Length-Scale Dependence of Hydration Free Energy: Effect of Solute Charge

Size and curvature are important determinants of particle wettability, in addition to surface chemistry and texture. Hydration free energy of a nonpolar solute scales with volume for small solutes and with surface area for larger ones. If the solute acquires a surface charge, the scaling regimes can be affected, with size-dependence of the charge playing a critical role. For isolated particles grown at fixed surface charge density, the Born approximation gives scaling of hydration free energy with volume. We consider a distinctly different but practically important scenario, where the charged solute and surrounding counterions are dissolved together. For this process, our molecular simulations demonstrate the electrostatic contribution to the solvation free energy, calculated per unit area of the solute, to be virtually independent of solute size. We explain this behavior in terms of counterion shielding effect on the curvature-dependent solute energy in the dehydrated state, an effect closely balanced by the influence of dielectric screening in water. As a result, for moderate surface charge densities of the solute, the net electrostatic contribution is dominated by counterion solvation, and scales with solute surface area independently of the ionic strength in the solution.     

Orientational correlations in liquid acetone and dimethyl sulfoxide: a comparative study

The structure of acetone and dimethyl sulfoxide in the liquid state is investigated using a combination of neutron diffraction measurements and empirical potential structure refinement (EPSR) modeling. By extracting the orientational correlations from the EPSR model, the alignment of dipoles in both fluids is identified. At short distances the dipoles or neighboring molecules are found to be in antiparallel configurations, but further out the molecules tend to be aligned predominately as head to tail in the manner of dipolar ordering. The distribution of these orientations in space around a central molecule is strongly influenced by the underlying symmetry of the central molecule. In both liquids there is evidence for weak methyl hydrogen to oxygen intermolecular contacts, though these probably do not constitute hydrogen bonds as such.     

The influence of enhanced UV-B radiation on Batrachium trichophyllum and Potamogeton alpinus -- aquatic macrophytes with amphibious character

The responses of two amphibious species, Batrachium trichophyllum and Potamogeton alpinus to different UV-B environments were studied. Plant material from natural environments, as well as from outdoor treatments was examined. In long-term outdoor experiments plants were grown under three different levels of UV-B radiation: reduced and ambient UV-B levels, and a UV-B level simulating 17% ozone depletion. The following parameters were monitored: contents of total methanol soluble UV-absorbing compounds and chlorophyll a, terminal electron transport system (ETS) activity and optimal and effective quantum yield of photosystem II. No effect of the different UV-B levels on the measured parameters was observed. The amount of UV-B absorbing compounds seems to be saturated, since no differences were observed between treatments and no increase was found in peak season, when natural UV-B levels were the highest. Physiological measurements revealed no harmful effects; neither on potential and actual photochemical efficiency, nor on terminal ETS activity. The contents of UV-B absorbing compounds were examined also in plant material sampled in low and high altitude environments during the growth season. Both species exhibited no seasonal dynamics of production of UV-absorbing compounds. The contents were variable and showed no significant differences between high and low altitude populations.     

Oxidation of AISI 304L stainless steel surface with atomic oxygen

Oxidation of stainless steel surface in oxygen atmosphere was investigated by Auger electron spectroscopy (AES) depth profiling. The samples made of AISI 304L stainless steel were exposed to highly non-equilibrium oxygen atmosphere at different temperatures between 300 and 800 K and for different periods between 5 and 600 s. The degree of dissociation of oxygen molecules was of the order of 10%. A thin oxide layer formed on the stainless steel surface consisted of the iron oxide. The thickness depended on the sample temperature. At room temperature it was 7 nm, and it remained the same up to 200 °C. With further increase of temperature, the thickness of the oxide layer increased and reached 40 nm at 450 °C. The thickness was independent of exposure time. The results were explained by two mechanisms of oxide growth. Up to 200 °C the oxidation was run by electro-migration, while at higher temperatures the thermal induced migration prevailed.     

Anti-bacterial treatment of polyethylene by cold plasma for medical purposes

Polyethylene (PE) is one of the most widely used polymers in many industrial applications. Biomedical uses seem to be attractive, with increasing interest. However, PE it prone to infections and its additional surface treatment is indispensable. An increase in resistance to infections can be achieved by treating PE surfaces with substances containing antibacterial groups such as triclosan (5-Chloro-2-(2,4-dichlorophenoxy)phenol) and chlorhexidine (1,1'-Hexamethylenebis[5-(4-chlorophenyl)biguanide]). This work has examined the impact of selected antibacterial substances immobilized on low-density polyethylene (LDPE) via polyacrylic acid (PAA) grafted on LDPE by low-temperature barrier discharge plasma. This LDPE surface treatment led to inhibition of Escherichia coli and Staphylococcus aureus adhesion; the first causes intestinal disease, peritonitis, mastitis, pneumonia, septicemia, the latter is the reason for wound and urinary tract infections.     

