Microplastics encapsulation in aragonite: efficiency, detection and insight into potential environmental impacts.

Plastic pollution in aquatic ecosystems has become a significant problem especially microplastics which can encapsulate into the skeletons of organisms that produce calcium carbonates, such as foraminifera, molluscs and corals. The encapsulation of microplastics into precipitated aragonite, which in nature builds the coral skeleton, has not yet been studied. It is also not known how the dissolved organic matter, to which microplastics are constantly exposed in aquatic ecosystems, affects the encapsulation of microplastics into aragonite and how such microplastics affect the mechanical properties of aragonite. We performed aragonite precipitation experiments in artificial seawater in the presence of polystyrene (PS) and polyethylene (PE) microspheres, untreated and treated with humic acid (HA). The results showed that the efficiency of encapsulating PE and PE-HA microspheres in aragonite was higher than that for PS and PS-HA microspheres. The mechanical properties of resulting aragonite changed after the encapsulation of microplastic particles. A decrease in the hardness and indentation modulus of the aragonite samples was observed, and the most substantial effect occurred in the case of PE-HA microspheres encapsulation. These findings raise concerns about possible changes in the mechanical properties of the exoskeleton and endoskeleton of calcifying marine organisms such as corals and molluscs due to the incorporation of pristine microplastics and microplastics exposed to dissolved organic matter.

Green Nanocoatings Prepared by Crosslinking Self-Assembled Fatty Acids on Metals.

Self-assembled monolayers (SAMs) are an important element of modern nanotechnology and surface functionalization. However, their application is still limited because they are easily removed from the surface of the object in corrosive environments. Crosslinking would make SAMs more resistant to the corrosive environment they are exposed to. In this work, how to strongly crosslink SAMs made of non-toxic and biodegradable fatty acids on metal surfaces using ionizing radiation has been demonstrated for the first time. The crosslinked nanocoatings are stable over time and have significantly improved properties compared to SAMs. Thus, crosslinking opens up the possibility of using SAMS in a variety of different systems and on different materials for surface functionalization to achieve stable and durable surface properties such as biocompatibility or selective reactivity.

Calcium carbonate: controlled synthesis, surface functionalization, and nanostructured materials.

Calcium carbonate (CaCO3) is an important inorganic mineral in biological and geological systems. Traditionally, it is widely used in plastics, papermaking, ink, building materials, textiles, cosmetics, and food. Over the last decade, there has been rapid development in the controlled synthesis and surface modification of CaCO3, the stabilization of amorphous CaCO3 (ACC), and CaCO3-based nanostructured materials. In this review, the controlled synthesis of CaCO3 is first examined, including Ca2+-CO32- systems, solid-liquid-gas carbonation, water-in-oil reverse emulsions, and biomineralization. Advancing insights into the nucleation and crystallization of CaCO3 have led to the development of efficient routes towards the controlled synthesis of CaCO3 with specific sizes, morphologies, and polymorphs. Recently-developed surface modification methods of CaCO3 include organic and inorganic modifications, as well as intensified surface reactions. The resultant CaCO3 can then be further engineered via template-induced biomineralization and layer-by-layer assembly into porous, hollow, or core-shell organic-inorganic nanocomposites. The introduction of CaCO3 into nanostructured materials has led to a significant improvement in the mechanical, optical, magnetic, and catalytic properties of such materials, with the resultant CaCO3-based nanostructured materials showing great potential for use in biomaterials and biomedicine, environmental remediation, and energy production and storage. The influences that the preparation conditions and additives have on ACC preparation and stabilization are also discussed. Studies indicate that ACC can be used to construct environmentally-friendly hybrid films, supramolecular hydrogels, and drug vehicles. Finally, the existing challenges and future directions of the controlled synthesis and functionalization of CaCO3 and its expanding applications are highlighted.

Design and Implementation of a Ball-Plate Control System and Python Script for Educational Purposes in STEM Technologies.

