Dissolution and gelation of α-chitin nanofibers using a simple NaOH treatment at low temperatures

In this study, both α-chitin powders and nanofibers were successfully dissolved in 20 wt% NaOH solutions at low temperatures. Elemental analysis confirmed that this NaOH-freezing treatment did not cause deacetylation of chitin. After heating and neutralizing with water, chitin hydrogels could be prepared. X-ray diffraction and field emission scanning electron microscope data demonstrated that these two hydrogels formed typical regenerated microporous structures with low crystallinity, which was caused by the dissolution process. Based on this result, cold ethanol was used for α-chitin nanofibers during the initial stages of neutralization, which effectively prevented the dissolution and decrease in crystallinity and was even able to preserve the continuous network structure of original nanofiber. This gelation behavior seems to be attributed to interdigitation and aggregation between neighboring nanofibers in cold alkali solution leading to the shrinkage of the hydrogel. In general, by avoiding the dissolution process, highly crystalline hydrogel based on α-chitin nanofibers was prepared by a simple NaOH treatment without use of any other chemical solvents or cross-linking agents. We expect this new type of hydrogel could be promoted to wide applications and research studies as novel green nanomaterials.     

Using TEMPO oxidation to tailor deacetylation of carboxyl β-chitin nanofibers from squid pen

Cellulose - 2,2,6,6-tetramethylpiperidine-1-oxyl-radical (TEMPO) oxidation is a classical method to obtain carboxyl chitin nanomaterials, but when the traditional TEMPO/NaBr/NaClO (TBN) oxidation...     

Preparation and characterization of crosslinked chitosan-based nanofibers

Crosslinked chitosan-based nanofibers were successfully prepared via electrospinning technique with heat mediated chemical crosslinking followed.The structure,morphology and mechanical property of nanofibers were characterized by attenuated total reflection-Fourier transform infrared spectroscopy(ATR-FTIR),scanning electron microscopy(SEM),Instron machine,respec- tively.The results showed that,nanofibers exhibited a smooth surface and regular morphology,and tensile strength of nanofibers improved with increasing of triethylene glycol dimethacrylate(TEGDMA)content.     

Observations on the Preparation of β-Lactose Octaacetate

Attempts to substantially increase the relative proportion of β-lactose octaacetate in products of acetylation of α-lactose monohydrate using various acetylation protocols failed. Nevertheless, the revised protocol for isolation and crystallization, based on the classical work by Hudson and Johnson, rendered preparation of β-lactose octaacetate less labor intensive. It is proposed that the melting point and [α]_D value are not reliable criteria of purity of β-lactose octaacetate, which can be confidently determined by 1H NMR spectroscopy.     

Synthesis of amphiphilic glycophospholipids based on β-cyclodextrins

An approach to the synthesis of amphiphilic glycophospholipids based on β-cyclodextrin (β-CD) was proposed. Distinctive features of the proposed method are the use of highly efficient trivalent phosphorus derivatives in the first steps of the synthesis and the regioselective monophosphorylation of nonprotected β-CD. The efficiency of using 13С NMR spectroscopy for the determination of the position and number of phospholipid residues introduced into the CD composition was shown.     

Preparation and enantioseparation characteristics of three chiral stationary phases based on modified β-cyclodextrin for liquid chromatography

In order to study the effect of the nature and the length of the spacer, three mixed 10-undecenoate/phenylcarbamate derivatives of β-cyclodextrin have been prepared and linked to allylsilica gel by means of a radical reaction. The chiral recognition ability of the resulting materials, when used as liquid chromatography chiral stationary phases (CSPs), was evaluated using heptane and either 2-propanol or chloroform as organic mobile-phase modifiers. A large variety of racemic compounds have been separated successfully on these CSPs (mainly pharmaceuticals and herbicides). Optimization of these separations was discussed in terms of mobile-phase composition and structural patterns of the injected analytes. The efficiencies of the three prepared materials were compared to those of previously described perphenylated-β-cyclodextrin column and to analogous cellulose derivative-based CSPs. Schematic illustration of the b-cyclodextrin/mandelic acid inclusion complex     

The Preparation of β-Hydroxysulfoxides

. Oxidation of β-hydroxy thioethers with MnO₂-aqu. 35%/HCl in methanol gives β-hydroxy sulfoxides in high yields.     

