Magnetic water treatment-A review of the latest approaches.

Understanding of magnetic field (MF) effects observed during and after its action on water and aqueous solutions is still a controversial issue although the effects have been reported for at least half of century. The purpose of this paper was a brief review of the literature which deals with the magnetic force treatment effects. However, it is especially focused on the latest approaches, published mostly in the last decade which have developed our understanding of the mechanisms accompanying the field action. Generally, the changes in water structure via hydrogen bonding changes, as well as in intraclusters and between interclusters were taken into account, but the most remarkable progress was achieved in 2012 by Coey who applied the non-classical theory of nucleation mechanism of the formation of dynamically ordered liquid like oxyanion polymers (DOLLOP) to explain the magnetic field action. His criterion for the magnetic field effect to occur was experimentally verified. It was also proved that the gradient of the magnetic field is more important than the magnetic field strength itself. Some interesting approaches explaining an enhanced evaporation rate of water by MF are also discussed. More experimental results are needed for further verification of the DOLLOP theory to achieve a more profound understanding of the MF effects.

Synthesis of hydroxyapatite for biomedical applications.

The current need for long lasting implants and bone substitutes characterized by biocompatibility, bioactivity and mechanical properties, without the immune rejection is a great challenge for scientists. These bone substitute structures should be prepared for individual patients with all details controlled on the micrometer level. Similarly, nontoxic, biocompatible targeted drug delivery systems which allow controlling the rate and time period of the drug delivery and simultaneously eliminating toxic and side effects on the healthy tissues, are of great interest. Extensive attempts have been made to develop a simple, efficient, and green method to form biofunctional scaffolds and implant coatings possessing the above mentioned significant biocompatibility, bioactivity and mechanical strength. Moreover, that could also serve as drug delivery systems. Hydroxyapatite (HA) which is a major mineral component of vertebrate bones and teeth is an excellent material for these purposes. In this literature review the biologically inspired scaffolds, bone substitutes, implants characterized by mechanical strength and biocompatibility, as well the drug delivery systems, based on hydroxyapatite are discussed.

Surface properties of Ti-6Al-4V alloy part I: Surface roughness and apparent surface free energy.

Titanium (Ti) and its alloys are the most often used implants material in dental treatment and orthopedics. Topography and wettability of its surface play important role in film formation, protein adhesion, following osseointegration and even duration of inserted implant. In this paper, we prepared Ti-6Al-4V alloy samples using different smoothing and polishing materials as well the air plasma treatment, on which contact angles of water, formamide and diiodomethane were measured. Then the apparent surface free energy was calculated using four different approaches (CAH, LWAB, O-W and Neumann's Equation of State). From LWAB approach the components of surface free energy were obtained, which shed more light on the wetting properties of samples surface. The surface roughness of the prepared samples was investigated with the help of optical profilometer and AFM. It was interesting whether the surface roughness affects the apparent surface free energy. It was found that both polar interactions the electron donor parameter of the energy and the work of water adhesion increased with decreasing roughness of the surfaces. Moreover, short time plasma treatment (1min) caused decrease in the surface hydrophilic character, while longer time (10min) treatment caused significant increase in the polar interactions and the work of water adhesion. Although Ti-6Al-4V alloy has been investigated many times, to our knowledge, so far no paper has been published in which surface roughness and changes in the surface free energy of the alloy were compared in the quantitative way in such large extent. This novel approach deliver better knowledge about the surface properties of differently smoothed and polished samples which may be helpful to facilitate cell adhesion, proliferation and mineralization. Therefore the results obtained present also potentially practical meaning.

Properties of Langmuir and solid supported lipid films with sphingomyelin.

