Reproducibility of inverse gas chromatography under infinite dilution: Results and interpretations of an interlaboratory study.

Over the last years, inverse gas chromatography (IGC) proved to be a versatile and sensitive analytical technique for physicochemical properties. However, the comparability of results obtained by different users and devices remains a topic for debate. This is the first time, an interlaboratory study using different types of IGC instruments is reported. Eight organizations with different IGC devices defined a common lab measurement protocol to analyse two standard materials, silica and lactose. All data was collected in a standard result form and has been treated identically with the objective to identify experimentally observed differences and not potentially different data treatments. The calculated values of the dispersive surface energy vary quite significantly (silica: 22 mJ/m2 - 34 mJ/m2, lactose 37 mJ/m2 - 51 mJ/m2) and so do the ISP values and retention volumes for both materials. This points towards significant and seemingly undiscovered differences in the operation of the instruments and the obtained underlying primary data, even under the premise of standard conditions. Variations are independent of the instrument type and uncertainties in flow rates or the injected quantities of probe molecules may be potential factors for the differences. This interlaboratory study demonstrates that the IGC is a very sensitive analytical tool, which detects minor changes, but it also shows that for a proper comparison, the measurement conditions have to be checked with great care. A publicly available standard protocol and material, for which this study can be seen as a starting point, is still needed to judge on the measurements and the resulting parameters more objectively.

Preparation of Thin Films Containing Modified Hydroxyapatite Particles and Phospholipids (DPPC) for Improved Properties of Biomaterials.

The main aims of thin biofilm synthesis are to either achieve a new form to promote the transport of drugs in oral delivery systems or as a coating to improve the biocompatibility of the implant's surface. In this study, the Langmuir monolayer technique was employed to obtain films containing Mg-doped hydroxyapatite with 0.5%, 1.0%, and 1.5% Mg(II). The obtained modified HA particles were analysed via the FT-IR, XRD, DLS, and SEM methods. It was shown that the modified hydroxyapatite particles were able to form thin films at the air/water interface. BAM microscopy was employed to characterized the morphology of these films. In the next step, the mixed films were prepared using phospholipid (DPPC) molecules and modified hydroxyapatite particles (HA-Mg(II)). We expected that the presence of phospholipids (DPPC) in thin films improved the biocompatibility of the preparing films, while adding HA-Mg(II) particles will promote antibacterial properties and enhance osteogenesis processes. The films were prepared in two ways: (1) by mixing DPPC and HA-Mg (II) and spreading this solution onto the subphase, or (2) by forming DPPC films, dropping the HA-Mg (II) dispersion onto the phospholipid monolayer. Based on the obtained π-A isotherms, the surface parameters of the achieved thin films were estimated. It was observed that the HA-Mg(II) films can be stabilized with phospholipid molecules, and a more stable structure was obtained from films synthesied via method (2).

Estimation of Stiffness of Non-Cohesive Soil in Natural State and Improved by Fiber and/or Cement Addition under Different Load Conditions.

The aim of this study was to compare the stiffness of gravelly sand under various load conditions-static conditions using the CBR test and cyclic conditions using the resilient modulus test. The tests were conducted on natural soil and soil improved by the addition of polypropylene fibers and/or 1.5% cement. The impacts of the compaction and curing time of the stabilized samples were also determined. The soil was sheared during the Mr tests, even after fiber reinforcement, so the resilient modulus value for the unbound sand could not be obtained. The cement addition improved Mr, and the curing time also had an impact on this parameter. The fiber addition increased the value of the resilient modulus. The CBR value of the compacted gravelly sand was relatively high. It increased after adding 0.1% fibers in the case of the standard compacted samples. The greater fiber addition lowered the CBR value. For the modified compacted samples, each addition of fibers reduced the CBR value reduced the CBR value. The addition of cement influenced the CBR increase, which was also affected by the compaction method and the curing time. The addition of fibers to the stabilized sample improved the CBR value. The relationship Mr=f(CBR) obtained for all data sets was statistically significant but characterized by a large error of estimate.

Chitosan - zeolite scaffold as a potential biomaterial in the controlled release of drugs for osteoporosis.