This paper presents the process of designing, fabricating, assembling, programming and optimizing a prototype nonlinear mechatronic Ball-Plate System (BPS) as a laboratory platform for engineering education STEM. Due to the nonlinearity and complexity of BPS, the task presents challenges such as: (1) difficulty in controlling the stabilization of a particular position point, known as steady-state error, (2) position resolution, known as specific distance error, and (3) adverse environmental effects-light-shadow error, which is also discussed in this paper. The laboratory prototype BPS for education was designed, manufactured and installed at Karlovac University of Applied Sciences in the Department of Mechanical Engineering, Mechatronics program. The low-cost two-degree BPS uses a USB HD camera for computer vision as a feedback sensor and two DC servo motors as actuators. Due to control problems, an advanced block diagram of the control system is proposed and discussed. An open-source control system based on Python scripts, which allows the use of ready-made functions from the library, allows the color of the ball and the parameters of the PID controller to be changed, indirectly simplifying the control system and performing mathematical calculations directly. The authors will continue their research on this BPS mechatronic platform and control algorithms.

Precipitation at Room Temperature as a Fast and Versatile Method for Calcium Phosphate/TiO2 Nanocomposites Synthesis.

The constantly growing need for advanced bone regeneration materials has motivated the development of calcium phosphates (CaPs) composites with a different metal or metal-oxide nanomaterials and their economical and environmentally friendly production. Here, two procedures for the synthesis of CaPs composites with TiO2 nanoplates (TiNPl) and nanowires (TiNWs) were tested, with the immersion of TiO2 nanomaterials (TiNMs) in corrected simulated body fluid (c-SBF) and precipitation of CaP in the presence of TiNMs. The materials obtained were analyzed by powder X-ray diffraction, spectroscopic and microscopic techniques, Brunauer-Emmett-Teller surface area analysis, thermogravimetric analysis, dynamic and electrophoretic light scattering, and their hemocompatibility and ability to induce reactive oxygen species were evaluated. After 28 days of immersion in c-SBF, no significant CaP coating was formed on TiNMs. However, the composites with calcium-deficient apatite (CaDHA) were obtained after one hour in the spontaneous precipitation system. In the absence of TiNMs, CaDHA was also formed, indicating that control of the CaP phase formed can be accomplished by fine-tuning conditions in the precipitation system. Although the morphology and size of crystalline domains of CaDHA obtained on the different nanomaterials differed, no significant difference was detected in their local structure. Composites showed low reactive oxygen species (ROS) production and did not induce hemolysis. The results obtained indicate that precipitation is a suitable and fast method for the preparation of CaPs/TiNMs nanocomposites which shows great potential for biomedical applications.

The Influence of Different Classes of Amino Acids on Calcium Phosphates Seeded Growth.

Amino acids (AAs) attract attention for elucidating the role of proteins in biomineralization and the preparation of functionalized biomaterials. The influence that AAs exert on calcium phosphate (CaP) mineralization is still not completely understood, as contradictory results have been reported. In this paper, the influence of the addition of different classes of AAs, charged (L-aspartic acid, Asp; L-lysine, Lys), polar (L-asparagine, Asn; L-serine, Ser; L-tyrosine, Tyr), and non-polar (L-phenylalanine, Phe), on CaP growth in the presence of octacalcium phosphate (OCP) and calcium hydrogenphosphate dihydrate (DCPD) seeds was investigated. In control systems (without AAs), a calcium-deficient apatite (CaDHA) layer was formed on the surface of OCP, while a mixture of CaDHA and OCP in the form of spherical aggregates was formed on the surface of DCPD crystals. Charged and non-polar promoted, while polar AAs inhibited CaDHA formation on the OCP seeds. In the case of DCPD, Lys, Asp, and Phe promoted CaP formation, while the influence of other AAs was negligible. The most efficient promotor of precipitation in both cases was non-polar Phe. No significant influence of AAs on the composition and morphology of precipitates was observed. The obtained results are of interest for understanding biomineralization processes and additive controlled material synthesis.

Tailoring the stability/aggregation of one-dimensional TiO2(B)/titanate nanowires using surfactants.