Synthesis and characterization of mechanically flexible and tough cellulose nanocrystals–polyacrylamide nanocomposite hydrogels

The unique combinations of hard and soft components with core/shell structures were proposed to synthesize high strength nanocomposite hydrogels. The elastomeric hydrogels containing rod-like cellulose nanocrystals (CNCs) core and polyacrylamide shell were made from aqueous solutions via free radical polymerization in the absence of chemical cross-links. The obtained hydrogels possessed greater tensile strength and elongation ratio when compared with chemically cross-linked counterparts. Oscillatory shear experiments indicated that CNCs interacted with polymer matrix via both chemical and physical interactions and contributed to the rubbery elasticity of the hydrogels. The nanocomposite hydrogels were more viscous than the chemical hydrogels, suggesting the addition of CNC led to the increase of energy dissipating and viscoelastic properties. The network structure model was proposed and it suggested that the high extensibilities and fracture stresses were related to the well-defined network structures with low cross-linking density and lack of noncovalent interactions among polymer chains, which may promote the rearrangements of network structure at high deformations.     

Crystalline alignment of metal ions templated by β-chitin ester

The highly crystalline β-chitin from diatom Thalassiosira weissflogii was esterified via intercalation with succinic anhydride followed by simple heating, maintaining the original crystalline order. Due to the introduced free carboxyl groups, the chitin ester crystal showed ion exchange ability for metal cations in aq. solution. Heavy metal cations such as Pb²⁺ bound to the β-chitin succinate gave characteristic X-ray diffraction patterns, indicating regular alignment of metal ions. Such materials represent a new type of organometallic architecture, possibly leading to novel functionalities.     

The rheology of hydrogels based on chitosan–gelatin (bio)polyelectrolyte complexes

Influence of the chitosan concentration in the low-concentrated acidic hydrogels formed by (bio)polyelectrolyte chitosan–gelatin complexes (at a constant gelatin concentration of 1%) was studied by shearing in steady flow and linear oscillations. These complexes, including native gelatin, demonstrate clearly expressed viscoelastic properties. Viscoelastic properties correlated well with the non-Newtonian behavior of hydrogels (according to the Cox–Merz rule). Increasing the chitosan concentration (from 0.1% to 0.6%) results in exponential growth of the apparent viscosity, yield stress, and storage modulus. However, a further increase in chitosan concentration to 0.8% leads to a reduction in these rheological parameters due to the electrostatic repulsion of similarly charged polyelectrolyte complexes under the high concentration of these complexes. The macro-rheological properties of chitosan–gelatin gels are mainly determined by the colloidal structure of sol-precursors in solutions. The yield stress dependence on the radius of the dispersed particles is of square type. Electron photomicrographs showed that the introduction of even small quantities of chitosan leads to radical changes in the supramolecular structure of the gelatin gel.     

Synthesis based on β-phenylethylamines. IX. Synthesis of sulfides of β-phenylethylamines and of N-benzyltetrahydroisoquinolines

New bimolecular sulfur-containing -phenylethylamines and N-benzyltetrahydroisoquinolines have been synthesized from formyl derivatives of diaryl sulfides. The possibility of using metals as catalysts for obtaining diaryl sulfides in the reaction of ortho-substituted benzaldehydes with SCl₂ has been shown for the first time.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 731–735, September–October, 1995. Original article submitted November 11, 1994.     

Electrocatalytic interaction of nano-engineered palladium on carbon nanofibers with hydrogen peroxide and β-NADH

The growing demands for reagentless hydrogen peroxide (H₂O₂) and β-nicotinamide adenine dinucleotide (β-NADH) sensors from food, pharmaceutical, chemical, and biochemical fields have stimulated extensive research interest on nano-engineered Pd. In this paper, Pd/carbon composite nanofibers were prepared by electrodepositing Pd onto electrospun carbon nanofibers to act as a catalyst toward the electrocatalytic redox reactions of H₂O₂ and β-NADH. The morphology of nano-engineered Pd was controlled by selectively adjusting the electrodeposition time and potential. Scanning electron microscopy and transmission electron microscopy results showed that nanocactus- and nanoflower-like Pd depositions were obtained on the surface of carbon nanofibers. Electrocatalytic analysis demonstrated a high electrocatalytic activity of the composite nanofibers for the redox of H₂O₂ and oxidation of β-NADH.     

Preparation of β-fluoro- and β,β-difluoro-histidinols

Nucleophilic attack of azide on 2-bromo-3-fluoro-3-(1-trityl-1H-imidazol-4-yl)-propan-1-ol (1a) in aprotic solvent occurs on the 2-position to give the 2-azido derivative (2a). Reduction of azide and removal of the trityl group produces β-fluorohistidinol (6a). Elimination of HBr from 1a followed by “FBr” addition to the resulting double bond gives 2-bromo-3,3-difluoro-3-(1-trityl-1H-imidazol-4-yl)-propan-1-ol (1b). Nucleophilic attack of azide followed by reduction and removal of the trityl group, as for the preparation of 6a, gives β,β-difluorohistidinol (6b). Initial attempts, under a variety of conditions, to oxidize the fluorinated histidinol precursors to carboxylic acids have not been successful.     