Chitosan scaffolds are a potential material in many biomedical applications. A particularly interesting application is their use in bone tissue engineering. Because of their biocompatibility and nontoxicity, they are an ideal material for this application. What is missing from chitosan scaffolds is controlled drug release. They can obtain this property by adding drug carriers. In this work, chitosan­calcium zeolite scaffolds were prepared and used in the controlled release of the drug for osteoporosis - risedronate. Their properties have been compared with those of the popular chitosan-hydroxyapatite scaffold. The zeolite was evenly distributed throughout the scaffold. More drug was retained on the scaffold with the addition of zeolite compared to that with the hydroxyapatite. The new scaffolds have proven to be able to retain the drug and slowly release it in small doses. The results obtained are promising and show great potential for this material in bone tissue engineering.

Tensile Strength of Class F Fly Ash and Fly Ash with Bentonite Addition as a Material for Earth Structures.

The behavior of soils under tensile stress is of interest to geotechnical engineers. Tensile strength of soils is often associated with tensile fractures that can generate a privileged flow path. The addition of bentonite improves the plastic properties of the soil, therefore the study was conducted for the compacted class F fly ash and fly ash with various bentonite additions. An amount of bentonite was: 5, 10 and 15%, calculated in weight relation to dry mass of samples. The tensile strength of compacted clay was also established, for comparison. Laboratory tests were carried out using the direct method (breaking) on cylindrical samples and the indirect method (the Brazilian test) on disc-shaped specimens. For this purpose, a universal testing machine with a frame load range of ±1 kN was used. It is stated that bentonite considerably influences the tensile strength of the fly ash evaluated with both methods. The tensile strength values obtained with the Brazilian method are comparable or higher than those obtained with the direct method. The achieved tensile strength values of compacted fly ash, improved by 10-15% of bentonite addition, are comparable with the results obtained for clay used in mineral sealing, while the strain at maximum tensile strength is similar in the direct test and lower in the indirect test.

Resilient Response of Cement-Treated Coarse Post-Glacial Soil to Cyclic Load.

Stabilisation with cement is an effective way to increase the stiffness of base and subbase layers and to improve the rutting of subgrade. The aim of the study is to investigate the effect of different percentages of cement additives (1.5%, 3.0%, 4.5% and 6.0%) on the resilient modulus of coarse-grained soil used on road foundations. The influence of the compaction method, the standard Proctor and the modified Proctor, as well as the sample curing time is analysed. The cement addition significantly increases the resilient modulus and reduces the resilient axial strain. Extending the curing time from 7 to 28 days also improves the resilient modulus. The change in the compaction energy from standard to modified does not increase the resilient modulus of the stabilised gravelly sand due to its compaction characteristics. The test results of the resilient modulus of the gravelly sand stabilised with cement indicate the possibility of using it as a material for the road base and subbase due to meeting the AASHTO requirements. However, the non-stabilised gravelly sand does not meet the above requirements. It has been sheared during cyclic tests at the first load sequence, regardless of the compaction method.

Characteristics of Compacted Fly Ash as a Transitional Soil.

Cohesive and non-cohesive soils show a number of properties typical of a given category. Cohesive soils are characterized by cohesion, and the properties of compacted soils closely depend on moisture at compaction. However, many researchers have found the existence of so-called mixed or transitional soils. Compacted transitional soils, macroscopically recognized as non-cohesive, are characterized by mechanical properties and hydraulic conductivity which are strictly dependent on the moisture content at compaction. The aim of this work is to show the influence of the content of fine particles in fly ash on the variation of California Bearing Ratio (CBR) values as a parameter strictly dependent on initial compaction. The CBR values were interpreted in terms of moisture at compaction, void ratio and intergranular void ratio. Three different research samples were selected with fine contents of 45%, 55% and 70%; all samples corresponded in terms of grading with sandy silt. Fly ash containing only non-plastic fines behaved as cohesive soils despite the lack of plasticity. The CBR values decreased with increasing moisture at compaction or void ratio. The CBR values, plotted as a function of the intergranular void ratio, have lower penetration resistance together with fine content.

