Spectroscopic Studies of R(+)-α-Lipoic Acid—Cyclodextrin Complexes

α-Lipoic acid (ALA) has a chiral center at the C6 position, and exists as two enantiomers, R(+)-ALA (RALA) and S(−)-ALA (SALA). RALA is naturally occurring, and is a cofactor for mitochondrial enzymes, therefore playing a major role in energy metabolism. However, RALA cannot be used for pharmaceuticals or nutraceuticals because it readily polymerizes via a 1,2-dithiolane ring-opening when exposed to light or heat. So, it is highly desired to find out the method to stabilize RALA. The purpose of this study is to provide the spectroscopic information of stabilized RALA and SALA through complexation with cyclodextrins (CDs), α-CD, β-CD and γ-CD and to examine the physical characteristics of the resultant complexes in the solid state. The RALA-CD structures were elucidated based on the micro fourier transform infrared (FT-IR) and Raman analyses. The FT-IR results showed that the C=O stretching vibration of RALA appeared at 1717 cm⁻¹ and then shifted on formation of the RALA-CD complexes. The Raman spectra showed that the S–S and C–S stretching vibrations for RALA at 511 cm⁻¹ (S–S), 631 cm⁻¹ (C–S) and 675 cm⁻¹ (C–S) drastically weakened and almost disappeared upon complexation with CDs. Several peaks indicative of O–H vibrations also shifted or changed in intensity. These results indicate that RALA and CDs form host-guest complexes by interacting with one another.     

Synthesis and Sulfonation of an Aluminum-Based Metal–Organic Framework with Microwave Method and Using for the Esterification of Oleic Acid

Journal of Inorganic and Organometallic Polymers and Materials - In this study, the synthesis of MIL-53(Al) (Material Institute Lavoisier, MIL) material, which is an aluminum-containing...     

Structural Analysis of Crystalline R(+)-α-Lipoic Acid-α-cyclodextrin Complex Based on Microscopic and Spectroscopic Studies

R(+)-α-lipoic acid (RALA) is a naturally-occurring substance, and its protein-bound form plays significant role in the energy metabolism in the mitochondria. RALA is vulnerable to a variety of physical stimuli, including heat and UV light, which prompted us to study the stability of its complexes with cyclodextrins (CDs). In this study, we have prepared and purified a crystalline RALA-αCD complex and evaluated its properties in the solid state. The results of ¹H NMR and PXRD analyses indicated that the crystalline RALA-αCD complex is a channel type complex with a molar ratio of 2:3 (RALA:α-CD). Attenuated total reflection/Fourier transform infrared analysis of the complex showed the shift of the C=O stretching vibration of RALA due to the formation of the RALA-αCD complex. Raman spectroscopic analysis revealed the significant weakness of the S–S and C–S stretching vibrations of RALA in the RALA-αCD complex implying that the dithiolane ring of RALA is almost enclosed in glucose ring of α-CD. Extent of this effect was dependent on the direction of the excitation laser to the hexagonal morphology of the crystal. Solid-state NMR analysis allowed for the chemical shift of the C=O peak to be precisely determined. These results suggested that RALA was positioned in the α-CD cavity with its 1,2-dithiolane ring orientated perpendicular to the plane of the α-CD ring.     

Synthesis of (S)-α-amino oleic acid

An efficient synthesis of (S)-α-amino oleic acid was developed. The fully protected FA derivative was obtained in four steps starting from methyl (2S)-2-[bis(tert-butoxycar-bonyl)amino]-5-oxopentanoate. These steps are (i) olefination of the starting aldehyde with the appropriate phosphonate anion, (ii) hydrogenation of the double bonds, (iii) controlled reduction of ω-ethyl ester to an aldehyde in the presence of α-methyl ester, and (iv) a Wittig reaction of the latter aldehyde with the suitable ylide. Free α-amino oleic acid was prepared after deprotection of the amino group followed by saponification in a total yield of 24%. N-tert-Butoxycarbonyl-protected amino oleic acid and the corresponding amino alcohol were prepared in high yield. The structures of the products have been established by various spectroscopic techniques.     

