The novel [(dME)2(HIM)P]2Ti(IV) complex: synthesize, characterization, and its utility in ROP of d,l-lactide

The novel {2,4-bis(1,1-dimethylethyl)-6-{[(2-hydroxyethyl)imino]methyl}phenoxy}₂ titanium(IV) complex {[(dME)₂(HIM)P]₂Ti(IV)} had been synthesized and characterized by EA, XRF, IR, and NMR methods. The [(dME)₂(HIM)P]₂Ti(IV) complex was reactive and promoted ring-opening polymerization (ROP) of d,l-lactide in the presence of benzyl alcohol (BnOH). And the results showed that ROP of d,l-lactide were produced upon addition of an excess (1–8?equiv.) of external BnOH. The complex showed a living and controlled fashion (M _w/M _n?=?1.15–1.32) for ROP of d,l-lactide and could produce the poly(d,l-lactide) with average molecular weight (M _n) up to 8.87?×?10⁴?g?mol^?1. The mechanism study by ¹H NMR spectrum of poly(d,l-lactide) with terminal benzyl ester group and [(dME)₂(HIM)P]₂Ti(IV) complex revealed that the polymerization proceeded through the traditional activated monomer mechanism and the acyl-oxygen bond cleavage mode of monomer. And the ¹³C NMR spectra and TG/DSC analysis showed that poly(d,l-lactide) was essential atactic and thermal stable polymer.     

The Catalytic Conversion of d-Glucose to 5-Hydroxymethylfurfural in DMSO Using Metal Salts

A wide range of metal halides and triflates were examined for the conversion of d-glucose to HMF in DMSO. Chromium and aluminium salts were identified as the most promising catalysts. The effect of process variables like initial d-glucose concentration (0.1?C1.5?M), reaction time (5?C360?min) and reaction temperature (100?C140?°C) on the yield of HMF were examined at a fixed Al(OTf)₃ concentration (50?mM). Highest yields of HMF (60?mol%) were obtained using 1?M d-glucose (16?wt%), Al(OTf)₃ (5?mol%) at a temperature of 140?°C. A reaction pathway involving initial isomerisation of d-glucose to d-fructose followed by a number of dehydration steps is proposed. Kinetic analysis reveals that the reaction is second order in d-glucose with an activation energy of 138?kJ?mol^?1.     

An Interesting Complex: [Cd(l -trp) (d-trp)] n

A novel coordination polymer [Cd(l-trp) (d-trp)] _n (where l-trp and d-trp are l-tryptophan and d-tryptophan or (S)-2-amino-3-(3-indolyl)propionic acid and (R)-2-amino-3-(3-indolyl)propionic acid) was prepared by a solvent-thermal method and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The compound(monoclinic space group P2(1)/c with a = 19.759(2) Å, b = 5.2496(10) Å, c = 9.7594(16) Å, β = 97.2760(10)°, Z = 2) shows a two-dimensional plane structure. The crystallized coordination polymer has a centrosymmetric space group. Each Cd²⁺ ion coordinates with a pair of racemes, and the complex is a mesomer. Although l-trp was used, both l-trp and d-trp appear in the complex.     

Facile synthesis of branched chitin by glycosylation of fully trimethylsilylated chitin with a glucosamine-derived oxazoline

A simple and straightforward procedure for synthesizing branched chitin and chitosan has been developed on the basis of the glycosylation of trimethylsilylated chitin with an oxazoline derived from d-glucosamine. Chitin was first trimethylsilylated, and the derivative was treated with the oxazoline to introduce peracetylated d-glucosamine branches into the chitin backbone. The extent of branching was dependent on the amount of the oxazoline and reaction time, and under appropriate conditions, it reached around 0.65. Selective O-deacetylation or thorough N,O-deacetylation of the resulting glycosylated product gave chitin having N-acetyl-d-glucosamine branches or chitosan having d-glucosamine branches.     