Biological cell membranes play a crucial role in various biological processes and their functionality to some extent is determined by the hydrophilic/hydrophobic balance. A significant progress in understanding the membrane structure was the discovery of laterally segregated lipid domains, called the lipid rafts. These raft domains are of ordered lamellar liquid-crystalline phase, while rest of the membrane exists in a relatively disordered lamellar liquid-crystalline phase. Moreover, the chemical constitution of the lipid rafts consists of a higher content (up to 50%) of cholesterol (Chol) and sphingomyelin (SM). Sphingomyelin also plays a significant role in the red cells of blood and nerves, in some diseases, as a precursor to ceramides, and other sphingolipid metabolites. In this paper properties of Langmuir and solid supported mixed lipid films of DPPC/SM, DOPC/SM, and Chol/SM are described. Special attention has been paid to wetting properties (hydrophobic/hydrophilic balance) of these films transferred onto a hydrophilic glass surface. To our knowledge such results have not yet been published in the literature. The properties were determined via contact angle measurements and then calculation of the films' apparent surface free energy. The films' wettability and their apparent surface free energy strongly depend on their composition. The energy is affected by both the structure of hydrocarbon chains of glycerophospholipids (DPPC and DOPC) and their interactions with SM. Properties of mixed Chol/SM monolayer depend also on the film stoichiometry. At a low Chol content (XChol=0.25) the interactions between SM and Chol are strong and hence the formation of binary complex is possible. This is accompanied by a decrease in the film surface free energy in comparison to that of pure SM monolayer, contrary to a higher Chol content where the monolayer energy increases. This suggests that cholesterol is excluded from the membrane thus increasing the film hydrophilicity. These results are consistent with the literature data and somehow confirm the hypothesis of lipid raft formation. The roughness of the investigated monolayer surfaces was also determined using optical profilometry. The roughness parameters of the DPPC, SM, and mixed DPPC/SM generally correlate with the changes of their apparent surface free energy, i.e. with the decreasing roughness the apparent surface free energy also decreases. However, this is not the case for mixed DOPC/SM monolayers. Although the roughness increases with SM content the apparent surface free energy decreases. Therefore some other factors, like the presence of unsaturated bonds in the DOPC molecule, influence the film phase state and the energy too. More experiments are needed to explain this hypothesis.

Comparison of contact angle hysteresis of different probe liquids on the same solid surface.

Advancing and receding contact angles of water, formamide and diiodomethane were measured on 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) layers deposited on three different solid supports-glass, mica and poly(methyl methacrylate). Up to five statistical monolayers were deposited on the surfaces by spreading DPPC solution. It was found that even on five statistical DPPC monolayers, the hysteresis of a given liquid depends on the kind of solid support. Also on the same solid support the contact angle hysteresis is different for each probe liquid used. The AFM images show that the heights of roughness of the DPPC films cannot be the primary cause of the observed hysteresis because the heights are too small to cause the observed hystereses. It is believed that the hysteresis is due to the liquid film present right behind the three-phase solid surface/liquid drop/gas (vapour) contact line and the presence of Derjaguin pressure. The value of contact angle hysteresis depends on both the solid surface and liquid properties as well as on intermolecular interactions between them.

Phenol adsorption on closed carbon nanotubes.

We present the results of systematic studies of phenol adsorption on closed commercially available, unmodified carbon nanotubes. Phenol adsorption is determined by the value of tube-specific surface area, the presence of small amount of surface groups influence adsorption only in very small amount. Phenol can be applied as a probe molecule for comparative analysis of tube surface areas. Tube curvature influences adsorption from solution, i.e., we observe increasing adsorption energy (and slower desorption process) with the decrease in tube curvature. This is in full accordance with molecular simulation results.

Surface modification of glass plates and silica particles by phospholipid adsorption.

The effect of phospholipid adsorption on the hydrophobicity of glass plates and on the surface charge of silica particles using contact angle and electrophoretic mobility measurements, respectively, was investigated. Deposition of successive statistical monolayers of dipalmitoylphosphatidylcholine (DPPC) on the glass surface showed zig-zag changes of water contact angle, especially on the first few monolayers. This behavior is qualitatively coherent with the oscillations observed in zeta potential values for increasing DPPC concentration. The results indicate that the phospholipid is adsorbed vertically on the plates, exposing alternately its polar head and non-polar hydrocarbon chains in successive layers. On the other hand, experiments conducted on glass plates prior hydrophobized by contact with n-tetradecane suggest that DPPC molecules may to some extent dissolve in the relatively thick n-alkane film and then expose their polar heads over the film surface thus producing polar electron-donor interactions. The effect of both DPPC and dioleoylphosphatidylcholine (DOPC) on the electrokinetic potential of silica spheres confirms adsorption of the phospholipids, leading to a decrease in the (originally negative) zeta potential of silica and even reversal of its sign to positive at acidic pH. Hydrophobic interactions between phospholipid molecules in the medium and those already adsorbed may explain the overcharging. The adsorption of neutral phospholipids may reduce the zeta potential as a consequence of the shift of the electrokinetic or slip plane. The effect is more evident in the case of DOPC, suggesting a less efficient packing of this phospholipid because of the presence of double bonds in its molecule, which in fact is well known.

Superhydrophilic and superwetting surfaces: definition and mechanisms of control.