Quantifying non-specific interactions via liquid chromatography.

Determinations of solute-cosolute interactions from chromatography have often resulted in problems, such as the "antibinding" (or a negative binding constant) between the solute and micelle in micellar liquid chromatography (MLC) or indeterminacy of salt-ligand binding strength in high-performance affinity chromatography (HPAC). This shows that the stoichiometric binding models adopted in many chromatographic analyses cannot capture the non-specific nature of solvation interactions. In contrast, an approach using statistical thermodynamics handles these complexities without such problems and directly links chromatographic data to, for example, solubility data via a universal framework based on Kirkwood-Buff integrals (KBI) of the radial distribution functions. The chromatographic measurements can now be interpreted within this universal theoretical framework that has been used to rationalize small solute solubility, biomolecular stability, binding, aggregation and gelation. In particular, KBI analysis identifies key solute-cosolute interactions, including excluded volume effects. We present (i) how KBI can be obtained directly from the cosolute concentration dependence of the distribution coefficient, (ii) how the classical binding model, when used solely as a fitting model, can yield the KBIs directly from the literature data, and (iii) how chromatography and solubility measurements can be compared in the unified theoretical framework provided via KBIs without any arbitrary assumptions about the stationary phase. To perform our own analyses on multiple datasets we have used an "app". To aid readers' understanding and to allow analyses of their own datasets, the app is provided with many datasets and is freely available on-line as an open-source resource.

The Physicochemical Characteristics of Prosthetic Materials and Their Influence on Their Clinical Properties.

The use of elastic materials favours degradation of their surface. The period of their clinical usefulness is then shortened, and their further utilisation in the oral cavity may have the reverse effect. The surface properties of such material as well as the influence of the humidity on their surface are very important as they determine the prosthetic materials behavior in the mouth. The surface of such material should be resistant to water. Inverse gas chromatography is an accurate, sensitive technique for studying surface properties. Thanks to using a unique equipment specially designed for IGC technique, Surface Energy Analyzer, it was possible to characterize the surface at 0 and 80% of humidity. Our results show that increased humidity does not affect surface properties of studied prosthetic materials. Their ability to dispersive and specific interactions change in very limited degree. IGC experiment was also applied for the estimation of Hansen solubility parameters that indicate ability of a material to dispersive, polar, and hydrogen-bonding interactions. Relation between the surface characteristics and practical use of soft lining materials with implications for their clinical usefulness is also discussed.

Inverse liquid chromatography as a tool for characterisation of the surface layer of ceramic biomaterials.

The novel technique for ceramic biomaterials surface characterisation was proposed. The examined bone substitute materials were two orthophosphates: hydroxyapatite, ß-tricalcium phosphate and the mixture of these two - biphasic calcium phosphate. The aim of this work was characterisation of the ceramic biomaterials surface expressed via the values of parameters e, s, a, b, v considered in linear free energy relationship. The values of these parameters reflect the ability of stationary phase to occur in different types of interactions. The sorption phenomena occurring on the bone substitute materials surface are responsible for the process of the multiplication of the osteoblasts. Thus the detailed description of this phenomena may contribute to the better understanding of bone loss regeneration mechanism. The data required for characterisation by using LFER model was collected by means of inverse liquid chromatography with the use of five different mobile phases: 98% ethanol, ethanol/water (50/50), water, 0.2M NaCl and SBF. The determination of the ceramic orthophosphates surface properties in SBF solution allowed to observe the behaviour of biomaterials in "natural environment" - in living organism.

Application of Inverse Liquid Chromatography for Surface Characterization of Biomaterials.

In the present study, a novel approach for surface characterization of ceramic biomaterials is proposed. Two ceramic biomaterials-hydroxyapatite and ß-tricalcium phosphate-were examined by means of inverse liquid chromatography. The Abraham LFER model was applied for physicochemical characteristics of the surface. Different compounds, characterized by different polarity and different donor-acceptor properties of functional group, were used as test solutes. The chromatographic experiments were carried out with two compositions of the mobile phase: pure acetonitrile (MeCN) and the mixture of acetonitrile and water in 80:20 ratio (MeCN/H2O). Thus, the influence of mobile phase on sorption properties of hydroxyapatite and tricalcium phosphate surface was also discussed.