Green Chemicals from d-glucose: Systematic Studies on Catalytic Effects of Inorganic Salts on the Chemo-Selectivity and Yield in Aqueous Solutions

The use of inorganic salts as catalysts for the reactions of d-glucose in aqueous solutions in a batch reactor is reported. The type of salt and effect of reaction time were examined in detail at a fixed salt (5 mM) and d-glucose concentration (0.1 M) and at a temperature of 140 °C. Al(III) and Cr(II) salts gave the highest conversion of d-glucose. Typical reaction products were organic acids like lactic acid, levulinic acid, furanics like hydroxymethylfurfural and insoluble products (humins). The chemo-selectivity is a clear function of the type of inorganic salt. For Al(III), the major water soluble product was lactic acid, for Zn(II) HMF was formed in the highest yields. A reaction scheme is proposed to explain the observed product compositions.     

Cellulose–chitin hybrids: synthesis of branched amino polysaccharides by regioselective introduction of (N-acetyl-)d-glucosamine branches into cellulose

Cellulose–chitin hybrid-type branched polysaccharides, β-1,4-d-glucans having amino sugar branches at the C-6 position, have been synthesized through a series of site-specific modification reactions. Cellulose was first transformed to two kinds of acceptors having a reactive group only at C-6. Glycosylation reactions of these acceptors with an oxazoline donor derived from d-glucosamine resulted in the introduction of amino sugar branches into cellulose. An acceptor carrying the O-trimethylsilyl group at C-6 was particularly suitable for glycosylation in solution to form branched celluloses with various degrees of substitution up to about 0.5 per pyranose unit in a controlled manner. Deprotection of the product afforded the cellulose having N-acetyl-d-glucosamine or d-glucosamine branches depending on the reaction conditions. The deprotected nonnatural branched polysaccharides were readily soluble in neutral water as well as common organic solvents and would be promising as a new type of water-soluble amino polysaccharides.     

Immobilized iron Schiff base histidine complexes on Al-MCM-41 and zeolite Y as catalyst for oxidation of cycloalkanes

Iron complexes of N-salicylidene-l-histidine with or without bipyridine ligand immobilized on Al-MCM-41 and zeolite Y designated as Fe(sal-l-his)(bipy)complex/Al-MCM-41 or Fe(sal-l-his)complex/Al-MCM-41 and Fe(sal-l-his)(bpy)complex/Y or Fe(sal-l-his)complex/Y respectively, were prepared and characterized by X-ray powder diffraction (XRD), FT-IR, N₂ adsorption/desorption and chemical analysis techniques. Fe(sal-l-his)/Al-MCM-41 and Fe(sal-l-his)(bipy)complex/Al-MCM-41 were found to successfully catalyze the oxidation of cyclohexane, methyl cyclohexane, cyclooctane and adamantane with H₂O₂. The oxidation results and promising catalytic behavior of Fe(sal-l-his)(bipy)complex/Al-MCM-41 for oxidation of cyclooctane with 90 % conversion and excellent selectivity toward the formation of cyclooctanone will be discussed in this presentation.     

Hydrogenation of l-Arabinose and d-Galactose Mixtures Over a Heterogeneous Ru/C Catalyst

Complete hydrogenation of d-galactose and l-arabinose mixtures on a Ru/C catalyst was achieved with excellent selectivities exceeding 95?%. No unexpected effects of temperature and pressure were observed. A detailed kinetic model was derived to describe the simultaneous hydrogenation of the monomeric sugars.     

Poly(ester amide)s based on l-lactic acid oligomers and glycine: the role of the central unit of the l-lactic acid oligomers and their molecular weight in the poly(ester amide)s properties

Novel biodegradable poly(ester amide)s (PEAs) based on l-lactic acid (l-LA) oligomers and glycine were successfully synthesized, through an easy and fast procedure, making use of inexpensive starting materials. The l-LA oligomers were prepared with different central units and different molecular weights in order to access the influence of such parameters in the final properties of the PEAs’. Both the central unit of the l-LA oligomer and its molecular weight have important influence in the PEAs’ final properties. The thermal stability is lower for the PEAs containing the l-LA with the shortest central unit and for the PEAs based on the l-LA oligomers of high molecular weight. The PEAs exhibit a semi-crystalline nature, except those derived from the l-LA oligomers with high molecular weight, which have an amorphous character. Both hydrolytic and enzymatic degradation are more pronounced in PEAs synthesized from the l-LA oligomers with low molecular weight. Different mechanisms of degradation were found for the PEAs: bulk erosion and surface erosion, for hydrolytic degradation and enzymatic degradation tests, respectively.     