The term superhydrophobicity was introduced in 1996 to describe water-repellent fractal surfaces, made of a hydrophobic material, on which water drops remain as almost perfect spheres and roll off such surfaces leaving no residue. Today, superhydrophobic surfaces are defined as textured materials (and coatings) on (nonsmooth) surfaces on which water forms contact angles 150° and larger, with only a few degrees of contact angle hysteresis (or sliding angle). The terms superhydrophilicity and superwetting were introduced a few years after the term superhydrophobicity to describe the complete spreading of water or liquid on substrates. The definition of superhydrophilic and superwetting substrates has not been clarified yet, and unrestricted use of these terms sometimes stirs controversy. This Letter briefly reviews the superwetting phenomenon and offers a suggestion on defining superhydrophilic and superwetting substrates and surfaces.

Surface free energy and topography of mixed lipid layers on mica.

The Langmuir-Blodgett/Schaefer (LB/LS) method, AFM technique and contact angle measurements were used to investigate the formation, structure and energetic properties of lipid films, which were constituted of single-component or binary systems formed by phospholipids: saturated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), unsaturated 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and triglyceride: glyceryl trioleate (GTO) or their mixture DPPC/DOPC and DPPC/GTO with a different DOPC or GTO molar ratio. The surface free energy and its components (apolar and polar interaction) for single and binary lipid mono- and bilayer systems were evaluated from the advancing and receding contact angles of water, formamide and diiodomethane, using two different models of interfacial interactions, namely, van Oss et al. (LWAB) and the contact angle hysteresis (CAH). The molecular structure of these layers was studied by means of atomic force microscopy (AFM). The thermodynamic analysis of the excess area and excess free energy of DPPC/DOPC mixture indicated that lateral phase separation took place for these two components. The AFM images also confirmed the phase separation, which was visualized as condensed DPPC-rich domains and a fluid DOPC matrix. Saturated DPPC mono- and bilayers exhibited much lower surface free energy than unsaturated DOPC ones, probably due to the differences in the packing of molecules. In the DPPC/DOPC mixed layers the energy increased with increasing mole fraction of DOPC in the layer. For DPPC/GTO layers a similar trend in the energy changes as a function of GTO amount was observed. These studies provided a fundamental framework for better understanding of the interactions occurring in the used lipid systems.

Effect of temperature on n-tetradecane emulsion in the presence of phospholipid DPPC and enzyme lipase or phospholipase A2.

Zeta potentials and effective diameters of n-tetradecane emulsions in 1 M ethanol were investigated in the presence of 1,2-dipalmitoyl- sn-glycero-3-phosphocholine (DPPC) (1 mg/100 mL), Candida cylindracea lipase (CCL), and phospholipase PLA2 (1 mg/100 mL) at 20, 37, and 45 degrees C. The enzyme was added at the beginning of mechanical emulsion homogenization or 1 min before the end of stirring for 10 min at 10,000 rpm. It was found that DPPC decreases the negative zeta potentials at all three temperatures. The decrease was largest at 20 degrees C and smallest at 45 degrees C. The influence of the enzymes on the zeta potentials depended on the enzyme kind, time of its injection, and temperature. More negative values of the zeta potentials relative to n-C14H30/DPPC droplets were obtained if the lipase was present. Generally, the effective diameters correlate with the zeta potentials, i.e., lower zeta potential corresponds with bigger effective diameter. Possible reasons for the observed changes of the measured parameters are discussed.

Surface free energy of sulfur--revisited I. Yellow and orange samples solidified against glass surface.

Surface free energy of two different samples of solidified sulfur (yellow and orange) was investigated, using several approaches for its determination. It was found that values determined about two decades ago for surface free energy of sulfur were overestimated. From current studies the apparent value of this energy ranges between 30 and 60 mJ/m(2), depending on the kind and age of the sulfur samples (up to 1 year old) and/or the probe liquid used for the advancing and receding contact angle measurements. The energy has been calculated from van Oss et al.'s approach (Lifshitz-van der Walls, electron-donor, and electron-acceptor components), the contact angle hysteresis approach proposed by Chibowski, the equation of Owens and Wendt (dispersion and polar components), and Neumann et al.'s equation of state, as well as from equilibrium contact angle using Tadmor's procedure. The lowest values of the energy for 3-day- and 3-month-old samples of sulfur were calculated from the equation of state; they were below the range mentioned above.

Surface free energy of sulfur--revisited II. Samples solidified against different solid surfaces.

