Interactions of aluminum(III) with the biologically relevant ligand d-ribose

Aluminum(III) can be absorbed when it is appropriately complexed. There are several plasma components which can bind weakly Al(III). Many proteins bind Al(III) in solution quite strongly. Carbohydrates bearing an abundance of electronegative functional groups can interact with metal cations. In solution, d-ribose exists as a mixture at equilibrium of many isomers and only a few of them bear a ‘complexing’ sequence of the hydroxyl groups. The presence of d-ribose in an Al(III) solution experiences a decrease of its Brönsted-acid sites. The lowering of the Brönsted acidity of an Al(III)-d-ribose mixture suggests the existence of attractive interactions (‘association’) between Al(III) ion and the complexing sequence of the hydroxyls of d-ribose. There is enhancement in the stability of the interaction complexes between Al(III) and d-ribose through strong intramolecular hydrogen bonding, which offers the possibility to investigate the kinetics of the subsequent proton release reactions. On the basis of the kinetic results, it may be concluded that proton release reactions, which are associated with the complexation reactions, are associatively activated. The complexes (Al(H₂O)_6−n(d-ribose_−nH)⁽³⁻ⁿ⁾⁺) resulting from the various ‘complexing’ forms of d-ribose are formed at mainly acidic pH. As the pH increases, the values of the activation enthalpy, ΔH^≠, are changing, because of the formation of mixed hydroxo-complexes (Al(H₂O)_6−n−m(OH)_m(d-ribose_−nH)^(3−n−m)+); finally, OH⁻ displaces d-ribose from the coordination sphere of Al(III) in a rather slow process, i.e. with high values of ΔH^≠; the activation enthalpy values, ΔH^≠, decrease with the progression of the displacement, becoming finally very small due to the formation of a precipitate. Chelate coordination of d-ribose with some divalent and trivalent metal ions has been also reported.     

(3R,4S)-3,4,5-Trihydroxy-4-methylpentylphosphonic acid, an isosteric phosphonate analogue of 2-C-methyl-d-erythritol 4-phosphate, a key intermediate in the new pathway for isoprenoid biosynthesis

2-C-Methyl-d-erythritol 4-phosphate (MEP) is the first intermediate in the mevalonate-independent pathway for isoprenoid biosynthesis presenting the branched C₅ isoprene skeleton. Enantiopure (3R,4S)-3,4,5-trihydroxy-4-methylpentylphosphonic acid (MEP_N), an isosteric phosphonate analogue of MEP was synthesized from 1,2-O-isopropylidene-α-d-xylofuranose.     

Host-guest interaction of L-tyrosine with beta-cyclodextrin

The inclusion complexes of beta-cyclodextrin (beta-CD) with l-tyrosine (l-TYN) were investigated by using spectrophotometers. The absorption and fluorescence enhancement occurs with beta-CD and l-TYN forms 1:1 inclusion complex. The unusual blue shift of hydroxyl ion in the beta-CD medium confirms OH groups present in the interior part of the beta-CD cavity and -COOH group present in the upper part of the beta-CD cavity. A mechanism is proposed to explain inclusion process. The inclusion interaction was examined and the thermodynamic parameters of inclusion process DeltaG, DeltaH and DeltaS were determined. The results indicated that the inclusion process was an exergonic and spontaneous process. Stable solid inclusion complexes were established and characterized by FT-IR, scanning electron microscope (SEM) methods.     

Improving mechanical and biological properties of macroporous HA scaffolds through composite coatings

Interconnected porous hydroxyapatite (HA) scaffolds are widely used for bone repair and replacement, owing to their ability to support the adhesion, transfer, proliferation and differentiation of cells. In the present study, the polymer impregnation approach was adopted to produce porous HA scaffolds with three-dimensional (3D) porous structures. These scaffolds have an advantage of highly interconnected porosity (≈85%) but a drawback of poor mechanical strength. Therefore, the as-prepared HA scaffolds were lined with composite polymer coatings in order to improve the mechanical properties and retain its good bioactivity and biocompatibility at the same time. The composite coatings were based on poly(d,l-lactide) (PDLLA) polymer solutions, and contained single component or combination of HA, calcium sulfate (CS) and chondroitin sulfate (ChS) powders. The effects of composite coatings on scaffold porosity, microstructure, mechanical property, in vitro mineralizing behavior, and cell attachment of the resultant scaffolds were investigated. The results showed that the scaffolds with composite coatings resulted in significant improvement in both mechanical and biological properties while retaining the 3D interconnected porous structure. The in vitro mineralizing behaviors were mainly related to the compositions of CS and ChS powders in the composite coatings. Excellent cell attachments were observed on the pure HA scaffold as well as the three types of composite scaffolds. These composite scaffolds with improved mechanical properties and bioactivities are promising bone substitutes in tissue engineering fields.     

