precipitates obtained from the same solutions after a slight alkalization of pH to the values reported for the conditions of clay pillaring. The materials were recovered by lyophilization and subsequently subjected to calcination at 500, 800 and 1000 °C. Of special interest was the effect of pH on the possible formation of mixed Ti, Zr-oxide species. Powder X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscope/energy dispersive spectrometer (SEM/EDS) analysis showed that even a relatively moderate alteration of pH in Ti-, Zr-, or Ti, Zr-precursor solutions caused substantial changes in the outcome of hydrolytic transformations, manifested by different phase and/or chemical composition of the resulting hydrolysates. Analysis of thermal evolution of hydrolysates showed that alkalization facilitated the transformation of anatase into rutile in materials obtained from Ti-pillaring solution, but retarded tetragonal to monoclinic zirconia conversion in samples derived from Zr-pillaring agent. The most striking effect was observed for the mixed Ti, Zr-pillaring solution, where an increase of pH enabled the formation of zirconium titanate as the only crystalline phase, rather than a multiphase mixture of anatase, monoclinic zirconia and zirconium titanate obtained from the more acidic precursor. The finding supports the model of mixed Ti-O-Zr network in props generated in Ti, Zr-pillared montmorillonites. [ABSTRACT FROM AUTHOR]