Synthesis of 6-Substituted 1-oxoindanoyl Isoleucine Conjugates and Modeling Studies with the COI1-JAZ Co-Receptor Complex of Lima Bean

The conjugates of 6-substituted 1-oxoindanoyl carboxylic acids with L-isoleucine are mimics of the plant hormone (+)-7-iso-JA-L-Ile (3) that controls and regulates secondary metabolism and stress responses. In order to generate ligands that can be used as hormone-like compounds possessing different biological activities, an efficient and short synthesis of 6-bromo-1-oxoindane-4-carboxylic acid opens a general route to 6-Br-1-oxoindanoyl L-isoleucine conjugate (Br-In-L-Ile) (9a) as a key intermediate for several bioactive 6-halogen-In-L-Ile analogs (7a, 8a, 10a). The 6-ethynyl-In-L-Ile analog (11a) might be a valuable tool to localize macromolecular receptor molecules by click-chemistry. The activities of In-Ile derivatives were evaluated by assays inducing the release of volatile organic compounds (VOCs) in lima bean (Phaseolus lunatus). Each compound showed slightly different VOC induction patterns. To correlate such differences with structural features, modeling studies of In-Ile derivatives with COI-JAZa/b/c co-receptors of P. lunatus were performed. The modeling profits from the rigid backbone of the 1-oxoindanonoyl conjugates, which allows only well defined interactions with the receptor complex.     

Amprometric detection of Glycine, l-Serine, and l-Alanine using glassy carbon electrode modified by NiO nanoparticles

Glassy carbon electrode modified with nickel oxide nanoparticles has been used to investigate the electrochemical oxidation of Glycine, l-Serine, and l-Alanine in an alkaloid solution. The electrochemical behavior of the modified electrode was characterized by cyclic voltammetry in detail. The electrocatalytic behavior is further exploited as a sensitive detection scheme for the above amino acids by hydrodynamic amperometry. Under optimized conditions, the calibration curves are linear in the concentration ranges of 1–200?μM for Glycine, 1–400?μM for l-Serine, and 30–200?μM for l-Alanine, respectively. The respective detection limit (S/N?=?3) and sensitivity are 0.9?μM and 24.3 nA μM^?1 for Glycine, 0.85?μM and 12.4 nA μM^?1 for l-Serine, and 29.67?μM and 0.4 nA μM^?1 for l-Alanine. The prepared electrode exhibits a satisfactory stability and long life-time, while it is stored at ambient conditions.     

Optimization of temperature swing strategy for selective cooling crystallization of α-form l-glutamic acid crystals

l-glutamic acid can be crystallized as metastable α-form and stable β-form crystal. The α-form is desired because of its prismatic shape. Production of α-form of l-glutamic acid by cooling crystallization is not well-defined and α-form solid is commercially not available. In this study, an optimal cooling strategy to selectively produce large and narrowly distributed α-crystals is found by modeling and optimizing the crystallization and polymorphic transformation of l-glutamic acid. The optimal temperature profile is found to be cooling-heating-cooling concept where short nucleation period is followed by growth period in metastable zone. The obtained α-form of L-glutamic acid by optimal strategy had improved mean size, distribution, and purity compared to constant cooling.     

Chiral Homobimetallic Palladium(II) Complexes Composed of Chirality-Organized Quinonediimines Bearing Amino Acid Moieties

The chirality-organized quinonediimine derivatives bearing amino acid moieties were demonstrated to react with 2 molar equiv. of Pd(OAc)₂, resulting in the formation of the chiral homobimetallic palladium(II) complexes. The crystal structures of the chiral conjugated complexes revealed the coordination of the quinonediimine nitrogen to a palladium center and a chiral propeller twist conformation of the π-conjugated backbone. The mirror image relationship of the CD signals around the quinonediimine moieties in acetonitrile was observed between l- and d-derivatives, indicating the preservation of the chirality-organized structures even in a solution.     

l-Carnitine and Long-Chain Acylcarnitines are Positively Correlated with Ambulatory Blood Pressure in Humans: The SABPA Study

