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.     

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.     

Poly(l-lactide) initiated by silver N-heterocyclic carbene complexes: synthesis, characterization and properties

Poly(l-lactide) (PLLA) was successfully synthesized by ring-opening polymerization (ROP) in bulk using silver N-heterocyclic carbene (Ag–NHC) complex. The effect of reaction time, temperature and monomer/initiator ratio on polymerization process were determined. The optimum conditions were found as 130 °C, 4 h and M/I molar ratio of about 100. The polymers were characterized by FTIR, ¹H-NMR, GPC and TG. High-molecular-weight PLLA (M _w = 3.78 × 10⁴, M _n = 1.91 × 10⁴, PDI = 1.97) was synthesized by the ROP of l-lactide (LLA) with bis-(N-methyl N′-dodecylimidazole) silver(I) di-bromo argentate (1a) in bulk. The effect of different N-substituted ligand groups on the polymerization was studied. The antimicrobial activity of the synthesized polymers were investigated by using minimum inhibitory concentration test against gram positive (Staphylococcus aureus) and gram negative (Escherichia coli and Pseudomonas aeruginosa). It was observed that the synthesized polymers displayed moderate antimicrobial activity.     

Thermo-mechanical properties of MWCNT-g-poly (l-lactide)/poly (l-lactide) nanocomposites

The thermo-mechanical properties of poly (l-lactide) (PLLA) biodegradable polymer reinforced with PLLA grafted from multiwalled carbon nanotubes (MWCNT-g-PLLA)s are characterized. The crystallinity of PLLA polymer matrix affected by MWCNT-g-PLLAs is illuminated. For this purpose, the PLLA chains are covalently grafted from the sidewall of aminated MWCNTs. Then, the MWCNT-g-PLLAs/PLLA composite films are prepared by solution casting using chloroform as solvent. It is found that the MWCNT-g-PLLAs well dispersed in PLLA matrix. The mechanical properties of PLLA enhanced gradually with the increasing concentrations of MWCNT-g-PLLAs up to 2 wt%. The MWCNT-g-PLLAs increase the glass transition temperature (T _g) and melting point of PLLA as revealed by the curves from differential scanning calorimeter (DSC). In addition, the dynamic mechanical analysis (DMA) results show that the T _g and Young modulus of PLLA increase with the increment in the concentrations of MWCNT-g-PLLAs. Due to the homogenous dispersion of MWCNT-g-PLLAs and the van der Walls force between grafted PLLA chains on the sidewall of MWCNTs and the PLLA matrix chains, the chain stiffness in amorphous phase of PLLA increases. In addition, the MWCNT-g-PLLAs as heterogeneous nucleation agents increase the crystallinity of PLLA.     

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.     

Synthesis and characterization of biodegradable poly(l-lactide)/layered double hydroxide nanocomposites

The effects of layered double hydroxide (LDH) composed by calcium/aluminum and magnesium/iron as divalent/trivalent cations and intercalated with dodecyl sulfate anion in the properties of poly(l-lactide) (PLLA) were analyzed. Two PLLA nanocomposites were produced by in situ intercalative bulk polymerization using 1 and 2 wt% of LDH. The PLLA nanocomposites were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and ultraviolet–visible spectroscopy (UV–VIS). XRD results demonstrated that PLLA nanocomposites showed a good dispersion of LDH in the polymeric matrix, which may have caused an increase in thermal stability indicated by thermogravimetric analysis. UV–VIS analyses showed that PLLA nanocomposites presented lower transmittance values when compared to the neat PLLA, which is an interesting characteristic for plastics used in food packaging. This enhancement in the properties of PLLA nanocomposites can enlarge the range of applications of this material in several areas.     

Aggregation of polylactide with carboxyl groups at one chain end in the presence of metal cations

Polylactides with one or more carboxyl groups at one chain end were synthesized by cationic polymerization according to activated monomer mechanism and by application of “thiol-yne” click chemistry for subsequent functionalization. End groups of such obtained polylactides were converted into ionic groups by neutralization of polymer solutions with metal oxides, mainly calcium oxide, and the aggregation of individual stereoisomers as well as that of the mixture of poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) was investigated. The extent and progress of the aggregation was followed by viscosity measurements, and aggregated polymers in the solid state were examined by SEM and DSC. Solution viscosity increase was observed upon the aggregation of individual PLA stereoisomers, whereas PLA stereocomplex precipitation occurred in the case of the aggregation of PLLA/PDLA/metal oxide mixture.     

