Synthesis of a homotrifunctional conjugation reagent based on maleimide chemistry

A novel homotrifunctional conjugation reagent, 1,3,5-tris-(N-maleimidomethyl)benzene has been synthesized in high yield with minimum purification. The reactivity of this compound was examined by using l-cysteine as a nucleophile.     

Synthesis and characterization of block copolymers from 2‐vinylnaphthalene by anionic polymerization

The anionic polymerization of 2‐vinylnaphthalene (2VN) has been studied in tetrahydrofuran (THF) at ?78 °C and in toluene at 40 °C. 2VN polymerization in THF, toluene, or toluene/THF (99:1 v/v) initiated by sec‐butyllithium (sBuLi) indicates living characteristics, affording polymers with predefined molecular weights and narrow molecular weight distributions. Block copolymers of 2VN with methyl methacrylate (MMA) and tert‐butyl acrylate (tBA) have been synthesized successfully by sequential monomer addition in THF at ?78 °C initiated by an adduct of sBuLi–LiCl. The crossover propagation from poly(2‐vinylnaphthyllithium) (P2VN) macroanions to MMA and tBA appears to be living, the molecular weight and composition can be predicted, and the molecular weight distribution of the resulting block copolymer is narrow (weight‐average molecular/number‐average molecular weight < 1.3). Block copolymers with different chain lengths for the P2VN segment can easily be prepared by variations in the monomer ratios. The block copolymerization of 2VN with hexamethylcyclotrisiloxane also results in a block copolymer of P2VN and poly(dimethylsiloxane) (PDMS) contaminated with a significant amount of homo‐PDMS. Poly(2VN‐b‐nBA) (where nBA is n‐butyl acrylate) has also been prepared by the transesterification reaction of the poly(2VN‐b‐tBA) block copolymer. Size exclusion chromatography, Fourier transform infrared, and ¹H NMR measurements indicate that the resulting polymers have the required architecture. The corresponding amphiphilic block copolymer of poly(2VN‐b‐AA) (where AA is acrylic acid) has been synthesized by acidic hydrolysis of the ester group of tert‐butyl from the poly(2VN‐b‐tBA) copolymer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4387–4397, 2002     

A study of some trace elements in infant foods

Seven trace elements were determined in milk formulas, powder milk and infant food. Instrumental neutron activation analysis was used for the analysis of Fe, Zn, Co, Cr and Rb, while As and Cu content was determined using radiochemical neutron activation analysis. Differences were found in the trace element content of foods of the same type. Milk formulas are comparable with human milk according to the results obtained for the elements analyzed. The samples of powder cow's milk presented similar concentrations of the elements studied. Liver with vegetables was found to have the highest Cu content. A meal prepared at home, made of beef and fresh vegetables showed a higher trace element content than its similar commercial one. An estimation of the daily intake of the elements analyzed was made and compared with minimum recommended daily ingestion.     

Mineralization mechanism of calcium phosphates under three kinds of Langmuir monolayers

Three kinds of Langmuir monolayers formed by dipalmitoylphosphatidylcholine (DPPC), arachidic acid (AA), and octadecylamine (ODA) were used as templates to study the initial stage of nucleation and crystallization of calcium phosphates. It was demonstrated that the combination of calcium ions (or phosphates) to the monolayer/subphase interface is a prerequisite for subsequent nucleation. It was found that calcium phosphate dihydrate (DPCD) formed at 25.0 degrees C for 12 h has a biphasic structure containing both amorphous and crystalline phases. These results showed that calcium phosphates were formed through a multistage assembly process, during which an initial amorphous phase DPCD was followed by a phase transformation into a crystalline phase and then the most stable hydroxyapatite (HAp). This provided new insights into the template-biomineral interaction and a mechanism for biomineralization.     

A facile synthesis of highly functionalized dihydrofurans based on 1,4-diazabicyclo[2.2.2]octane (DABCO) catalyzed reaction of halides with enones

Treatment of halides 5 with electrophilic alkenes 2 afforded the corresponding dihydrofurans 3 and 4 in the presence of 1, 4-diazabicyclo[2.2.2]octane (DABCO) with good to excellent yields and in a stereoselective manner in most cases. Moreover, the stereoisomers 3 and 4 could be easily transformed each other in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).     