Optimization of Enzymatic Synthesis of n-Propyl Acetate (Fruit Flavor Ester) – Effect of the Support on the Properties of Biocatalysts

The present study deals with the optimization of the enzymatic synthesis of n-propyl acetate using response surface methodology (RSM). The biocatalysts were prepared by physical adsorption of lipase from Thermomyces lanuginosus (TLL) on mesoporous hydrophobic supports – poly-hydroxybutyrate (PHB) and poly-methacrylate (PMA) particles. Their catalytic properties were also assayed in the hydrolysis of olive oil emulsion. The biocatalyst TLL–PMA presented the highest immobilization yield (IY, 90.6 ± 2.8%), immobilized protein concentration (36.5 ± 0.4 mg/g of PMA), and catalytic activity in esterification reaction. TLL–PHB was more active in the hydrolysis of olive oil emulsion by a four-fold factor (1240.5 ± 29.2 IU/g of PHB). Maximum acid consumption percentage of 84.3% was observed after 50 min of reaction catalyzed by TLL–PMA using 2000 mM of each reactant (n-propanol and acetic acid) in heptane medium. The purified ester was confirmed by gas chromatography mass spectrometry (GC–MS) analysis. After six consecutive cycles of esterification reaction, the biocatalyst retained around 50% of its initial activity. The results show that PMA may be an interesting support to prepare active biocatalysts in the synthesis of fruit flavor ester by esterification reaction.     

Synthesis and Structural Characterization of Triorganotin(IV) Derivatives with 2,2′-Thiodiglycolic Acid and 3,3′-Thiodipropionic Acid

The synthesis and structural characterization of four novel triorganotin(IV) complexes, {(R₃Sn)₂[C₂H₄S(COO)₂]} _n (R = Me: 1), {(R₃Sn)₄[C₂H₄S(COO)₂]₂} _n (R = nBu: 2), {(R₃Sn)₂[C₄H₈S(COO)₂]} _n (R = Me: 3; nBu: 4) were obtained by the reaction of 2,2′-thiodiglycolic acid, 3,3′-thiodipropionic acid and the corresponding R₃SnCl (R = Me, nBu) with potassium hydroxide in methanol. All the complexes were characterized by elemental analysis, Fourier transform infrared and nuclear magnetic resonance (¹H, ¹³C, ¹¹⁹Sn) spectroscopies, X-ray crystallography and thermogravimetric analyses. The crystal structures show that 1 has 2D network structure in which 2,2′-thiodiglycolic acid acts as a tetradentate ligand coordinating to the trimethyltin(IV) ions. Complexes 2, 3, and 4 are 3D metal-organic framework structures in which the deprotoned acids act as a tetradentate ligand afforded by four oxygen atoms.     

Synthesis and Characterization of Poly(Ethyleneimine)-Modified Poly(Acrylic Acid)-Grafted Nanocellulose/Nanobentonite Superabsorbent Hydrogel for the Selective Recovery of β-Casein From Aqueous Solutions

A novel adsorbent, poly(ethyleneimine)-modified poly(acrylic acid)-grafted nanocellulose/nanobentonite superabsorbent hydrogel (PEI-PAA-g-NC/NB) was prepared by free radical graft copolymerization technique and well characterized. Swelling behavior of adsorbent was studied under different pH and temperatures. The various adsorption parameters for the adsorption of the protein, β-Casein (βCN) onto the PEI-PAA-g-NC/NB were investigated. Sips adsorption isotherm and pseudo-first-order kinetic model were best suited for the present adsorbent. The adsorption-desorption experiments were conducted with 0.1 M NaSCN for four cycles. The results of the present investigation proved that PEI-PAA-g-NC/NB is highly effective for the separation of βCN from aqueous solutions.     

Synthesis of Octa(maleimidophenyl) silsesquioxane–SiO2/TiO2 Hybrid Nanocomposites: Adsorption Behavior for the Removal of an Organic Methylene Blue Dye and Antimicrobial Activity against Pathogens

In this study, a sol–gel process was used to prepare hybrid nanocomposite consisting of octa(maleimidophenyl) silsesquioxane-silica/titania (maleimide–POSS (polyhedral oligomeric silsesquioxanes)–SiO₂/TiO₂) to use in methylene blue (MB) adsorption and as an antibacterial agent. The structure, surface, and morphological characteristics were confirmed through Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The optical and thermal stabilities were studied by conducting UV–visible and thermogravimetric analysis–differential scanning electron calorimetry analysis. The experimental results showed a maximum dye adsorption capacity of 92% achieved using 0.5?g of hybrid nanocomposite after 2.5?h at pH 9. We also investigated the effect that the adsorbent dosage, pH, and contact time had on the removal efficiency of the MB dye in aqueous solution. The recycling experiment showed a good adsorption capacity of the MB dye, even after five repeated cycles. Furthermore, the hybrid nanocomposite was tested against pathogenic bacteria, such as Bacillus cereus, Lactobacillus, Escherichia coli, and Pseudomonas aeruginosa. The nanocomposite was observed to be highly sensitive to E. coli, B. cereus, and P. aeruginosa, as confirmed by the size of the zone inhibition.     