The apparent surface free energy of yellow and orange samples of sulfur crystallized at the surface of gold, silicon, and Teflon and in air was evaluated from the advancing and receding contact angles of water. The samples were prepared by casting melted rhombic mineralogical specimen sulfur onto the surface of the above-noted solids. Yellow samples were obtained when just melted sulfur (ca. 120 degrees C) was cast onto the surfaces, and the orange ones, when the melted sulfur was heated longer to a higher temperature (ca. 160 degrees C) and then cast onto the surfaces. The obtained results show that the apparent surface free energy depends on which surface it crystallized. The greatest value is for the sample crystallized at the gold surface, which is 35% higher than that crystallized in air. Generally, the surface free energy of orange samples is slightly higher than that of yellow ones. It is believed that the differences in the energy result from changes in the packing and structural orientation of sulfur atoms on the surfaces.

Effects of a static magnetic field on water and electrolyte solutions.

Water and electrolyte solutions were exposed for 5 min to a weak static magnetic field (B = 15 mT). Their conductivity and the amount of evaporated water were then measured as a function of time. Simultaneously, these quantities were determined for magnetically untreated samples, as reference systems. It was found that a magnetic field influences these two parameters and their changes depend on the thermodynamic functions of hydration of these ions. A roughly linear change in conductivity versus 'scaled' functions was obtained. On this basis it was concluded that the magnetic field causes changes in the hydration shells of the ions.

Wettability and topography of phospholipid DPPC multilayers deposited by spin-coating on glass, silicon, and mica slides.

The surface free energy of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) layers deposited on glass, silicon, or mica by the spin-coating method was estimated. For this purpose, the advancing and receding contact angles of water, formamide, and diiodomethane were measured, and then two concepts of the interfacial interactions were applied. In the contact angle hysteresis approach, the apparent total surface free energy is calculated from the advancing and receding contact angles of the probe liquids, and in the Lifshitz-van der Waals/acid-base approach, the total surface free energy is calculated from previously determined components of the energy, that is, the apolar Lifshitz-van der Waals and the polar electron-donor and electron-acceptor, which are calculated from the advancing contact angles of the probe liquids alone. Comparison of the results obtained using these two approaches provided more information about changes in the hydrophobic/hydrophilic character of the DPPC layers and, simultaneously, a verification of the approaches. Moreover, the roughness and topography of the investigated layers were also examined by atomic force microscopy measurements. The hydrophilic character of the DPPC layers decreased if up to 0.5 mg of DPPC/mL was used to deposit on the substrates by the spin-coating method. Then it increased and leveled off if up to 2-2.5 mg of DPPC/mL was used. The changes in the energy were correlated with the changes in topography of the surfaces.

On some relations between advancing, receding and Young's contact angles.

Problems of experimental determination and theoretical verification of equilibrium contact angles are discussed basing on the literature data. A relationship between the advancing and receding contact angles versus the equilibrium contact angle is described and then verified using the literature contact angles determined on paraffin wax and polypropylene. Using the proposed relationship and experimentally determined equilibrium contact angles, obtained by plotting the advancing and receding contact angles versus the contact angle hysteresis or by applying vibration of the system liquid drop/solid surface, it is found that the same value of the surface free energy for paraffin wax is calculated from the contact angles of water and ethylene glycol. However, in the case of polypropylene some inconsistency appears between the equilibrium contact angles of the probe liquid used and the calculated surface free energy. More experimental data of the equilibrium contact angle are needed to verify further the relationship.

Topography and surface free energy of DPPC layers deposited on a glass, mica, or PMMA support.

An investigation of energetic properties of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) layers deposited on glass, mica, and PMMA (poly(methyl methacrylate)) surfaces was carried out by means of contact angles measurements (advancing and receding) for three probe liquids (diiodomethane, water, and formamide). DPPC was deposited on the surfaces from water (on glass and mica) or methanol (on PMMA) solutions. The topography of the tested surfaces was determined with a help of scanning electron microscopy (SEM) and atomic force microscopy (AFM). Using the measured contact angles, the total apparent surface free energy and its components of the studied layers were determined from van Oss et al.'s (Lifshitz-van der Waals and acid-base components, LWAB) and contact angle hysteresis (CAH) approaches. It allowed us to learn about changes in the surface free energy of the layers (hydrophobicity/hydrophilicity) depending on their number and kind of support. It was found that the changes in the energy greatly depended on the surface properties of the substrate as well as the statistical number of monolayers of DPPC. However, principal changes took place for first three monolayers.

Investigation of the electrokinetic properties of paraffin suspension. 2. In cationic and anionic surfactant solutions.