The increased utilization of one-dimensional (1D) TiO2 and titanate nanowires (TNWs) in various applications was the motivation behind studying their stability in this work, given that stability greatly influences both the success of the application and the environmental impact. Due to their high abundance in aqueous environments and their rich technological applicability, surfactants are among the most interesting compounds used for tailoring the stability. The aim of this paper is to determine the influence of surfactant molecular structure on TNW stability/aggregation behavior in water and aqueous NaBr solution by dynamic and electrophoretic light scattering. To accomplish this, two structurally different quaternary ammonium surfactants (monomeric DTAB and the corresponding dimeric 12-2-12) at monomer and micellar concentrations were used to investigate TNW stability in water and NaBr. It was shown that TNWs are relatively stable in Milli-Q water. However, the addition of NaBr induces aggregation, especially as the TNW mass concentration increases. DTAB and 12-2-12 adsorb on TNW surfaces as a result of the superposition of favorable electrostatic and hydrophobic interactions. As expected, the interaction of TNWs with 12-2-12 was stronger than with DTAB, due to the presence of two positively charged head groups and two hydrophobic tails. As a consequence of the higher adsorption of 12-2-12, TNWs remained stable in both media, while DTAB showed an opposite behavior. In order to gain more insight into changes in the surface properties after surfactant adsorption on the TNW surface, a surface complexation model was employed. With this first attempt to quantify the contribution of the surfactant structure on the adsorption equilibrium according to the observed differences in the intrinsic log K values, it was shown that 12-2-12 interacts more strongly with TNWs than DTAB. The modelling results enable a better understanding of the interaction between TNWs and surfactants as well as the prediction of the conditions that can promote stabilization or aggregation.

In Vitro Coral Biomineralization under Relevant Aragonite Supersaturation Conditions.

The biomineralization of corals occurs under conditions of high and low supersaturation with respect to aragonite, which corresponds to day- or night-time periods of their growth, respectively. Here, in vitro precipitation of aragonite in artificial seawater was investigated at a high supersaturation, allowing spontaneous nucleation and growth, as well as at low supersaturation conditions, which allowed only the crystal growth on the deliberately introduced aragonite seeds. In either chemical systems, soluble organic matrix (SOM) extracted from Balanophyllia europaea (light sensitive) or Leptopsammia pruvoti (light insensitive) was added. The analyses of the kinetic and thermodynamic data of aragonite precipitation and microscopic observations showed that, at high supersaturation, the SOMs increased the induction time, did not affect the growth rate and were incorporated within aggregates of nanoparticles. At low supersaturation, the SOMs affected the aggregation of overgrowing crystalline units and did not substantially change the growth rate. On the basis of the obtained results we can infer that at high supersaturation conditions the formation of nanoparticles, which is typically observed in the skeleton's early mineralization zone may occur, whereas at low supersaturation the overgrowth on prismatic seeds observed in the skeleton fiber zone is a predominant process. In conclusion, this research brings insight on coral skeletogenesis bridging physicochemical (supersaturation) and biological (role of SOM) models of coral biomineralization and provides a source of inspiration for the precipitation of composite materials under different conditions of supersaturation.

Supramolecular Hydrogels with Properties Tunable by Calcium Ions: A Bio-Inspired Chemical System.

Boc-L-DOPA(OBn)2-OH is a simple synthetic molecule that promotes hydrogelation through electrostatic and π-π stacking interactions. Hydrogelation can occur in alkaline conditions by the use of triggers. Four hydrogels were prepared varying the base, NaOH or Na2CO3, and the trigger, GdL or CaCl2. When the hydrogel formed in the presence of Na2CO3 and CaCl2, the concomitant production of CaCO3 crystals occurred, generating an organic/inorganic composite material. It was observed that the hydrogel once self-assembled preserved its status even if the trigger, the calcium ions, was removed. The viscoelastic behavior of the hydrogels was analyzed through rheological experiments, which showed a solid-like behavior of the hydrogels. The corresponding xerogels were analyzed mainly by scanning electron microscopy (SEM) and synchrotron X-ray diffraction analysis (XRD). They showed differences in structure, morphology, and fiber organization according to their source. This research presents a hydrogel system that can be applied as a soft biomaterial for tissue engineering, cosmetics, food, and environmental science. Moreover, it represents a model for biomineralization studies in which the hydrogel structure can act as an analogue of the insoluble matrix that confines the calcification site, provides Ca2+, and preserves its structure.

