New vertex invariants and topological indices of chemical graphs based on information on distances

By applying information theory to the set of topological distances from one vertex to all other graph vertices, one obtains four new types of vertex invariants (u _i,v _i,x _i,Y _i) which are real numbers (as opposed to integers). They may be combined in many ways to afford new topological indices. One such type leads to indicesU, V, X andY which show no degeneracy for alkanes with up to 15 vertices.     

Potential use of cyclodextrins in soil bioremediation

Bioavailability and toxic effect of contaminants are the main limitations during soil bioremediation. Cyclodextrins may influence bioavailability of the contaminants during biodegradation and also toxicity of the pollutant on soil microbes and plants since their ability to form inclusion complei with organic compounds. The effect of cyclodextrins on bioremediation and on toxic effect of hydrocarbons was investigated by testing the activity of hydrocarbon degrading microflora and of plant growth. The effect of cyclodextrins could be demonstrated in both cases: biodegradation of hydrocarbons could be enhanced and toxic effect of hydrocarbons on plants and soil microbes could be decreased by adding cyclodextrins.     

Biogas Production from N-Methylmorpholine-N-oxide (NMMO) Pretreated Forest Residues

Lignocellulosic biomass represents a great potential for biogas production. However, a suitable pretreatment is needed to improve their digestibility. This study investigates the effects of an organic solvent, N-Methylmorpholine-N-oxide (NMMO) at temperatures of 120 and 90 °C, NMMO concentrations of 75 and 85 % and treatment times of 3 and 15 h on the methane yield. The long-term effects of the treatment were determined by a semicontinuous experiment. The best results were obtained using 75 % NMMO at 120 °C for 15 h, resulting in 141 % increase in the methane production. These conditions led to a decrease by 9 % and an increase by 8 % in the lignin and in the carbohydrate content, respectively. During the continuous digestion experiments, a specific biogas production rate of 92 NmL/gVS/day was achieved while the corresponding rate from the untreated sample was 53 NmL/gVS/day. The operation conditions were set at 4.4 gVS/L/day organic loading rate (OLR) and hydraulic retention time (HRT) of 20 days in both cases. NMMO pretreatment has substantially improved the digestibility of forest residues. The present study shows the possibilities of this pretreatment method; however, an economic and technical assessment of its industrial use needs to be performed in the future.     

Use of a new type of 8-hydroxyquinoline-5-sulphonic acid cellulose (sulphoxine cellulose) for the preconcentration of trace metals from highly mineralised water prior their GFAAS determination

Sulphoxine cellulose microcolumn was used in an FI-GFAAS system for the preconcentration of trace metals, Cd, Co, Ni, Pb and V from water and from highly mineralised water and also in the presence of complexing agent, e.g. citrate. The recovery was quantitative at pH 5 for all of the elements from NIST 1643c trace elements in water SRM and from highly mineralised water samples. No significant difference was found in the sorption of V(IV) and V(V) during preconcentration. The preparation of the 8-hydroxyquinoline-5-sulphonic acid cellulose (sulphoxine-cellulose) by Mannich reaction from aminoethyl cellulose or via chlorodeoxy and ethylenediamine cellulose is also described.     

Capillary columns with in situ formed porous monolithic packing for micro high-performance liquid chromatography and capillary electrochromatography.

Capillary columns with monolithic stationary phase were prepared from silanized fused-silica capillaries of 75 microns I.D. by in situ copolymerization of divinylbenzene either with styrene or vinylbenzyl chloride in the presence of a suitable porogen. The porous monolithic support in this study was used either directly or upon functionalization of the surface to obtain a stationary phase that was appropriate for the separation of peptides by capillary electrochromatography (CEC). The main advantages of monolithic columns are as follows. They do not need retaining frits, they do not have charged particles that can get dislodged in high electric field, and they have relatively high permeability and stability. Whereas such columns are designed especially for CEC, they find application in micro high-performance liquid chromatography (mu-HPLC) as well. Five different porogens were employed to prepare the monolithic columns that were examined for permeability and porosity. The flexibility of fused-silica capillaries was not adversely affected by the monolithic packing and the longevity of the columns was satisfactory. This may also be due to the polymerization technique, which resulted in a fluid-impervious outer layer of the monolith that precluded contact between the fused-silica surface and the liquid mobile phase. For the most promising columns, the conductivity ratios and the parameters of the simplified van Deemter equation, both in mu-HPLC and CEC, were evaluated. It was found that the efficiency of the monolithic columns in CEC was significantly higher than in mu-HPLC in the same way as observed with capillary columns having conventional particulate packing. This is attributed to the relaxation of band-broadening with electroosmotic flow (EOF) with respect to that with viscous flow. It follows then that the requirement of high packing uniformity to obtain high efficiency may also be relaxed in CEC. Angiotensin-type peptides were separated by CEC with columns packed with a monolithic stationary phase having fixed n-octyl chains and quaternary ammonium groups at the surface. Plate heights of about 8 microns were routinely obtained. The mechanism of the separation is based on the interplay between EOF, chromatographic retention and electrophoretic migration of the positively charged peptides. The results of the complex migration process, with highly nonlinear dependence of the migration times on the organic modifier and the salt concentration, cannot be interpreted within the framework of classical chromatography or electrophoresis.     