Characterization of ceramic hydroxyapatite surface by inverse liquid chromatography in aquatic systems.

The novel approach for hydroxyapatite (HA) surface characterization was proposed. The main aim of this investigation was to estimate surface properties of HA as a biomaterial in real system i.e. in simulated body fluid (SBF). One of the method, which might be used to reflect the influence of liquid environment on sorption properties of material being surrounded by this liquid, is called inverse liquid chromatography (ILC). The lowercase letters of LFER equation (e, s, a, b, v) served for this characterization. The sorption abilities of examined material were also estimated for two different aqueous mobile phases: deionized water and water solution of 0.1M Na2HPO4. It enabled to observe the change in physiochemical properties of surface, considered in Abraham model, dependence on ions concentration in the mobile phase. Moreover pH of every aquatic solution, normally about 7, was adjusted to 5.5 and 9 to observe the influence of hydrogen and hydroxyl ions concentration on HA sorption properties.

Solubility parameter used to predict the effectiveness of monolithic in-needle extraction (MINE) device for the direct analysis of liquid samples.

The sorbent/eluent systems combined from three macroporous poly(styrene-divinylbenzene) (PS-DVB) monoliths and four solvents as eluents were used for the extraction of phenol, 4-chlorophenol and p-benzochinon from water samples. Monolithic in-needle extraction (MINE) devices were used in the preparation of a series of test water samples for chromatographic analysis. The extraction of phenolic compounds from water samples was carried out by pumping liquid samples through the MINE device. Solubility parameter concept was applied for estimation of effectiveness of MINE. Solubility parameters for (PS-DVB) monoliths were determined according to Small, considering different molar fraction of the monomers used for synthesis. Effectiveness of these systems was estimated according to difference of solubility parameter value in analyte/sorbent, sorbent/eluent, analyte/eluent pairs. The procedure enabling easy prediction of, e.g. the strength of the interactions between the analyte and sorbent, eluent efficiency or the extraction efficiency in MINE system was proposed.

Characterization of surface of trifluorophenylketoiminepropyl stationary phase coated porous layer open tubular columns.

A series of 3 fluorinated adsorbents were prepared by bonding 4,4,4-trifluoro-1-phenyl-1,3-ketoiminepropyl silane onto 5µm Nucleosil silica. The first one contained sole fluoroketoimine groups, while the other two adsorbents were derivatives of the first one with copper(II) chloride and copper(II) acetylacetonate bound through the fluoroketoimine groups. A description of syntheses of these adsorbents is given and the course of each stage of the syntheses is characterized by elemental analysis, surface area determination, UV-vis, EPR, ICP-OES, IR, (29)Si NMR, (13)C NMR and thermogravimetric analysis. For the columns coated with the adsorbents obtained the donor-acceptor character of the adsorption layer was established and the enthalpy of adsorption was determined for a selected group of hydrocarbons. The evenness of capillary column walls coating and mechanical stability of the stationary phases was evaluated on the basis of the flow restriction factor and SEM images. Efficiency of the columns obtained and their comparison with commercial counterparts are presented.

[Artichoke--herbal drug]. / Karczoch zwyczajny--lek roslinny.

The liver is the gland most vulnerable to the toxic effects of xenobiotics, as responsible for their metabolism. Significant impact on the functioning of this gland has a style of life: alcohol consumption, diet with high fats ingredients and prooxidative substances and synthetic drugs. Very improtant aspect in herbal medicaments is protective properties on parenchymal organ-damaging. Concomitant intake of plant extracts containing cytoprotective compounds, may increase the efficacy of treatment and reduce side effects. One of the plants of the hepatoprotective action is artichoke (Cynara scolymus L.). Artichoke with multiple therapeutic properties and practically no side effects is recommended not only in disorders of the liver, but also in the prevention of atherosclerosis and hyperlipidemia or dyspeptic disorders.

Inverse gas chromatography as a source of physiochemical data.

Inverse gas chromatography (IGC) is presented as a useful method for the examination of physicochemical properties of various materials. The advantages of IGC are presented. However, the uncertainties and sources of possible errors are also indicated and discussed.