Synthesis and Properties of Poly(l-lactide)-b-poly (l-phenylalanine) Hybrid Copolymers

Hybrid materials constituted by peptides and synthetic polymers have nowadays a great interest since they can combine the properties and functions of each constitutive block, being also possible to modify the final characteristics by using different topologies. Poly(l-lactide-b-l-phenylalanine) copolymers with various block lengths were synthesized by sequential ring-opening polymerization of l-lactide and the N-carboxyanhydride of l-phenylalanine. The resulting block copolymers were characterized by NMR spectrometry, IR spectroscopy, gel permeation chromatography, MALDI-TOF and UV-vis, revealing the successful incorporation of the polyphenylalanine (PPhe) peptide into the previously formed poly(l-lactide) (PLLA) polymer chain. X-ray diffraction and DSC data also suggested that the copolymers were phase-separated in domains containing either crystalline PLLA or PPhe phases. A peculiar thermal behavior was also found by thermogravimetric analysis when polyphenylalanine blocks were incorporated into polylactide.     

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.     

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.     

Synthesis and properties of novel star-shaped polyesters based on l-lactide and castor oil

The topology of biodegradable polyesters can be adjusted by incorporating multifunctional polyols into the polyester backbone to obtain branched polymers. The aim of this study was to prepare the biodegradable-branched polyester polyols based on l-lactide and castor oil using the trifluoromethanesulfonic acid as a catalyst. FTIR and ¹H NMR spectroscopy measurements were used to estimate the molecular structure of the novel materials. The polyester polyol was synthesized by ‘‘core-first” method which involves a polymerization of l-lactide by using a castor oil as multifunctional initiator. Molar masses estimated by gel permeation chromatography and vapor pressure osmometry were in good correlation with calculated values based on hydroxyl number of obtained polymers. DSC measurements confirmed high crystallinity degree of the synthesized material. It was assessed that the molar masses of obtained polymers-influenced glass transition temperature significantly. The thermal stability was investigated by TG analysis, and the results have shown the dependence of weight loss on the arm length of the star-shaped polyesters. The thermal stability of star-shaped polyesters significantly decreased with degradation of polyester polyol obtained in acid solution.     

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.     

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.     

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.     

Fabrication of macroporous chitosan/poly(l-lactide) hybrid scaffolds by sodium acetate particulate-leaching method

For tissue engineering applications, 3-D macroporous chitosan/poly(l-lactide) (PLLA) scaffolds were prepared by the particulate-leaching method using sodium acetate as the porogen in an acidic water/dioxane solution. The stability and dispersity of chitosan on the chitosan/PLLA hybrid scaffolds were determined by measuring water contact angles, establishing crystallinity using X-ray diffraction, and using eosin staining to observe the chitosan under a light microscope. The porous structure of the particulate-leached chitosan/PLLA scaffolds was investigated in terms of pore morphology, interconnectivity, etc. by using scanning electron microscopy. Chitosan/PLLA scaffolds produced by particulate-leaching showed a highly porous structure and improved stability and dispersity of chitosan as compared to pure PLLA and chitosan-coated PLLA scaffolds. The highly porous structure that resulted from a high concentration of chitosan improved the efficiency of cell adhesion after culturing cells for 4?h. After 48?h, the cultured cells showed increased cell proliferation on the hybrid scaffolds. Thus, particulate-leached chitosan/PLLA scaffolds can be applied to tissue engineering of various types, including the industrial membrane field.     

Polymeric scaffolds based on blends of poly-l-lactic acid (PLLA) with poly-d-l-lactic acid (PLA) prepared via thermally induced phase separation (TIPS): demixing conditions and morphology

Porous scaffolds based on blends of high crystalline Poly-l-lactic acid (PLLA) with low crystalline poly-d-l-lactic acid (PLA) were prepared via Thermally Induced Phase Separation (TIPS), with the aim of exploring the possibility to control the degradation behaviour of the PLA-based scaffold, simultaneously preserving the morphological characteristics required for tissue engineering applications. Porous foams with different PLLA/PLA weight ratios (from 95/5 to 60/40) were produced and characterised in terms of pore size, porosity, and thermal properties. The scaffolds present an open porosity, with average pore sizes ranging from 30 to 70 μm. Results showed that, when dealing with a PLLA/PLA blend, some relevant processing conditions of the preparation process (above all demixing temperature and total polymer concentration) must be carefully tuned, in order to attain suitable structures in term of pore size and porosity. In particular, with increasing amounts of PLA in a PLLA/PLA blend, the demixing temperature must be decreased and the overall polymer concentration decreased. Moreover, a preliminary investigation regarding the in vitro biodegradation rate of the blends was attempted, based on the determination of the crystallinity through wide angle X-ray diffractometry.     