Highly selective recognition of monosaccharide based on two-component system in aqueous solution

A highly selective switch for d-fructose was formed by water-soluble conjugated polymer PP-S-BINOL and tetraboronic acid functionalized benzyl viologen ToBV. The two-component system showed a high selectivity and sensitivity only for d-fructose in familiar d-monosaccharides. The high selectivity of the sensing system for d-fructose may be depended on stable pyranose ester form of d-fructose with ToBV. A desirable linear response of the sensing system to low concentrations of d-fructose (<10.0 mM) was observed with 0.9936 linear dependent coefficient at pH 7.4.     

Improved Enantioselective Synthesis of Protected (3S,4S)-4-Amino-3,5-dihydroxypentanoic Acid (ADPA)

An improved enantioselective synthesis of protected (3S,4S)-4-amino-3,5-dihydroxypentanoic acid (ADPA) from L-serine has been developed. Enantioselectivity is improved by replacing the methyl ester with the tert-butyl ester and using neutral magnesium salt of esters to give β-keto ester.     

An efficient approach to d-threo-3-hydroxyaspartic acid for the synthesis of novel l-threo-oxazolines as selective blockers of glutamate reversed uptake

An efficient, stereoselective synthetic strategy to d-threo-3-hydroxyaspartic acid was developed. Starting from l-(2S,3S)-N-benzoyl-3-hydroxyaspartic acid dimethyl ester by a Deoxo-fluor-catalyzed cyclization reaction, an inversion of configuration at the β-center (erythro isomer), was observed. A base-induced epimerization reaction led to the d-trans-isomer, which was hydrolyzed to give d-threo-3-hydroxyaspartic acid with excellent stereoselectivity and overall yield. Starting from d-threo-3-hydroxyaspartic acid, l-threo-oxazolines can be stereoselectively synthesized.     

Studies on the Conformation of Polyhydroxyalkylpyrazolo (3,4-b) Quinoxalines

¹H NMR spectral studies on polyhydroxyalkylpyrazolo-(3,4-b)-quinoxaline derivatives of sugars having five to seven carbon atoms have shown that the polyhydroxyalkyl chain exists in a conformation in which a hydrogen bond is formed between the l'-hydroxyl group and N-2 of the pyrazolo(3,4-b)-quinoxaline base moiety. The polyhydroxyalkyl chain exists in the planar zigzag conformation, where no 1,3 syn axial interaction is present. Substitution in the base moiety did not change the extent of the population of the planar zigzag conformation.     

Influence of the nature of the ligand on the microstructure of poly d,l-lactides prepared with organoaluminum initiators

The polymerization of d,l-lactide with organoaluminum initiators bearing two different ligands, acetylacetone (1) and achiral Schiff’s base (2), has been studied. The microstructure of the obtained polymers analyzed by high resolution ¹³C NMR (125 MHz) is strongly influenced by the nature of the ligand. Al(acac)₃ (1) leads to stereocopolymers having random repartition of configurational units while polylactides prepared with aluminum methoxide derivatives bearing as ligand Schiff’s base (2) present some degree of stereoregularity with preferential formation of isotactic sequences.Variation of the ligand linked to the initiator appears as one of the best tools for the moulding of the microstructure of obtained polylactides.     

Concise and practical synthesis of (2S,3R,4R,5R) and (2S,3R,4R,5S)-1,6-dideoxy-1,6-iminosugars

The syntheses of (2S,3R,4R,5R) and (2S,3R,4R,5S)-1,6-dideoxy-1,6 iminosugars 1a and 1b, respectively, from d-glucose are described. The key transformations in this reaction sequence include regio-selective epoxide ring opening with N-benzylamine followed by intramolecular reductive amination of amino-aldehyde.     