Surface Treatment of ZrO2 Nanoparticles with Biosafe Citric Acid and Its Utilization for the Synthesis of L-leucine Based Poly(Amide–Imide) Nanocomposites

This study aimed at preparing three nanocomposites of optically active poly(amide–imide) and zirconium dioxide (ZrO₂) inorganic nanoparticles through the ultrasonic process. First, the surface of ZrO₂ nanocomposites was chemically modified with bio-active citric acid in the basic media. Then, the poly(amide–imide) was reinforced with modified nanocomposites and three poly(amide–imide)/ZrO₂-citric acid nanocomposites were synthesized by ultrasonic irradiation. The poly(amide–imide) was prepared by polycondensation of N-trimellitylimido-L-leucine with 4,4′-diaminodiphenylsulfone using of triphenyl phosphite and molten tetra-n-butylammonium bromide as green media. The obtained poly(amide–imide)/ZrO₂-citric acid nanocomposites were characterized by different techniques.     

Preparation and Performance of Poly(Lactic Acid)-γ-Cyclodextrin Inclusion Complex-Poly(Lactic Acid) Multibranched Polymers by the Reactive Extrusion Process

The poly(lactic acid)-γ-cyclodextrin inclusion complex-poly(lactic acid) multibranched polymers were prepared by reactive extrusion process with L-lactide as raw material, stannous octoate as catalyst and the carboxyl poly(lactic acid)-γ-cyclodextrin inclusion compound as cores prepared by ultrasonic coprecipitation and carboxylation reaction. It was shown that the comprehensive performance of poly(lactic acid)-γ-cyclodextrin inclusion complex-poly(lactic acid) had been significantly improved compared with liner poly(lactic acid) by the study of structure and properties. Thus, the novel poly(lactic acid)-γ-cyclodextrin inclusion complex-poly(lactic acid) multibranched polymers have a potential use in biomedical materials. This study provided a simple and feasible preparation method for improving the performance of poly(lactic acid).     

Microwave-Assisted Solvothermal Synthesis and Photocatalytic Activity of Bismuth(III) Based Metal–Organic Framework

This study aims to synthesize and evaluate the photocatalytic activity of bismuth terephthalate material (Bi-BDC) synthesized by solvothermal (ST) and microwave-assisted solvothermal (MW) methods. Differences in the crystal structure and crystal shape were assessed by analytical methods such as X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared (FT-IR) spectrum, X-ray photoelectron spectroscopy (XPS), N₂ adsorption/desorption, Raman spectrum, and thermal gravimetric analysis (TGA). From XRD, IR, Raman, and XPS results, the fully crystallized Bi-BDC materials were achieved regardless of the preparation router. Bi-BDC-MW exhibited spherical-like morphologies, producing between stacked lamellar, while Bi-BDC-ST method exhibited a heterogeneous structure. The TGA data indicated that Bi-BDC is thermally stable up to 300 °C, suggesting the excellent thermal stability of Bi-BDC. The surface area and pore volume of Bi-BDC-MW (18 m²/g and 85 × 10^?3 cm³/g) are higher than those of Bi-BDC-ST (16 m²/g and 52 × 10^?3 cm³/g), which is due to its well-defined lamellar microstructure and homogeneity of the crystals. Compared to Bi-BDC-ST, Bi-BDC-MW has a higher value in the content of oxygen vacancy. Moreover, the photocatalytic efficiency of Bi-BDC-MW was significantly higher than that of Bi-BDC-ST, in which 99.44% rhodamine B (RhB) is removed after 360 min of irradiation. The improved photocatalytic efficiency of Bi-BDC-MW is ascribed to the morphology, specific surface area, and oxygen defects, which exhibited the good separation of electrons and holes, as confirmed by the photoluminescence (PL). The results should open a new approach to enhancing the photocatalytic activity of bismuth terephthalate materials.