The prevalence of hypertension in sub-Saharan Africa is increasing rapidly, and treatment remains challenging. Although the use of l-carnitine in treatment has received much attention, studies reporting on physiological l-carnitine levels in hypertensives are limited. Our aim was to determine physiological levels of l-carnitine and acylcarnitines in African and Caucasian men, and to investigate associations between ambulatory blood pressure (BP) and carnitine levels. Participants included 101 African and 101 Caucasian teachers. Ambulatory BP measurements were conducted, and l-carnitine and acylcarnitine levels determined. African men showed significantly higher systolic BP (p < 0.001), diastolic BP (p < 0.001) and l-carnitine levels (p = 0.01). In both ethnic groups, partial regression analyses revealed a positive association between BP and l-carnitine, although in Caucasians it was with systolic (r = 0.20, p = 0.045), and in Africans with diastolic BP (r = 0.23, p = 0.023). After adjusting for confounders, an independent positive association between systolic (R ² = 0.37, β = 0.12, p = 0.041) and diastolic BP (R ² = 0.39, β = 0.14, p = 0.018) and l-carnitine and long-chain acylcarnitines (R ² = 0.38, β = 0.17, p = 0.005 and R ² = 0.39, β = 0.15, p = 0.011) were found, independent of ethnicity. Physiological l-carnitine levels were not only higher in Africans than in Caucasians but also above the expected reference range. Despite promising results on l-carnitine (and its short-chain derivatives) in hypertension treatment regimens, our findings paradoxically show that elevated BP is significantly associated with higher physiological l-carnitine and long-chain acylcarnitine levels.     

l-Lactic acid biosensor based on multi-layered graphene

Pristine graphene platelets and graphene oxide were used as electrode modifiers, aiming the investigation of their electrochemical efficacy towards β-nicotinamide adenine dinucleotide (NADH). The electrochemical detection of NADH is one of the most studied areas of bioelectroanalysis because of the ubiquity of NAD(P)H-based enzymatic reactions in nature. Commercially available graphene and laboratory prepared graphene oxide were used to modify glassy carbon electrodes and the behaviour of such modified electrodes against potassium ferricyanide (III) and NADH was reported. Relying on the graphene-modified transducer, l-lactic dehydrogenase (l-LDH) was successfully immobilised in a 1 % Nafion^® membrane. The developed biosensor, working at +250 mV versus Ag/AgCl reference electrode, was used to assess l-lactic acid in four different types of yogurts, revealing an l-lactic acid concentration ranging between 0.3 and 0.6 %.     

Porous chitosan-based adhesive patch filled with poly(l-3,4-dihydroxyphenylalanine) as a transdermal drug-delivery system

Bioadhesives have been widely used on surgical areas for more than 50 years. Despite their numerous advantages, drawbacks such as cytotoxicity and low efficiency of transdermal drug delivery have limited their applications. Consequently, bioadhesives are mainly used during emergencies. To improve the physical properties of bioadhesive materials, poly(l-3,4-dihydroxyphenylalanine) or poly(l-DOPA) was synthesized and used to fill 2 kinds of porous chitosan patches (high and medium molecular weight). Bioaddisive and patch properties such as bond strength, drug-delivery efficiency, morphology, cytotoxicity, and histology were characterized. We ascertained that the optimal combination for high bond strength was 77.9 % polymethacrylic acid (PMA, molecular weight: 9,500 Da) and 22.1 % l-DOPA. Drug release was 1.5 times faster from the poly(l-DOPA)-filled chitosan patch of medium molecular weight than from the high molecular weight patch. Further, the medium molecular weight chitosan patch was more efficient at wound healing than commercial glue. These results indicate that chitosan-based materials filled with poly(l-DOPA) can be used as adhesive patches in various fields.     