Dynamics of capillary electrochromatography. II. Comparison of column efficiency parameters in microscale high-performance liquid chromatography and capillary electrochromatography.

In capillary electrochromatography (CEC) the flow of the mobile phase is generated by electrosmotic means in high electric field. This work compares band spreading measured experimentally in several packed capillaries with electrosmotic flow (EOF) and viscous flow under otherwise identical conditions. The data were fitted to the simplified van Deemter equation for the theoretical plate height, H = A + B/u + Cu, in order to evaluate parameters A and C in each mode of flow in the different columns. The ratio of these two parameters obtained with the same column in microscale HPLC (mu-HPLC) and CEC was used to quantify the attenuation of their contribution to band spreading upon changing from viscous flow (in mu-HPLC) to electrosmotic flow (in CEC). The capillary columns used in this study were packed with stationary phases of different pore sizes as well as retentive properties and measurements were carried out under different mobile phase conditions to examine the effects of the retention factor and buffer concentration. In the CEC mode, the value of both column parameters A and C was invariably by a factor of two to four lower than in the mu-HPLC mode. This effect may be attributed to the peculiarities of the EOF flow profile in the interstitial space and to the generation of intraparticle EOF inside the porous particles of the column packing. Thus, band spreading due to flow maldistribution and mass transfer resistances is significantly lower when the mobile phase flow is driven by voltage as in CEC, rather than by pressure as in mu-HPLC.     

Nitrogen bridgehead compounds. Part 35. Structures of α-formyl-2,3-polymethylene-3,4-dihydroquinazolin-4-ones

The structures of the title compounds bearing a five-, six- or seven-membered A ring have been investigated by uv and ¹H and ¹³C nmr spectroscopy. The imine-enol-enamine (I-II-III) tautomerism of these compounds depends greatly on the ring size. A significant solvent-dependence is observed only for the five-membered-ring compounds 1 and 2 , which in ethanolic solution exist predominantly in the imine form I, and in chloroform solution in the enol form II. The compounds with a six-membered A ring, 3 and 4 , are mainly in the enamine form III. On protonation, 3 and 4 change into the E and Z isomeric mixture of the enol tautomer II. The seven-membered-ring compound 5 is a mixture of the imine I and the enamine III tautomers.     

Improvement of pesticide adsorption capacity of cellulose fibre by high-energy irradiation-initiated grafting of glycidyl methacrylate

Cellulose as a renewable raw material was used for preparation of adsorbent of organic impurities in wastewater treatment. Hydrophobic surface of cellulose substrate was developed by grafting glycidyl methacrylate in simultaneous grafting using gamma irradiation initiation. Water uptake of cellulose significantly decreased while adsorption of phenol and a pesticide molecule (2,4-dichlorophenoxyacetic acid: 2,4-D) increased upon grafting. Adsorption equilibrium data fitted the Freundlich isotherm for both solutes.     

Surface-enhanced vibrational investigation of adsorbed analgesics

Adsorption properties of acetylsalicylic acid (AA), ibuprofen and acetaminophen deposited from volatile solvents with varying protic/aprotic properties on vacuum-evaporated silver films were characterized using surface-enhanced infrared absorption (SEIRA) and surface-enhanced Raman spectroscopy (SERS). SERS preferentially enhances monolayer Raman shifts, while SEIRA can enhance the infrared absorbance of the monolayer and multilayers. To our best knowledge, this is the first reported study of these molecules using a combination of SERS/SEIRA. SERS revealed that AA and ibuprofen adsorbed ionically in monolayers, independent of the deposition solvents used in the process. SEIRA experiments showed that AA multilayers condensed molecularly using a deposition solvent with polar bonds. However, when an alkane deposition solvent with non-polar bonds such as n-heptane was used, AA adsorbed as acetylsalicylate ions in the first few multilayers, while ibuprofen always adsorbed as the free acid in the multilayer. These ionization trends depend upon the affinity of AA and ibuprofen for the underlying silver film. TPD experiments on silver powders further demonstrated that ibuprofen affinity for silver was less than AA. Furthermore, SEIRA indicated that acetaminophen adsorbed as multilayers of metastable polymorphs using protic or polar aprotic deposition solvents. Protic deposition solvents gave higher quality SERS spectra of an acetaminophen monolayer in comparison to polar aprotic deposition solvents. Such studies could find significant applications in biochemical and nanotechnology processes such as drug delivery, catalysis, and tissue engineering and will contribute to the understanding of the impact and fate of analgesics released into the environment.