Preparations and reactions of alkyl ethers of some aldohexoses

Aldohexose, such asd-glucose,d-galactose ord-mannose, reacted with acetone to give the following O-isopropylidene derivatives: 1,2;5,6-di-O-isopropylidene-d-glucofuranose (IA), 1,2;3,4-di-O-isopropylidene-d-galactopyranose (IB) or 2,3;5,6-di-O-isopropylidene-D-mannofuranose (IC). The O-isopropylidene derivative (IA～IC) reacted with alkyl/alkenyl halogenide to yield aldohexose ether compounds containing di-O-isopropylidene group, 3-O-alkyl-1,2;5,6-di-O-isopropylidene-d-glucofuranose (II), 6-O-alkyl-1,2;3,4-di-O-isopropylidene-d-galactopyranose (III) or 1-O-alkyl-2,3;5,6-di-O-isopropylidene-d-mannofuranoside (IV), in good yields. The Williamson ether synthesis was carried out using phase-transfer catalysis (PTC). The derived aldohexose alkyl ether containing di-O-isopropylidene group was hydrolyzed to give 3-O-alkyl-1,2-O-isopropylidene-d-glucofuranose (V) as a partial hydrolysis product; the complete hydrolysis of I～IV gave, as expected, 3-O-alkyl-glucopyranose (VI), 6-O-alkyl-galactopyranose (VII) or 1-O-alkyl-mannofuranoside (VIII). Further alkylation of (V) with Mel under PTC and subsequent acid hydrolysis gave 3-O-alkyl-5,6-di-O-methyl-d-glucofuranose (X). Methanolysis of III with catalytic amounts of H₂SO₄ gave 1-O-methyl-6-O-alkyl-d-galactofuranoside (XI). The elucidation of the galactofuranoside skeleton of (XI) was determined by means of its¹³C nuclear magnetic resonance spectra. The O-alkyl aldohexoses, e.g., X and XI, were evaluated and found to be emulsifiers.     

Random copolymerization of ε-caprolactone and l-lactide with molybdenum complexes

Dioxomolybdenum complexes were examined as catalysts for the copolymerization of ε-caprolactone (ε-CL) and l-lactide (l-LA). The bis-[(5-OMe)salicylaldehydato]dioxomolybdenum complex completed the copolymerization after 20 h at 110 °C with 0.05 mol% of the catalyst to produce a copolymer in high yield. The microstructure of the copolymer was analyzed using ¹H and ¹³C NMR spectroscopy and was determined to have a random structure. The r values calculated from the heterodiad analysis of the ¹H NMR data were r _LA = 0.91 and r _CL = 0.93, and the L values calculated from the triad analysis of the ¹³C NMR data were L _LA = 1.58 and L _CL = 1.81. Other dioxomolybdenum complexes, such as cis-α MoO₂[(3-MeO)DiMeSaltn], MoO₂(acac)₂ and (NH₄)₈[Mo₁₀O₃₄] exhibited comparable or slightly lower reactivity for the copolymerization. Consecutive polymerization of ε-CL followed by l-LA afforded a block copolymer without trans-esterification.     

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 %.     

Investigation of cracks in GaN films grown by combined hydride and metal organic vapor-phase epitaxial method

Dissipative particle dynamics (DPD), a mesoscopic simulation approach, is used to investigate the effect of volume fraction of polyethylene (PE) and poly(l-lactide) (PLLA) on the structural property of the immiscible PE/PLLA/carbon nanotube in a system. In this work, the interaction parameter in DPD simulation, related to the Flory-Huggins interaction parameter χ, is estimated by the calculation of mixing energy for each pair of components in molecular dynamics simulation. Volume fraction and mixing methods clearly affect the equilibrated structure. Even if the volume fraction is different, micro-structures are similar when the equilibrated structures are different. Unlike the blend system, where no relationship exists between the micro-structure and the equilibrated structure, in the di-block copolymer system, the micro-structure and equilibrated structure have specific relationships.