Antibacterial activity of cyclo(L-Pro-L-Tyr) and cyclo(D-Pro-L-Tyr) from Streptomyces sp. strain 22-4 against phytopathogenic bacteria

Two bioactive cyclic dipeptides, cyclo(L-Pro-L-Tyr) and cyclo(D-Pro-L-Tyr), were isolated from the culture broth of Streptomyces sp. strain 22-4 and tested against three economically important plant pathogens, Xanthomonas axonopodis pv. citri, Ralstonia solanacearum and Clavibacter michiganensis. Both cyclic dipeptides were active against X. axonopodis pv. citri and R. Solanacearum with MIC of 31.25 μg/mL. No activity could be observed against C. michiganensis.     

Separation and determination of l-tyrosine and its metabolites by capillary zone electrophoresis with a wall-jet amperometric detection

A method of capillary electrophoresis with wall-jet amperometric detection (AD) has been developed for separation and determination of l-tyrosine (Tyr) and its metabolites, such as Tyramine (TA), p-hydroxyphenylpyruvic (pHPP), homogentisic acid (HGA) and some dipeptides containing Tyr, such as Tyr-Gly-Gly (YGG), Tyr-Arg (YR) and Tyr-d-Arg (Y-d-R). A carbon disk electrode was used as the working electrode and the optimal detection potential was 1.00 V (versus Ag/AgCl). At 18 kV of applied voltage, the seven compounds were completely separated within 20 min in 110 × 10⁻³ mol/L Na₂HPO₄–NaH₂PO₄ buffer (pH 7.10) containing 3 × 10⁻³ mol/L β-cyclodextrin (β-CD). Good linear relationship was obtained for all analytes and the detection limits of seven analytes were in the range of 0.95–4.25 ng/mL. The proposed method has been applied to examine the metabolic process of l-tyrosine in rabbit's urine.     

Efficient desulfurization of 2-thiopyrimidine nucleosides to the corresponding 4-pyrimidinone analogues using trans-2-(phenylsulfonyl)-3-phenyloxaziridine

A brief treatment of 2-thiopyrimidine nucleosides (s²U^∗) with trans-2-phenylsulfonyl-3-phenyloxaziridine (PSO) results in efficient substrate desulfurization leading to the corresponding 4-pyrimidinone analogues (H²U^∗). The key transformation proceeds through oxidation of the 2-thiocarbonyl group to a sulfur oxyacid derivative and subsequent elimination of sulfur dioxide. 4-Pyrimidinone 1-β-d-riboside (H²U) has been transformed into the respective phosphoramidite, a ready-to-use monomer for the introduction of a modified nucleoside into an oligonucleotide chain. Moreover, the effective desulfurization of the 2-thiouridine nucleotide could be achieved directly at the oligonucleotide level, by treatment of the TdA(s²U)dGdC oligonucleotide with PSO, as verified by MALDI-TOF mass spectrometry.     

Ab-initio and density functional study of L- and D-forms of alanine and serine in gas phase and bulk aqueous medium

The molecular geometry of L and D-forms of alanine and serine in gas phase have been studied by using ab-initio quantum chemical calculations at the restricted Hartree-Fock (RHF) level by employing 6-31G and 6-311++G** basis sets. Subsequently, for considering the electron correlations, Density functional Calculations at the Becke3LYP (B3LYP) and Moller-Plesset second order (MP2) level of calculations have been carried out with the same basis sets for these optimized geometries. Effect of solvation in water on the optimized geometries was studied using the polarized continuum model of the self-consistent reaction field (SCRF) theory. The dipole moment, energy, polarizabilities and vibrational frequencies have been calculated in all cases. Frequency analysis was carried out to ensure that optimized geometry corresponds to a total energy minimum.     

Complex formation of curium(III) with amino acids of different functionalities: L-threonine and O -phospho-L-threonine

The speciation of curium(III) with L-threonine and O-phospho-L-threonine was determined by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at trace Cm(III) concentrations (3?×?10^?7?M). Curium species of the type M_pH_qL_r were identified in the L-threonine- and O-phospho-L-threonine system. These complexes are characterized by their individual luminescence spectra and luminescence lifetimes. The following formation constants were determined (a) for L-threonine: log?β₁₀₁?=?6.72?±?0.07, log?β₁₀₂?=?10.22?±?0.09, and log?β_1–22?=?(7.22?±?0.19) at ionic strength I?=?0.5?M and (b) for O-phospho-L-threonine: log?β₁₂₁?=?18.03?±?0.13 and log?β₁₁₁?=?14.17?±?0.09 at ionic strength I?=?0.154?M. Possible structures of the identified curium species are discussed on the basis of the luminescence lifetime measurements and the magnitude of the formation constants.     