Effect of l-Histidine Substitution on Sol–Gel of Transition Metal Coordinated Poly Ethyleneimine: Synthesis and Biochemical Characterization

The study was aimed to investigate the effect of chemical modification of branched poly ethyleneimine (PEI) on chelation of transition metal ions (Me²⁺) including Zn²⁺, Cu²⁺ or Ni²⁺ and sol–gel conversion thereof. To modulate chelation property of PEI, imidazole moieties were introduced into the polymer backbone by carbodiimide chemistry at different molar ratios of fmoc-protected l-histidine. The synthesis was characterized by ¹H-NMR spectroscopy and size exclusion chromatography. Potentiometric titration of PEI/Me²⁺ aqueous dispersions showed formation of stable complexes at pH above 5 depending on the degree of l-histidine substitution. FT-IR spectroscopy showed the imidazole ring of l-histidine was involved in the coordination interactions between PEI and Me²⁺. Addition of Zn²⁺ to PEI solution induced sol–gel conversion at a critical molar ratio decreasing by a higher degree of l-histidine modification. The gelation process led to formation of stable globular nanostructures as confirmed by atomic force microscopy with projected mean diameters less than 200 nm. Cellular experiment showed that l-histidine substitution enhanced cyto-compatibility of PEI, moreover cytotoxicity decreased significantly upon coordination of Zn²⁺ with the polymers. Conclusively, the coordination complexes of Zn²⁺ and l-histidine substituted PEI could serve as a nano system for biomedical applications.     

Synthesis of ε-caprolactone-b-l-lactide block copolymers by mean sequential polymerization,using diphenylzinc as initiator

Block copolymers of ε-caprolactone (CL) and l-lactide (l-LA) were synthesized by sequential polymerization using diphenylzinc as initiator. The composition of the copolymers was adjusted changing the comonomers in ratio. Copolymers were characterized by ¹H-NMR, ¹³C-NMR, DSC, and GPC. Results indicate that poly(ε-caprolactone)-b-poly(l-lactide) (PCL-b-PLA) block copolymers had a narrow molecular weight distribution and well-controlled sequences without random placement.     

The total synthesis of phosphatidyl(Dioleoyl)hydroxy-l-proline and its activity in blood-clotting systems

The phthalimidomethyl ester ofN-anisyloxycarbonyl-hydroxy-l-proline was combined with phosphorus oxychloride andrac-1,2-diolein. The diolein was made by large-scale preparative application of the method of Krabisch and Borgström (1). The protected phosphatide, obtained by the phosphorylation reaction, was stripped of its protective groups under mild conditions. The phosphatidyl(dioleoyl)-hydroxy-l-proline was purified by TEAE cellulose (acetate) chromatography, as developed by Rouser (6), also by silicic acid chromatography. Aqueous dispersions of the material were tested for anticoagulant activity in the antithrom-boplastin test and the Hicks-Pitney test. The new phosphatide had about one-tenth of the activity of beef brain phosphatidylserine.     

Transition Metal Free Catalytic Aerobic Oxidation of Methyl-α-d-Glucopyranoside Under Mild Conditions Using Stable Nitroxyl Free Radicals

The selective oxidation of alcohols to the corresponding aldehydes, ketones or acids is an essential transformation in organic synthesis and a large number of reagents have been developed for this reaction (Kirk-Othmer, Encyclopedia of chemical technology, 1992; Hudlicky, Oxidations in organic chemistry, 1990; Sheldon and Kochi, Metal-catalyzed oxidations of organic compounds, 1981). Many of these well established procedures require the use of a toxic stoichiometric oxidant, transition metal catalyst and/or halogenated solvents. In this respect, the TEMPO (2,2,6,6,-tetramethylpiperidine-N-oxyl) based compositions have emerged as highly selective catalyst systems for the oxidation of primary alcohols to the corresponding aldehydes or acids (Holum, J Org Chem 26:4814, 1961; Lee and Spitzer, J Org Chem 35:3589, 1970). Here, we report on a new catalyst composition for the aerobic oxidation of methyl-??-d-glucopyranoside (1) to the corresponding methyl-??-d-glucuronic acid (2). The catalyst system is based on 4-acetamido-2,2,6,6-tetramethylpiperidine N-oxyl (AA-TEMPO, 3b) and a nitrate source. It utilizes ecologically friendly solvents and does not require any transition metal co-catalyst. It has been shown that the described process represents an efficient oxidation protocol that can easily and safely be scaled up to commercial scale. The influence of the most critical reaction parameters such as the nature of the substituent on the TEMPO structure, the nitrate source and the temperature?Cpressure matrix have been studied. By a detailed analysis of the effect of each of the reaction variables on the oxidation rate, a reaction pathway including a multistep cascade is presented.