The theoretical basis of column chromatography in multicomponent separations. Part 2: Peak capacity. Column systems with good selectivity

The selectivity of a column system, S, defined by equation 28, includes a variation coefficient (β) of plate number with capacity ratio which has a large influence on the peak capacity, as shown in Fig. 18. Some typical chromatograms are given. In order to predict S for a column system from Kovat's Index, equations 40 and 41 are given to calculate the constant of the carbon number rule for squalane at different temperatures or for different stationary phases. The specific retention value of heptane on squalane at different temperatures can be calculated from equation 42. The nonpolarity index, defined by equation 43, was used to calculate the retention value of heptane on various stationary phases. In liquid chromatography, the order of elution may be reversed by changing the composition of the eluent on the same chemically bonded silica (manufactured in China). The linear relations between the log retention values of different kinds of solutes or of a single solute on the silicas of different surface areas when using the same eluent are given.     

Molecular sensing of 3-chloro-1,2-propanediol by molecular imprinting

A covalent interaction-based molecularly imprinted polymer (MIP) material for 3-chloro-1,2-propanediol (3-MCPD), a post-testicular anti-fertility agent and possible carcinogen and mutagen in food products containing acid-hydrolyzed vegetable proteins, has been successfully fabricated using 4-vinylphenylboronic acid as the functional monomer. Rebinding assay revealed that the binding constant, K_B, for the receptor sites and non-specific sites are 1.93±0.1×10⁴ and 2.74±0.7×10² M⁻¹, respectively. The estimated number of receptor site, B_max, imprinted is 123.3±3 μmol/g of MIP. The MIP material is able to act as a potentiometric chemosensor for 3-MCPD via increase in Lewis acidity of the receptor sites upon reaction of the arylboronic acid with 3-MCPD to form the more acidic arylboronic acid esters. A simple pH glass electrode is sufficient to monitor the analyte-specific rebinding. In unbuffered aqueous media, linear potentiometric response from 0 to 350 ppm of 3-MCPD can be achieved. The MIP-based chemosensing in a soya sauce matrix has also been attempted. It is found that the dynamic range of the potentiometric chemosensing response of the MIP material is much reduced, probably due to the blocking or deactivation of receptor sites by interferents in soya sauces. Nevertheless, the present work demonstrated the feasibility of using MIP-based chemosensors as semi-quantitative analytical tools for screening purposes in quality control of food products.     

Use of Tetramethylthiuram Disulfide in Synthesis of Nitrogen-containing Heterocyclic Compounds

We have developed a method for synthesis of aryl isothiocyanates by means of thiocarbamoylation of aromatic amines by tetramethylthiuram disulfide followed by degradation of the intermediate N₍₁₎-aryl-N,N-dimethylthiourea by concentrated HCl. We have shown that thiocarbamoylation of 4-amino-5-ethyl-4H-1,2,4-triazole-3-thiol occurs at the 2 position of the triazole ring, while thiocarbamoylation of 4-amino-3-methyl-6-phenyl-4,5-dihydro-1,2,4-triazin-5-one leads to the dihetaryl-substituted thiourea. We consider the possibility of using N₍₁₎-aryl-N,N-dimethylthioureas as analogs of isothiocyanates in reactions with N-nucleophiles.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 775–780, May, 2005.     

L-(-)-Menthol in the Synthesis of Key Synthons for Optically Active Methyl-Branched Insect Pheromones

A synthesis of optically active 4S-methylhexanal, 1-bromo-3S-methylheptane, and 1-bromo-3S-methylundecane, which are key synthons for several methyl-branched insect pheromones, that is based on chemically selective transformations of 6-tosyloxy- and 6-iodoisopropyl-4R-methylhexanoates that are available from L-(-)-menthol was proposed. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 592–593, November–December, 2005.     

On the Synthesis of Some 2-Arylhydrazono-3-oxothieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridines by Reaction of Nitrilimines with 2-Mercaptonicotinic Acid

Summary. Nitrilimines prepared from N-arylhydrazono chlorides reacted with 2-mercaptonicotinic acid yielding the corresponding addition products, 2-[(2-oxo-1-arylhydrazonopropan-1-yl)mercapto] nicotinic acids, which were treated with 1,1-carbonyldiimidazole in THF affording by cyclocondensation the corresponding hitherto unknown 2-arylhydrazono-3-oxothieno[2,3-b]pyridines.     