Noncovalent columnar structures based on β-cyclodextrin

A new method for the synthesis of associates of cyclodextrins (CDs) of the columnar type consisting of the precipitation of CDs from aqueous solutions into acetone at lowered temperatures is developed. It is shown that columnar structures exist in both a crystalline state and in aqueous solutions. Hydrodynamic radii and molecular masses of noncovalent columnar structures (NCSs) in aqueous solutions are determined by the dynamic and static light scattering methods. The degree of association of noncovalent columnar polymers is ～40. It is revealed the NCS associates based on β-CD are stable and their hydrodynamic radius R _h is equal to 100 ± 10 nm. The kinetics of interactions of initial β-CD and NCS with poly(propylene oxide) (PPO) is studied. The pattern of kinetic curves of R _h growth upon interaction between NCS and PPO indicates that the aggregation of the particles of polymer inclusion complex proceeds in the regime of reaction-limited cluster-cluster aggregation. Kinetic curves describing the interaction processes between β-cyclodextrin and PPO are characterized by the presence of induction period t ₀. At t > t ₀, R _h ∞ t ^0.56 which is typical for the diffusion-limited cluster-cluster aggregation. Schemes of the formation of polymer inclusion complexes between initial β-CD or NCS and poly(propylene oxide) are proposed. Comparison of kinetic data on the complexation of β-CD in solution in the form of associates of two types with PPO demonstrates that columnar forms of associates are reactive species acting as macroreceptors.     

Giant macrolactams based on β-sheet peptides

This paper reports the use of natural amino acids, the tripeptide β-strand mimic Hao, and the β-turn mimic δ-linked ornithine to generate water-soluble 54-, 78-, and 102-membered-ring macrolactams. These giant macrocycles were efficiently prepared by synthesis of the corresponding protected linear peptides, followed by solution-phase cyclization and deprotection. The protected linear peptide precursors were synthesized on 2-chlorotrityl chloride resin by conventional Fmoc-based solid-phase peptide synthesis. Macrocyclization was typically performed using HCTU and N,N-diisopropylethylamine in DMF at ca. 0.5 mM concentration. The macrocycles were isolated in 13-45% overall yield after HPLC purification and lyophilization. 1D, 2D TOCSY, and 2D ROESY (1)H NMR studies of the 54- and 78-membered-ring macrolactams establish that these compounds fold to form β-sheet structures in aqueous solutions.     

Preparation of the β-aminoethyl ether of dimethylethynylcarbinol

Summary A method is proposed for preparation of the -aminoethyl ether of dimethylethynylcarbinol from the -cyanoethyl ether of dimethylethynylcarbinol.     

Preparation of stable micropatterns of gold oncell-adhesion-resistant hydrogels assisted by ahetero-bifunctional macromonomer linker

Surface patterning is very useful in biomaterial studies, yet it is not easy to prepare a micropattern with cell-adhesion contrast that is stable in a wet environment. Recently, a platform technique of transfer photolithography was invented to fabricate stable metal microarrays on the surface of a cell-adhesion resistant and mechanically biomimetic poly(ethylene glycol) hydrogel; the linker is the key chemical in such a transfer strategy. This article reports the design and synthesis of a hetero-bifunctional macromonomer linker with a thiol group at one end and an acryloyl group at the other end. The bifunctional linker was characterized by GPC and ¹H NMR, and the average number of thiol groups in the bifunctional linker was detected by Ellman’s reagent. The regent stability under wet conditions was also confirmed by the model reactants. The resultant micropatterned surfaces are meaningful for future studies of cell behaviors on mechanically biomimetic matrixes.     

Preparation of α-alkyl-β-amino acids via β-alanine Ni(II) complex

A new β-amino acrylic acid Ni(II) complex has been developed and used for the synthesis of α-alkyl-β-amino acids via alkylation with alkyl halides under operationally convenient conditions. The pivotal α-alkylated intermediate can be converted into the corresponding α-alkyl-β-amino acids via two steps with a wide range of substituents.     

Effect of NaOH on the solubility of fluorocarbon in alcohol–NaOH systems

We propose a dechlorination process that allows safe and environmental conversion of chlorinated fluorocarbons. Starting with dissolving a fluorocarbon in an alcohol–NaOH solution, the fluorocarbons are reacted with alcohol–NaOH solvents at room temperature and pressure. In this work, the effect of the NaOH concentration on the solubility of CCl₂F₂ (CFC-12), CH₂F₂ (HFC-32), C₂HF₅ (HFC-125), C₂H₂F₄ (HFC-134a) and C₂H₄F₂ (HFC-152a) in methanol–NaOH, ethanol–NaOH and 1-propanol–NaOH solutions was measured. The experimental salting-out effects can be explained by solvation of a few alcohol molecules on sodium ion. Setchenov coefficients were determined and found to be independent of temperature.