     

4-(Succinimido)-1-butane Sulfonic Acid as a Brönsted Acid Catalyst for Synthesis of 4,4′-(arylmethylene)bis(1H-pyrazol-5-ol)s Derivatives under Solvent-Free Conditions

4-(Succinimido)-1-butane sulfonic acid as a efficient and reusable Brönsted acid catalyzed the synthesis of 4,4′-(arylmethylene)bis(1H-pyrazol-5-ol) derivatives under solvent-free conditions. The catalyst can be prepared by mixing succinimide and 1,4-butanesultone that is simpler and safer than the preparation of succinimide sulfonic acid. This method has the advantages of high yield, clean reaction, simple methodology, and short reaction time. The catalyst could be recycled without significant loss of activity.     

Synergistic Extraction and Separation of Heavy Lanthanide by Mixtures of Bis(2,4,4‐trimethylpentyl)phosphinic Acid and 2‐Ethylhexyl Phosphinic Acid Mono‐2‐Ethylhexyl Ester

Abstract

The extraction of Yb³⁺ from chloride solution has been studied using mixtures of bis(2,4,4‐trimethylpentyl)phosphinic acid (Cyanex272) and 2‐ethylhexyl phosphinic acid mono‐2‐ethylhexl ester (P507). The results show that Yb³⁺ is extracted into heptane as YbA₃(HA)₃ with Cyanex272, YbL₃(HL)₃ with P507, and YbA₂L₄H₃ with synergistic mixture. The equilibrium constants, formation constants, and thermodynamic functions have been determined. Extraction mechanism and extraction process are also proposed. The extraction of heavy lanthanide ions by mixtures of Cyanex272 and P507 is studied and the possibility of separating heavy rare earth ions is discussed.     

Synthesis and Characterization of New Cobalt(II)–Pyrazine Coordination Polymer as Precursor for Preparation of Co(II) Oxide Nanoparticles: Surprising Coordination,DFT Calculation and Spectroscopic Studies

The new 2-D cobalt(II) coordination polymer with pyrazine was synthesized surprisingly from reaction of CoCl₂ and tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2?,3?-j]phenazine (tpphz) in methanol as medium and characterized by means of Fourier transform infrared spectroscopy (FT-IR), UV–Vis spectroscopy and X-ray single crystal analysis. The results showed that coordination polymer consist of cobalt(II) chain with pyrazine-bridged which crystallizes in orthorhombic unit cell (a?=?10.1307, b?=?10.1310, c?=?10.6838 Å) and space group Pban. Density functional theory (DFT) calculations were also done to figure out the electronic structure of the compound from theoretical aspect. The electronic spectrum of coordination polymer was investigated and the DFT/TDDFT procedures were employed to assign the absorption bands. The thermal decomposition of the title compound resulted in formation of cobalt(II) oxide nanoparticles with average size of 50 nm.     

Synthesis, Structure and Luminescence Property of Cadmium(II) Coordination Polymer with Mixed 5-(Oxidediphenylphosphino)isophthalic Acid and 4,4′-Bipyridine Ligands

A new metal–organic framework {[Cd(L)(4,4′-bpy)]₂·5H₂O} _n (1) had been synthesized by hydrothermal reaction of 5-(oxidediphenylphosphino)isophthalic acid, Cd(II) nitrate, NaOH and 4,4′-bipyridine (4,4′-bpy) as co-ligand. The novel compound was characterized by single crystal X-ray diffractometry as well as FTIR spectrum. Adjacent eight-member (C₂Cd₂O₄) rings are connected each other through pairs of L^2? ligands to result in a 1D double chain. Such ribbons are interconnected together by 4,4′-bpy to generate a 2D pillared layer, which are further held together by rich O–H···O hydrogen bonds to give a 3D supramolecular network. Solvent water molecules play an important role to bridge adjacent layers to form a 3D supramolecular architecture. The luminescence property and thermogravimetric analysis of title complex were investigated.     

A Hybrid Membrane of Poly(vinyl alcohol) and Phosphotungstic Acid for Fuel Cells

Proton conducting membranes composed of phosphotungstic acid (PWA) and poly(vinyl alcohol) (PVA) were prepared. Conductivity and Fourier transform infrared spectrometer(FTIR) measurements show that most of the acid embedded are stable in the PVA matrix when the membrane is immerged in water or methanol solution at room temperature. Conductivity of the composite membranes scatters around 10-3S·cm-1 at room temperature. The methanol crossover through the membranes is about an order of magnitude lower than that through Nafion 117 membrane.