Laboratory compaction of fly ash and fly ash with cement additions.

The use of power-industry wastes as a material for earthen structures depends on its compactibility. It has been confirmed that a fly ash/bottom ash mix compacted several times in Proctor's moulds are not representative. The relationship between dry density of solid particles and water content for re-used waste samples was determined. The re-compaction effect on grain-size distribution, density of solid particles, specific surface and sand equivalent of wastes was investigated. Tests were conducted on fly ash samples compacted by the Standard and Modified Proctor methods. Another aim of the paper was to investigate the influence of cement additions on the compactibility of a fly ash/bottom ash mix. Waste samples in the natural state and with different percentages of cement additions (2, 5 and 10%) were compacted by both impact compaction methods to obtain compactibility curves rhod(w). It was found that cement addition resulted in an increased rhod max value, while wopt decreased. Linear regression relationships for changes in compaction parameters after cement stabilisation are also given.

Selection of solubility parameters for characterization of pharmaceutical excipients.

The solubility parameter (delta(2)), corrected solubility parameter (delta(T)) and its components (delta(d), delta(p), delta(h)) were determined for series of pharmaceutical excipients by using inverse gas chromatography (IGC). Principal component analysis (PCA) was applied for the selection of the solubility parameters which assure the complete characterization of examined materials. Application of PCA suggests that complete description of examined materials is achieved with four solubility parameters, i.e. delta(2) and Hansen solubility parameters (delta(d), delta(p), delta(h)). Selection of the excipients through PCA of their solubility parameters data can be used for prediction of their behavior in a multi-component system, e.g. for selection of the best materials to form stable pharmaceutical liquid mixtures or stable coating formulation.

Hansen solubility parameters for polyethylene glycols by inverse gas chromatography.

Inverse gas chromatography (IGC) has been applied to determine solubility parameter and its components for nonionic surfactants--polyethylene glycols (PEG) of different molecular weight. Flory-Huggins interaction parameter (chi) and solubility parameter (delta(2)) were calculated according to DiPaola-Baranyi and Guillet method from experimentally collected retention data for the series of carefully selected test solutes. The Hansen's three-dimensional solubility parameters concept was applied to determine components (delta(d), delta(p), delta(h)) of corrected solubility parameter (delta(T)). The molecular weight and temperature of measurement influence the solubility parameter data, estimated from the slope, intercept and total solubility parameter. The solubility parameters calculated from the intercept are lower than those calculated from the slope. Temperature and structural dependences of the entopic factor (chi(S)) are presented and discussed.

A novel framework for sib pair linkage analysis.

Sib pair linkage analysis of a dichotomous trait is a popular method for narrowing the search for genes that influence complex diseases. Although the pedigree structures are uncomplicated and the underlying genetic principles straightforward, a surprising degree of complexity is involved in implementing a sib pair study and interpreting the results. Ascertainment may be based on affected, discordant, or unaffected sib pairs, as well as on pairs defined by threshold values for quantitative traits, such as extreme discordant sib pairs. To optimize power, various domain restrictions and null hypotheses have been proposed for each of these designs, yielding a wide array of choices for the analyst. To begin, we systematically classify the major sources of discretion in sib pair linkage analysis. Then, we extend the work of Kruglyak and Lander (1995), to bring the various forms into a unified framework and to facilitate a more general approach to the analysis. Finally, we describe a new, freely available computer program, Splat (Sib Pair Linkage Analysis Testing), that can perform any sib pair statistical test currently in use, as well as any user-defined test yet to be proposed. Splat uses the expectation maximization algorithm to calculate maximum-likelihood estimates of sharing (subject to user-specified conditions) and then plots LOD scores versus chromosomal position. It includes a novel grid-scanning capability that enables simultaneous visualization of multiple test statistics. This can lead to further insight into the genetic basis of the disease process under consideration. In addition, phenotype definitions can be modified without the recalculation of inheritance vectors, thereby providing considerable flexibility for exploratory analysis. The application of Splat will be illustrated with data from studies on the genetics of diabetic nephropathy.