Preparation and Properties of Aramid-Silica Hybrids with Inter-Phase Bonding Through (3-glycidoxypropyl)-trimethoxysilane

Nano-composites from aramid-silica system have been prepared via sol-gel process. Poly (phenyleneterephthalamide) copolymer chains were prepared by reacting a mixture of p- and m-phenylenediamines with terephthaloyl chloride in dimethylacetamide used as solvent. The sol-gel process in the polymer matrix was carried out through hydrolysis and condensation of a mixture of tetraethoxysilane and (3-glycidoxypropyl) trimethoxysilane. The latter was used to develop linkage, on one hand with silica network structure using alkoxy groups and on the other hand with aramid chains at its secondary amine groups through glycidal groups of silane. Mutual interaction between the two disparate phases aramid and silica network was thus created. Thin films of the composites containing different proportions of silica ranging from 5.0 to 25.0-wt% were cast by the solvent elution technique. The α-relaxation temperature associated with the glass transition was measured by the dynamic mechanical thermal analysis. The results showed an increase in the glass transition temperature from 328°C for the pure aramid to 352°C for the hybrid materials containing 25-wt% silica, an indicative of the increased interfacial interaction between the two phases. Films having relatively low silica content were flexible and transparent, but those with high silica content were opaque and brittle. These films were tested for their tensile strength, modulus and toughness. The mechanical strength of the composites as compared to the pure aramid increased initially but with further addition of silica the strength decreased. The initial increase can be explained due to increased interfacial interaction between the two phases, however agglomeration of silica particles was responsible for decreasing strength at higher silica contents.     

Preparation and Characterisation of Meloxicam Hydroxy Propyl <Emphasis Type="Italic">β</Emphasis>-Cyclodextrin Inclusion Complex

Meloxicam is a non steroidal anti inflammatory drug, used in the treatment of rheumatoid and osteoarthiritis. It is practically insoluble in water and its prolonged use is associated with the incidence of side effects like gastro intestinal perforations, ulcerations and bleeding. Therefore, an attempt has been made to improve the aqueous solubility of the drug by making an inclusion complex using hydroxy propyl β cyclodextrin(HPβ-CD). The complexes were prepared by physical mixture and freeze drying method. The different methods employed for evaluation such as DSC, XRD, SEM and FT-IR studies indicated complete formation of the complex by freeze drying method in a molar ratio of 1:2. The prepared complexes showed improved in-vitro dissolution profile as compared to the pure drug.     

The effect of humidity on thermal process of zinc acetate

The thermal decomposition of zinc acetate dihydrate Zn(CH₃CO₂)₂·2H₂O in some humidity-controlled atmospheres has been successfully investigated by novel thermal analyses, which are sample-controlled thermogravimetry (SCTG), thermogravimety combined with evolved gas analysis using mass spectrometry (TG–MS) and simultaneous measurement of differential scanning calorimetry and X-ray diffractometry (XRD–DSC). The thermal processes of anhydrous zinc acetate in dry gas atmosphere by conventional linear heating experiment initiated with the sublimation around 180 °C, followed by the fusion and the decomposition over 250 °C. SCTG was useful to interpret clearly the successive reaction because the high-temperature parallel decompositions were effectively inhibited. The thermal behavior changed dramatically by introducing water vapor in the atmosphere and the thermal process was quite different from that in dry gas atmosphere. Zinc oxide (ZnO) was formed only in a humidity-controlled atmosphere, and could be easily synthesized at temperatures below 300 °C. XRD–DSC equipped with a humidity generator revealed directly the crystalline change from Zn(CH₃CO₂)₂ to ZnO. A detailed thermal process of Zn(CH₃CO₂)₂·2H₂O and the effect of water vapor are discussed.     

Polyol-Metall-Komplexe. 25. rac-Mannose,rac-Arabit und L-Threit als deprotonierte Liganden in Ferraten(III)

Polyol Metal Complexes. 25. rac-Mannose, rac-Arabitol and L -Threitol as Deprotonated Ligands in Ferrates(III ) Ba₂[Fe₂(β-rac-ManfH_?5)₂] · 12H₂O ( 1 ), Sr₄[Fe₄(rac-Arab1,2,3,5H_?4)₄(OH)₂]CO₃ · 33 H₂O ( 2 ), and Ba₂[Fe₂(L-ThreH_?4)₂(OH)₂] · 12.5 H₂O ( 3 ) (Man = mannose, Arab = arabitol, Thre = threitol) have been crystallized from alkaline aqueous solution. Crystal structure analysis revealed dinuclear ferrate(III ) ions for 1 and 3 , the former being a C_i-symmetrical homoleptic ferric complex with pentadentate pentaanions derived from racemic β-mannofuranose. In 3 , besides tetradentate L -threitolato ligands, there is one terminal hydroxo ligand at each ferric center. Hydroxo ligands are also present in the C_i-symmetrical hexaanions of 2 , which are tetranuclear planar entities built up from four edge-sharing FeO₆ octahedra. However arabitol is a pentitol, the tetraanionic ligands are only tetradentate for steric reasons.