Electrical phenomena at nonionogenic hydrophobic surfaces (solid or liquid) in water, electrolyte, and/or surfactant solutions still attract research. In part 1 of this paper we described the electrokinetic behavior of paraffin wax suspension in water and electrolyte solutions (NaCl or LaCl3). On the basis of the latest data of water structure near hydrophobic surfaces it was concluded that immobilized water dipoles at the interface can play an essential role in the zeta potential formation. In this paper were investigated the zeta potentials of paraffin wax in cationic surfactants cetyltrimethylammonium bromide, C16H33(CH3)3NBr, and octadecyltrimethylammonium chloride, C18H37(CH3)3NCl, and anionic surfactant sodium dodecyl sulfate, C12H25SO4Na. Also changes in wettability of the paraffin surface due to the surfactant's adsorption were studied via wetting contact angle measurements and calculation of the surface free energy. It was concluded that at a low surfactant concentration (10(-6) M) the water dipole structure still contributes to the zeta potential, but at a higher one the zeta potential is determined by the surfactant molecules' adsorption. A special role of OH- ions is also clearly seen. Moreover, a functional relationship was found between the surface free energy of the surfactant-covered paraffin surface and the zeta potential.

Influence of sodium dodecyl sulfate and static magnetic field on the properties of freshly precipitated calcium carbonate.

Properties of calcium carbonate precipitated from aqueous solutions of CaCl(2) and Na(2)CO(3) in the presence of sodium dodecyl sulfate (SDS) and S-S 0.1 T magnetic field (MF) were studied. The nucleation and precipitation processes of CaCO(3) were investigated by pH and zeta potential measurements at 20 +/- 1 degrees C up to 2 h after mixing the solutions. Also the amounts of calcium carbonate deposited on the glass surfaces and its structure were examined. It was found that SDS influences the kinetics of precipitation, crystallographic forms, and crystal size of CaCO(3). The SDS effects are more pronounced in MF presence. A small amount of SDS accelerates transformation of vaterite into calcite, whereas increasing surfactant concentration moderates such a transformation. On the other hand, in all the systems, MF in the presence of SDS causes a slower transformation of vaterite into calcite. These effects are reflected in pH and zeta potential changes, although there is no clear dependence between the SDS amount present during the precipitation and changes of the parameters investigated. It seems that MF effect is most significant at a defined optimal SDS concentration. The results, however, do not allow suggestion of any detailed mechanism of the field interaction.

Investigation of the electrokinetic properties of paraffin suspension. 1. In inorganic electrolyte solutions.

Although electrical properties of nonionogenic hydrophobic surface (solid or liquid) in water and/or electrolyte solutions have been studied for many decades, they are still not well recognized, especially as for the nature of the charge and potential origin. Similarly, water structure at such a surface is still extensively studied. One such system is paraffin wax/water (electrolyte). The zeta potentials and the particle diameters of this system were investigated in this paper. To obtain the suspension of paraffin in water or electrolyte solution (NaCl or LaCl3), the mixture was heated to ca. 70 degrees C and then stirred during cooling. For thus obtained suspensions, the zeta potential was determined as a function of time at 20 degrees C. Also the pH effect on the zeta potentials was investigated. The zeta potentials were calculated from Henry's equation. The results obtained by us are in agreement with those obtained earlier by others. They confirm that although H+/OH- are not surface charge creating ions, OH- ions to some extent are zeta potential determining for the paraffin surface. By use of the potentials and diameters, the electric charge for a spherical particle in the shear plane was calculated. These values are small in the range of 10(-3) C/m2. On the basis of the findings of water structure near hydrophobic surface and the calculated charges, it is concluded that in fact the potential may be created by immobilized and oriented water dipoles.

Surface free energy and wettability of silyl layers on silicon determined from contact angle hysteresis.

Using the literature data of the advancing and receding contact angles for water, diiodomethane and hexadecane measured on various hydrophobic silyl layers (mostly monolayers) produced on silicon wafers the apparent surface free energies gamma(s)(tot) were calculated by applying new model of the contact angle hysteresis interpretation. It was found that, for the same silyl layer, the calculated gamma(s)(tot) values to some degree depended on the probe liquid used. Therefore, thus calculated the surface free energies should be considered as apparent ones. Moreover, also the values of the dispersion component gamma(s)(d) of these layers depend on the probe liquid used, but to a less degree. This must be due to the strength of the force field originating from the probe liquid and the spacing between the interacting molecules. The relationships between gamma(s)(tot) and gamma(s)(d) are discussed on the basis of the equations derived. It may be postulated that applying proposed model of the contact angle hysteresis and calculating the apparent total surface free energies and the dispersion contributions better insight into wetting properties of the silyled silicon surface can be achieved.