On oxidative degradation of parchment and its non-destructive characterisation and dating

Historic parchment is an extremely complex material, not only due to the various methods of production used and various past environmental histories of objects, but also due to its inhomogeneous structure. Many traditional methods of characterisation are empirical, but useful since they have gained recognition by the end-users. In this paper, we investigated the shrinkage temperature of collagen and the influence of lipids contained in parchment on the measurements. While the content of lipids does not seem to significantly affect shrinkage temperature measurements themselves, it strongly affects the decrease of shrinkage temperature of collagen during degradation, and thus its thermomechanical properties. This confirms the high importance of lipid peroxidation during degradation of parchment.     

The surface modification of cellulose fibres to create super-hydrophobic, oleophobic and self-cleaning properties

The surface modification of cellulose fibres was performed with the use of low-pressure water vapour plasma, followed by the application of a pad-dry-cure sol–gel coating with the water- and oil-repellent organic–inorganic hybrid precursor fluoroalkyl-functional siloxane (FAS), with the aim of creating the “lotus effect” on the cotton fabric surface. The tailored “lotus effect” was confirmed by measurements of the contact angle of water (154°) and n-hexadecane (140°), as well as by measurements of the water sliding angle (7°), which were used to identify the super-hydrophobic, oleophobic and self-cleaning properties of the modified fibres. The chemical and morphological changes caused by modifications of the fibres were investigated by XPS, FTIR, AFM and SEM. The results show that the plasma pre-treatment simultaneously increased the surface polarity, average roughness, and surface area of the fabric. The application of the FAS coating after plasma pre-treatment caused only a slight increase in the surface roughness, accompanied by a decrease in the surface area, indicating that the architecture of the surface was significantly changed. This result suggests that the surface pattern affected the “lotus effect” more than the average surface roughness. The plasma pre-treatment increased the effective concentration of the FAS network on the fabric, which resulted in enhanced repellency before and after repetitive washing, compared with that of the FAS-coated fabric sample without the plasma pre-treatment. Despite the fact that the plasma pre-treatment increased the concentration of the oxygen-containing functional groups on the fabric surface, this phenomenon insignificantly contributed to the adhesion ability and, consequently, the washing fastness of the FAS coating.     

Creating cellulose fibres with excellent UV protective properties using moist CF4 plasma and ZnO nanoparticles

Weakly ionised gaseous plasma created in a moist tetrafluoromethane gas at a low pressure with an electrodeless radiofrequency discharge was applied to modify the surface properties of cellulose fibres. The plasma was used to increase the adsorption of zinc oxide (ZnO) nanoparticles such that cellulose fibres with good ultraviolet (UV) protective properties could be created. The UV protection factor (UPF) values of the ZnO-functionalised fibres were determined as a function of the plasma treatment time. The chemical and physical surface properties of the plasma-treated fibres were examined using scanning electron microscopy, X-ray photoelectron spectroscopy, and wettability tests. The quantity of zinc on the fibres was determined using inductively coupled plasma mass spectroscopy. The results indicated that 30 s of plasma treatment resulted in ZnO-functionalised samples with lower UPF values than samples without plasma treatment due to the creation of fluorine-rich functional groups on cellulose fibres and the agglomeration of ZnO nanoparticles. The highest UPF values (50+) were obtained when samples were treated with plasma for 10 s. These high UPF values were a result of the increased adsorption of uniformly distributed ZnO nanoparticles caused by fibres surface functionalization and roughening upon plasma treatment. Furthermore, the mechanical properties of textiles treated with moist CF₄ plasma for 10 s were slightly improved.     

The effect of high frequency electric pulses on muscle contractions and antitumor efficiency in vivo for a potential use in clinical electrochemotherapy

Muscle contractions present the main source of unpleasant sensations for patients undergoing electrochemotherapy. The contractions are a consequence of high voltage pulse delivery. Relatively low repetition frequency of these pulses (1 Hz) results in separate muscle contractions associated with each single pulse that is delivered. It would be possible to reduce the number of unpleasant sensations by increasing the frequency of electric pulses above the frequency of tetanic contraction, provided that the antitumor efficiency of electrochemotherapy remains the same. These assumptions were investigated in the present paper by measuring the muscle torque at different pulse repetition frequencies and at two different pulse amplitudes in rats and studying the antitumor efficiency of electrochemotherapy at different pulse repetition frequencies on tumors in mice. Measurements of muscle torque confirmed that pulse frequencies above the frequency of tetanic contraction (>100 Hz) reduce the number of individual contractions to a single muscle contraction. Regardless of the pulse amplitude, with increasing pulse frequency muscle torque increases up to the frequency of 100 or 200 Hz and then decreases to a value similar to that after application of a 1 Hz pulse train. Electrochemotherapy in vivo with higher repetition frequencies inhibits tumor growth and is efficient at all pulse frequencies examined (1 Hz-5 kHz). These results suggest that there is a considerable potential for clinical use of high frequency pulses in electrochemotherapy.     

Quality assurance in daily practice

 A report based on the workshop on "Quality Assurance in Daily Practice", organised by the study group "Quality Assurance and Accreditation" from the Division of Analytical Chemistry of the Federation of European Chemical Societies (SGQAA/DAC/FECS) held at the EUROANALYSIS-10 conference in Basle, 6–11 September 1998.