Long term stability of organic selenium species in aqueous solutions

Long term stability of organic selenium compounds (selenocystine, selenomethionine, trimethylselenonium ion) has been studied over a one year period for 2 analyte concentrations: 25 and 150 μg/L Se, at pH 4.5 in the dark, under different storage conditions: temperature of –20°C, 4°C, 20°C, 40°C; in Pyrex, Teflon, or polyethylene containers; in an aqueous matrix or in the presence of a chromatographic counter ion (pentyl sulfonate at 10^–4 mol/L concentration). Light effects have also been tested. The stability of the selenium species was monitored by HPLC-ICP/MS. Storage conditions can drastically alter the stability of organic selenium species. Organoselenium compounds were shown to be stable in the dark over a one year period in an aqueous matrix at pH 4.5 in Pyrex containers at both 4°C and 20°C. Pyrex vials exposed to natural sunlight at room temperature resulted in a steady decrease of the selenoamino acid concentration. Teflon containers caused losses of less than 25% at both 4° C and 20° C in the dark. However, polyethylene vials presented, at all temperatures tested, a rapid decrease of the TMSe⁺ concentration. The stability of the Se species studied did not show significant differences between 4° C and 20° C in any container material used. Storage of solutions at 40° C led to slight differences between the Pyrex and Teflon containers. However, polyethylene presented a drastic decrease of the three species over time at this higher temperature. Solutions frozen at –20° C in polyethylene vials did not stabilize the TMSe⁺ signal. Finally, concentrations and matrices of the samples did not significantly affect the stability of the species. Received: 15 July 1996 / Revised: 14 July 1997 / Accepted: 18 July 1997     

Hydralazine-selective PVC membrane electrode based on hydralazinium tetraphenylborate

A hydralazine ion-selective PVC membrane electrode based on hydralazinium tetraphenylborate has been prepared with dioctyl phthalate as plasticizer. The electrode showed linear response with a slope factor of 57.5 mV/concentration decade at 20 degrees over the concentration range from 4 x 10(-4) to 10(-1)M hydralazine. The effects, on the electrode performance, of membrane composition, pH of the test solution and the time of soaking were studied. The electrode exhibited good selectivity for hydralazine with respect to a large number of inorganic cations and organic substances of biological importance. The standard-addition method and potentiometric titrations were used to determine hydralazine concentrations in pure solutions and in a pharmaceutical preparation, with satisfactory results.     

Nonlinear evolution of thin liquid films dewetting near soft elastomeric layers

The nonlinear evolution of thin liquid films dewetting near soft elastomeric layers is examined in this work. Evolution equations are derived by applying the lubrication approximation and assuming that van der Waals forces in the liquid cause the dewetting and that the solid can be described as a linear viscoelastic material. Two cases are examined: (i) a liquid layer resting on an elastomer bounded from below by a rigid substrate, and (ii) an elastomer overlying a thin liquid film bounded from below by a rigid substrate. Linear stability analysis is carried out to obtain asymptotic relations which are then compared against solutions of the full characteristic equations. In the liquid-on-solid case, numerical solutions of the evolution equations show that van der Waals forces cause thinning of the liquid film and thickening of the elastomeric solid beneath film depressions. Inclusion of a short-range repulsive force suggests that regular patterns may form in which ridges of fluid rest on depressions in the solid. In the solid-on-liquid case, the van der Waals forces cause the solid layer to break up before the liquid film can dewet. The results presented here support the idea that the dewetting of thin liquid films might be exploited to create topographically patterned surfaces on soft polymeric solids.     

Catalyzed Asymmetric Arylation Reactions

Addition and substitution reactions with carbon nucleophiles are fundamental processes in organic synthesis, and the development of general catalytic asymmetric variants thereof is still a major challenge today. In contrast to enantioselective alkyl transfer reactions, the corresponding arylations have not yet reached a high level of maturity. The existing protocols are either of no general applicability or are limited in terms of selectivity. This article summarizes established routes for catalytic asymmetric aryl transfer together with the latest developments in this area. The scope and limitations of this reaction are discussed.     

Atomic Force Microscopy Study of TiO2 Films Obtained by the Sol-Gel Method

Atomic Force Microscopy (AFM) was used to study the influence of thermal treatments on the structural and textural properties of the sol-gel TiO2 films obtained from Ti(OC3H7i)4. X-ray diffraction (XRD), ellipsometric and porosity measurements have also been made.The TiO2 sol-gel films were homogeneous, transparent and amorphous. Heat treatments in the 400–600°C range indicate that the films have a strong tendency to crystallization. The high initial homogeneity of the TiO2 films was preserved during the crystallization process. AFM shows that the thermally treated films exhibit uniform, monodispersed crystals.