The effect of hydrodynamic and thermodynamic factors and the addition of citric acid on the precipitation of calcium oxalate dihydrate.

This paper reports on the investigation of experimental conditions relevant for spontaneous precipitation of significant amount of pure calcium oxalate dihydrate (COD). For this purpose, the hydrodynamic and thermodynamic parameters, such as mode of agitation, temperature, supersaturation and concentration of additives (citrate ions), have been studied. The results show that in the model systems, without the citrate addition and applied mechanical stirring, calcium oxalate monohydrate (COM) was observed as dominant modification after 20 min of aging, while the magnetic stirring resulted in a formation of a mixture of COM and calcium oxalate trihydrate (COT), regardless of the temperature applied. In the mechanically stirred systems, the addition of citrate ions in the range of concentrations, 0.001 mol dm-3 < c i (Na3C6H5O7) < 0.012 mol dm-3, caused the formation of COM and COD mixture at all temperatures. At the same conditions and in the magnetically stirred systems formation of COD, in a mixture with COT or COM, has been observed. The highest COD content in the mechanically stirred system was obtained at 45 °C and c i (Na3C6H5O7) = 0.001 mol dm-3 (w = 89.5%), while in the magnetically stirred system almost pure COD was obtained at 37 °C and c i (Na3C6H5O7) = 0.008 mol dm-3 (w = 96.5%).

Development of the quality assessment model of EHR software in family medicine practices: research based on user satisfaction.

BACKGROUND: Family medicine practices (FMPs) make the basis for the Croatian health care system. Use of electronic health record (EHR) software is mandatory and it plays an important role in running these practices, but important functional features still remain uneven and largely left to the will of the software developers. OBJECTIVE: The objective of this study was to develop a novel and comprehensive model for functional evaluation of the EHR software in FMPs, based on current world standards, models and projects, as well as on actual user satisfaction and requirements. METHODS: Based on previous theoretical and experimental research in this area, we made the initial framework model consisting of six basic categories as a base for online survey questionnaire. Family doctors assessed perceived software quality by using a five-point Likert-type scale. Using exploratory factor analysis and appropriate statistical methods over the collected data, the final optimal structure of the novel model was formed. Special attention was focused on the validity and quality of the novel model. RESULTS: The online survey collected a total of 384 cases. The obtained results indicate both the quality of the assessed software and the quality in use of the novel model. The intense ergonomic orientation of the novel measurement model was particularly emphasised. CONCLUSIONS: The resulting novel model is multiple validated, comprehensive and universal. It could be used to assess the user-perceived quality of almost all forms of the ambulatory EHR software and therefore useful to all stakeholders in this area of the health care informatisation.

Evidence of structural variability among synthetic and biogenic vaterite.

Recently, the results of experimental and theoretical investigations have revealed that, in vaterite, two or even more crystalline structures coexist. In this communication we report evidence of diverse vaterite structures in biogenic samples of different origin. In addition, it is shown that the synthetic vaterite precipitated in the presence of poly-l-aspartate has structures similar to those of biogenic samples.

Structural changes in a protein fragment from abalone shell during the precipitation of calcium carbonate.

Mineralized tissues grow through biologically controlled processes in which specific macromolecules are involved. Some of these molecules, which are present in very low concentrations and are difficult to localize and characterize, become entrapped inside the mineralized tissue. Herein, a protein fragment, GP, which was obtained by the alkaline digestion of the green sheet of the abalone shell, is used as a probe to study the changes in molecular structure that occur during the precipitation of calcium carbonate. This important goal was achieved by exploiting a fluorescent tag in GP. The experimental results that were obtained by using spectroscopic-, chromatographic-, and microscopic techniques indicate that GP controls the precipitation kinetics and morphology of calcium carbonate crystals, and that it only undergoes structural reorganization when entrapped inside calcium carbonate crystals. To the best of our knowledge, this report represents one of the first studies on the conformational changes of a protein fragment that is involved in biomineralization processes on moving from the solution phase into the mineral phase.

