Synthesis of novel optical isomers of α-methylpolyamines

Earlier unknown (R)- and (S)-α-methylspermidine, (R)- and (S)-α-methylspermine, (R,R)-, (S,S)-, and (R,S)-α,ω-dimethylspermine were synthesized in gram scale from readily available (R)- and (S)-2-aminopropanols in high overall yields.     

A novel strategy for the preparation of naturally occurring phosphocitrate and its partially esterified derivatives

A novel method for the synthesis of phosphocitrate (1, PC) starting from triethyl ester of citric acid and MeOPCl2 is described. The method is based on selective stepwise hydrolysis of ester moieties from the intermediate Me-O-P(O)(Cl)(Z) (Z = triethylcitrate), 4a, which also allows one to prepare partially esterified derivatives of PC with good yield and purity without chromatographic purifications.     

Step algebras of semi-simple subalgebras of Lie algebras

For each pair (G,K) where G is a complex finite-dimensional Lie algebra and K a semi-simple subalgebra of G, we construct an associative algebra (step algebra) $\text{Y}$ (G,K) and a homomorphism i_*: $\text{Y}$ (G,K)→E(G) is the enveloping algebra of G. $\text{Y}$ (G,K) has the following properties: (1) If V is any G-module and x ? V a K-maximal vector, then sx = i_* (s)x is K-maximal for any s ? $\text{Y}$ (G,K); (2) If V is irreducible and a certain simple criteria is fulfilled, then any K-maximal vector can be written in the form sx_m, s ? $\text{Y}$ (G,K), where x_m is some fixed K-maximal vector. Because of these properties $\text{Y}$ (G,K) has great practical value when constructing irreducible representations of Lie algebras in a form which makes the reduction with respect to a semi-simple subalgebra explicit.     

Trees and Ehrenfeucht–Fraïssé games

Trees are natural generalizations of ordinals and this is especially apparent when one tries to find an uncountable analogue of the concept of the Scott-rank of a countable structure. The purpose of this paper is to introduce new methods in the study of an ordering between trees whose analogue is the usual ordering between ordinals. For example, one of the methods is the tree-analogue of the successor operation on the ordinals.     

Channel selective scanning tunneling spectroscopy

In this paper we simulate STM and STS experiments for CO monomers and dimers on Cu(1 1 1) surface. We show that the contrast of STM images can be attributed to interference effects between tunneling channels, and suggest that functionalizing the microscope tip improves the channel selectivity of STM. Furthermore, we show that voltage and position dependent tunneling spectra also reflect the same interference effects, but adds the energy resolution to the channel analysis. Especially in the case of nonresonant tunneling, STS measures local density of states only indirectly. The present study suggests that STS in constant height mode can be used in investigating the phase and energy sensitivity of tunneling channels in adsorbate molecules and nanostructures.     

Sulfonated cellulose nanofibrils obtained from wood pulp through regioselective oxidative bisulfite pre-treatment

The consecutive pre-treatment of cellulose with periodate and bisulfite was used as a new potential method to promote nanofibrillation of hardwood pulp and to obtain nanofibrils with sulfonated functionality. Nanofibrils having typical widths of 10–60 nm were obtained from sulfonated celluloses having low anionic charge densities (0.18–0.51 mmol/g) by direct high-pressure homogenization without the use of any mechanical pre-treatments. The aqueous nanofibrils existed as highly viscous and transparent gels and possessed cellulose I crystalline structures with crystallinity indexes of approximately 40 %. A transparent film was obtained from sulfonated nanofibrils having tensile strength of 164 ± 4 MPa and Young’s modulus of 13.5 ± 0.4 MPa. Oxidative sulfonation was shown to be a potential green method to promote nanofibrillation of cellulose, as it avoids the production of halogenated wastes, because the periodate used can be efficiently regenerated and recycled as shown in the preliminary experiments.     

New Heteroaromatic Complexing Agents and Luminescence of Their Europium(III) and Terbium(III) Chelates

Twelve heteroaromatic complexing agents 9a–I were synthesized with the purpose to develop suitable labels for time-resolved luminescence-based bioaffinity assays. The relative luminescence yields, excitation maxima, and emission decay constants of their europium(III) and terbium(III) chelates were determined. According to these results, 2,2′,2″,2?-[(2,2′-bipyridine-6,6′-diyl)bis(methylenenitrilo)]tetrakis (acetic acid) ( 9e ) and 2,2′,2″,2?-[(2,2′:6′,2″-terpyridine-6,6″-diyl)bis(methylenenitrilo)] tetrakis(acetic acid) ( 91 ) are the most promising agents.     

Layer-by-layer polyelectrolyte coating of low molecular weight poly(lactic acid) nanoparticles

Low molecular weight (M(w)) poly(L-lactic acid) (PLA) nanoparticles were coated with polyelectrolytes (PEs) by layer-by-layer (LbL) technique using a filtration approach. Poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate) were applied as PEs in coating. LbL coating is aimed to use in producing (nano)particulate drug delivery systems with improved biocompatibility and sustained or targeted release of drug substances. Nanoparticles of rapidly biodegradable polymers, like the low M(w) PLA, open up a possibility to control the release of the encapsulated substance by the coating, but set challenges to the coating process due to increased aggregation tendency and degradation rate of the polymer. When the core PLA nanoparticles were prepared by nanoprecipitation, surface properties of the nanoparticles were affected by solvent selection. Successful LbL coating of the PLA nanoparticles was obtained only with chloroform, but not with dichloromethane as the solvent during nanoprecipitation. Reason for this was found to be the more charged surface of the nanoparticles prepared with chloroform compared to the nanoparticles prepared with dichloromethane.     

Synthesis of novel (1-alkanoyloxy-4-alkanoylaminobutylidene)-1,1-bisphosphonic acid derivatives

A novel strategy for the synthesis of (1-alkanoyloxy-4-alkanoylaminobutylidene)-1,1-bisphosphonic acid derivatives (1a-d) via (1-hydroxy-4-alkanoylaminobutylidene)-1,1-bisphosphonic acid derivatives (2a-d), starting from alendronate has been developed with reasonable 51-77% overall yields. Intermediate products, (1-hydroxy-4-alkanoylaminobutylidene)-1,1-bisphosphonic acid derivatives (2a-d), were prepared in water with reasonable to high yields (52-94%).     

Novel Bioreversible Prodrugs of Clodronate

Abstract

Clodronate (1) belongs to family of bisphosphonates which are used to inhibit mineralization of soft tissues as well as bone formation and resorption disorders.[I] The clinical use of bisphosphonates is limited due to their poor bióvailability which is mostly attributed to their hydrophilic structure. More lipophilic molecules are obtained if some or all of the anionic sites are converted to covalent bonds. We herein report a new prodrug serie for clodronate: the anhydrides 2 and 3. Previously we have reported that the simple alkyl esters 4 do not release clodronate via chemical or enzymatic hydrolysis.[2] The prepared new derivatives are stable in water (pH 5–7.5) but clodronate isrelased rapidly with enzymatic hydrolysis.