Kinetics of thermo-oxidative and thermal degradation of poly(d,l-lactide) (PDLLA) at processing temperature

Poly(d,l-lactide) (PDLLA) degraded at processing temperature under air and nitrogen. A random chain scission model was established and used to determine the activation energy E_a, and FT-IR, ¹H and ¹³C NMR were used to elucidate the degradation behavior under different atmospheres. Results showed that there were two to three stages. The 1st stage was dominated by the oligomers containing carboxylic acid groups and hydroxyl groups, during which oxygen and nitrogen had little effect on the degradation, thus they share similar E_a. When the oligomers were consumed over or evaporated, the 2nd stage began, and oxygen had a promoting effect on the thermo-oxidation process, resulting in the great decrease in E_a. The third stage of PDLLA was observed when it degraded under nitrogen over 200 °C, which was caused by the appearance of carboxylic acid substance.     

Bulk-modified modified screen-printing carbon electrodes with both lactate oxidase (LOD) and horseradish peroxide (HRP) for the determination of L-lactate in flow injection analysis mode

A screen-printed carbon electrode modified with both HRP and LOD (SPCE–HRP/LOD) has been developed for the determination of l-lactate concentration in real samples. The resulting SPCE–HRP/LOD was prepared in a one-step procedure, and was then optimised as an amperometric biosensor operating at [0, −100] mV versus Ag/AgCl for l-lactate determination in flow injection mode. A significant improvement in the reproducibility (coefficient variation of about 10%) of the preparation of the biosensors was obtained when graphite powder was modified with LOD in the presence of HRP previously oxidised by periodate ion (IO₄⁻). Optimisation studies were performed by examining the effects of LOD loading, periodation step and rate of the binder on analytical performances of SPCE–HRP/LOD. The sensitivity of the optimised SPCE–HRP/LOD to l-lactate was 0.84 nA L μmol⁻¹ in a detection range between 10 and 180 μMol. The possibility of using the developed biosensor to determine l-lactate concentrations in various dairy products was also evaluated.     

Chitosan modified poly(L-lactide) microspheres as cell microcarriers for cartilage tissue engineering

The surfaces of poly(l-lactide) (PLLA) microspheres were modified by chitosan via a method of hydrolysis and grafting-coating to improve their compatibility to chondrocytes. The PLLA microspheres with a diameter of 74-150mum were fabricated by an oil/water emulsion solvent evaporation method, followed by hydrolysis in alkaline solution to produce a larger number of carboxyl groups. Using water-soluble carbodiimide as a coupling reagent, chitosan was covalently grafted onto the microspheres. Due to the physical entanglement and insolubility at neutral pH, unbonded chitosan molecules were stably remained to yield a large amount of coated chitosan. Biological performance of the control PLLA and the chitosan-coated PLLA microspheres were assessed by in vitro culture of rabbit auricular chondrocytes. After 24h and 7d culture, the chitosan-coated PLLA microspheres, especially the ones with larger chitosan amount, exhibited stronger ability to promote cell attachment and proliferation, and maintain the secretion function of the chondrocytes. Therefore, the chitosan-coated PLLA microspheres can be potentially used as the injectable cell microcarriers for chondrogenesis in cartilage tissue engineering.     

Influence of cellulose nanowhiskers on the hydrolytic degradation behavior of poly(d,l-lactide)

This paper reports the preparation of bionanocomposites based on poly(d,l-lactide) and cellulose nanowhiskers (PDLLA/CNWs) and studies the influence of the CNWs on the hydrolytic degradation behavior of the polylactide. The hydrolytic degradation process was studied in a phosphate buffer medium through the sample weight loss and also by FTIR, DSC and TGA measurements. The presence of CNWs induced a strong delay in the hydrolytic degradation of the PDLLA, even when the concentration of the nanofillers was only 1%. This effect was related to the physical barrier created by the highly crystalline CNWs that inhibited water absorption and hence retarded the hydrolytic degradation of the bionanocomposites. In addition, the incorporation of cellulose nanocrystals in the PDLLA also made the biopolymer more thermally stable, increasing the initial temperature of mass loss even after the degradation in phosphate medium. The results presented here show the possibility of controlling the biodegradability and prolonging the service life of a polylactide through the incorporation of a small quantity of nanofillers obtained from renewable materials.