Interactions of salicylic acid derivatives with calcite crystals.

Investigation of basic interactions between the active pharmaceutical compounds and calcium carbonates is of great importance because of the possibility to use the carbonates as a mineral carrier in drug delivery systems. In this study the mode and extent of interactions of salicylic acid and its amino acid derivates, chosen as pharmaceutically relevant model compounds, with calcite crystals are described. Therefore, the crystal growth kinetics of well defined rhombohedral calcite seed crystals in the systems containing salicylic acid (SA), 5-amino salicylic acid (5-ASA), N-salicyloil-l-aspartic acid (N-Sal-Asp) or N-salicyloil-l-glutamic acid (N-Sal-Glu), were investigated. The precipitation systems were of relatively low initial supersaturation and of apparently neutral pH. The data on the crystal growth rate reductions in the presence of the applied salicylate molecules were analyzed by means of Cabrera & Vermileya's, and Kubota & Mullin's models of interactions of the dissolved additives and crystal surfaces. The crystal growth kinetic experiments were additionally supported with the appropriate electrokinetic, spectroscopic and adsorption measurements. The Langmuir adsorption constants were determined and they were found to be in a good correlation with values obtained from crystal growth kinetic analyses. The results indicated that salicylate molecules preferentially adsorb along the steps on the growing calcite surfaces. The values of average spacing between the adjacent salicylate adsorption active sites and the average distance between the neighboring adsorbed salicylate molecules were also estimated.

A methodology to assess experiences in implementing e-Health solutions in Croatian family medicine.

The central information system of primary health care of the Republic of Croatia is in an early stage of implementation which for now covers integration of all family doctors' offices into a single comprehensive eHealth network connecting their software solutions with the national payer institute and public health authority. Measuring the quality and efficiency of information systems at an early stage of development is a very difficult task. The main goal of this work is establishing the foundation for a formal methodology to measure and quantify the experience of family doctors in the current use of this system. A questionnaire has been created to support the work which, on one side carefully follows our assumptions for quality criteria, and on the other collects valuable input from the users of the technology and solutions implemented. Our work is closely aligned with worldwide accepted standards and recommendations carefully analyzed and localized to reflect the current environment and health policy. This paper presents some preliminary results based on the survey conducted with family doctors on the field.

Effects of initial supersaturation on spontaneous precipitation of calcium carbonate in the presence of charged poly-L-amino acids.

Spontaneous precipitation of calcium carbonate was investigated in two precipitation systems: (1) with initial supersaturation lower than that corresponding to the solubility of amorphous calcium carbonate (ACC), at which vaterite precipitated, and (2) with initial supersaturation higher than that of ACC solubility, at which a mixture of calcite and vaterite was formed. After the addition of an acidic polypeptide, poly-L-glutamic acid (pGlu) or poly-L-aspartic acid (pAsp), into (1) a significant inhibition of nucleation, expressed as an increase in induction time, and growth of vaterite, perceived as a dead zone, was observed. Extent of inhibition decreased in the order: Inh(pAps)>Inh(pGlu)>>Inh(pLys). The addition of a polypeptide into (2) caused the inhibition of precipitation and changed the morphology and polymorphic composition of the precipitate; only vaterite appeared at approximately c(pAsp)=3 ppm, c(pGlu)=6 ppm, or c(pLys)=7 ppm. This finding is explained as a consequence of kinetic constraints through the inhibition of calcite nucleation and stronger binding of acidic polypeptide by the calcite surfaces than by the vaterite surfaces. Laboratory precipitation studies using conditions that resemble those in living organism should be run at an initial supersaturation corresponding to the solubility of ACC as a limiting condition.

Precipitation of different calcite crystal morphologies in the presence of sodium stearate.

The influence of sodium stearate (NaSt) on the precipitation of calcium carbonate during the semicontinuous process of slaked lime carbonation was studied in the systems in which process parameters, like concentration of total dissolved calcium, temperature, CO(2) flow rate and initial addition rate of slaked lime, were controlled. It was found that calcite was the only calcium carbonate polymorph that appeared under the investigated experimental conditions, while FT-IR spectroscopy and thermogravimetric analysis of samples confirmed the presence of stearate on the surface of precipitated calcium carbonate (PCC). Specific surface area of PCC increased with increasing stearate content: the highest value, s = 52.8 m(2) g(-1), was obtained at t = 20 degrees C, c(tot) = 17.0 mmol dm(-3) and the stearate content of m(NaSt)/m(CaO) = 0.03. It was also found that hydrophobic calcite crystals in the form of rhombohedral and scalenohedral morphology can be produced at m(NaSt)/m(CaO) > 0.01. The exception is the case of nanosized PCC production, when much higher concentration of NaSt is needed, m(NaSt)/m(CaO) = 0.22. Minimal amount of stearate necessary to build up the monolayer and corresponding cross sectional area of one stearate molecule were estimated for the obtained calcite morphologies.

Kinetics of struvite to newberyite transformation in the precipitation system MgCl2-NH4H2PO4NaOH-H2O.

The influence of the initial reactant concentrations on the composition of the solid phases formed in the precipitation system MgCl(2)-NH(4)H(2)PO(4)-NaOH-H(2)O was investigated. The precipitation diagram constructed shows the approximate concentration regions within which struvite, newberyite, and their mixtures exist at 25 degrees C and an aging time of 60 min. It was found that immediately after mixing the reactant solutions, struvite (MgNH(4)PO(4).6H(2)O) precipitated in nearly the whole concentration area, while newberyite (MgHPO(4).3H(2)O) appeared mostly within the region of the excess of magnesium concentration. It was also found that after aging time of 60 min the precipitation domain of struvite alone is much broader than that of newberyite or the domain of their coexistence, and shows that struvite is more abundant in the systems in which the initial concentration of ammonium phosphate is higher than that of magnesium. The kinetics of struvite to newberyite transformation (conversion) was systematically studied under the conditions of different initial reactant concentrations and different initial pH in the systems in which a mixture of both phases precipitated spontaneously. The struvite to newberyite conversion period was found to be strongly related to the ratio of initial supersaturations, S(N)/S(S), rather than to the any particular physical quantity that can describe and predict the behavior of the precipitation system. Experimental data suggest a solution-mediated process as a most possible transformation mechanism. Along with a continuous monitoring of the changes in the liquid phase, the content of struvite in the solid phase was estimated by means of a Fourier transform infrared (FT-IR) method, developed for this particular precipitation system.

Effect of inorganic anions on the morphology and structure of magnesium calcite.

Calcium carbonate was precipitated from calcium hydroxide and carbonic acid solutions at 25 degrees C, with and without addition of different magnesium (MgSO(4), Mg(NO(3))(2) and MgCl(2)) and sodium salts (Na(2)SO(4), NaNO(3) and NaCl) of identical anions, in order to study the mode of incorporation of magnesium and inorganic anions and their effect on the morphology of calcite crystals over a range of initial reactant concentrations and limited c(i)(Mg(2+))/c(i)(Ca(2+)) molar ratios. The morphology, crystal size distribution, composition, structure, and specific surface area of the precipitated crystals, as well as the mode of cation and anion incorporation into the calcite crystal lattice, were studied by a combination of optical and scanning electron microscopy (SEM), electronic counting, a multiple BET method, thermogravimetry, FT-IR spectroscopy, X-ray diffraction (XRD), and electron paramagnetic resonance (EPR) spectroscopy. In the systems of high initial relative supersaturation, precipitation of an amorphous precursor phase preceded the formation of calcite, whereas in those of lower supersaturation calcite was the first and only polymorphic modification of calcium carbonate that appeared in the system. The magnesium content in calcite increased with the magnesium concentration in solution and was correlated with the type of magnesium salt used. Mg incorporation caused the formation of crystals elongated along the calcite c axis and, in some cases, the appearance of new [011] faces. Polycrystalline aggregates were formed when the c(i)(Mg(2+))/c(i)(Ca(2+)) molar ratios in solution were increased. Addition of sulfate ions, alone, caused formation of spherical calcite polycrystalline aggregates.