Structure of the tetramer of α-methylstyrene

The structure of the tetrameric dianion formed by α-methylstyrene in tetrahydrofuran by reaction with sodium has been examined. Mass spectral, NMR, infrared, and kinetic data all indicate that the structure is rather than the structure which had previously been assumed for this species.     

Fabrication of Light‐Guiding Core/Sheath Fibers by Coaxial Electrospinning

Light‐guiding core/sheath fibers are fabricated from two different refractive index (RI) polymers by coaxial electrospinning. The morphology and fiber diameter are analyzed with scanning electron and fluorescence microscopies. It is found that the diameter of the core and the thickness of the sheath could be varied from 100 to 400 nm by changing the concentration of the outer solution. The incorporation of a chromophore into the inner material confirmed the uniformity of the core/sheath structure in long segments of the fibers. The boundary is clearly seen: the core diameter and the thickness of the sheath are constant along the fiber axis in fluorescence images. The ejected beam is circular and light‐guided along the fiber axis as in an optical fiber.

     

Novel C‐acylated triazole derivatives of ravuconazole,an azole antifungal agent

Novel C‐acylated triazoles were synthesized from ravuconazole via bicyclic triazole lactone. The synthesis and antifungal activity of these C‐acylated derivatives are described.     

A Catalytic Approach to Functional Poly(1,4‐ketone)s Bearing Pendant Monosaccharide Fragments

Summary: Novel alternating polyketone‐based polymers bearing pendant saccharide units that are accessible by polymerization catalysis are presented. The materials were synthesized by polymerization of carbon monoxide and α‐olefins containing protected glucose or N‐acetyl glucosamine residues. The dicationic Pd^II bis(phoshine) complex [Pd(dppp)(NCCH₃)₂](BF₄)₂ was used as a catalyst precursor. An O‐deacetylation of the copolymers afforded materials with amphiphilic character.

Structure of the poly(1,4‐ketone) copolymers synthesized here.     

Alpha vinylation of haloquinoline‐5,8‐diones with methyl acrylate and methyl vinyl ketone under baylis‐hillman reaction conditions

A synthesis of mono‐ and di‐vinylquinolinediones based on substitution of the halogens in 6,7‐dihaloquinoline‐5,8‐diones by DABCO‐assisted enolate ion is described. Divinylquinolines undergo 6π‐electrocyclization by thermally to give the benzo[g]quinoline derivatives.     

Environmentally Friendly Negative Resists Based on Acid‐Catalyzed Acetalization for 193‐nm Lithography

Novel water‐developable negative resists were designed to induce both crosslinking and polarity change upon exposure and bake. The matrix polymers were synthesized by copolymerization of glyceryl methacrylate and methacrolein. The acid‐catalyzed acetalization of the polymer induced crosslinking, polarity change, and an increase in dry‐etch resistance. The resist formulated with this polymer and cast in a water/ethanol mixture showed 0.7 μm line and space patterns using a mercury–xenon lamp in a contact printing mode and pure water as a developer.

The acid‐catalyzed acetalization of poly(GMA‐co‐MA) to form the water‐insoluble acetal.     

Interfaces between coexisting phases in polymer mixtures: What can we learn from Monte Carlo simulations?

Symmetric binary polymer mixtures are studied by Monte Carlo simulation of the bond fluctuation model, considering both interfaces between coexisting bulk phases and interfaces confined in thin films. It is found that the critical behavior of interfacial tension and width is compatible with that of the Ising model, as expected from the universality principle. In the strong segregation limit, only qualitative but not quantitative agreement with the self-consistent field (SCF) theory is found. It is argued that the SCF theory requires but for the short chains studied (N = 32 effective monomer units per chain), the limit is only reached for close to unity. Also, the effective χ-parameter decreases in the interface. It is shown that the interfacial width w does not increase by the adsorption of block copolymers as long as their areal density is still dilute (“mushroom” regime). But a broadening of interfaces does occur for thin films confined between walls at distance D, due to fluctuations that lead to for short-range forces, in agreement with experiment.     

Molecular confirmation and crystal structure of the β form of poly(ethylene oxybenzoate)

The crystal structure of the β form of poly(ethylene oxybenzoate) was analyzed by x-ray diffraction. Four nearly extended molecular chains pass through a unit cell with parameters a = 8.19 Å, b = 11.07 Å, c (fiber axis) = 19.05 Å, β = 114.8°, and the space group P2₁/n-C. The structural difference between the α and β forms is mainly due to the internal rotation angles for the virtual bond and the ? CH₂? CH₂? bond. They are essentially in trans confirmation in the β form, while the α form contains cis and gauche (? CH₂? CH₂? ) conformations.     

Organically Modified Layered Titanate: A New Nanofiller to Improve the Performance of Biodegradable Polylactide

Summary: The preparation and characterization of a new type of nanocomposite material that is based on biodegradable polylactide (PLA) and organically modified layered titanate, is reported. Layered titanate, modified with a N‐(cocoalkyl)‐N,N‐[bis(2‐hydroxyethyl)]‐N‐methylammonium cation, was used as a new nanofiller (OHTO) for the nanocomposite preparation. Wide‐angle X‐ray diffraction and transmission electron microscopy (TEM) analyses confirmed that titanate layers were intercalated and nicely distributed in the PLA matrix. The materials properties of neat PLA improved remarkably after nanocomposite preparation.

UV/vis transmission spectra of neat PLA and a nanocomposite.     

High yield synthesis of 4H‐1,4‐benzothiazine‐1,1‐dioxide derivatives

4H‐1,4‐Benzothiazine‐1,1‐dioxide derivatives were synthesized through a sequence of almost quantitative reactions. The commercial starting material 2‐(methylsulfanyl)aniline was Boc‐protected, N‐acylated and oxidized at the sulfur atom to obtain a sulfonyl derivative. An anionic transposition of the acyl group followed by asimultaneous deprotection‐cyclization gave the title products in excellent yields. All products and intermediates were fully characterized.     

Zur Darstellung von (Triorganosilylmethyl)-organophosphin-chalkogeniden

Synthesis of (Triorganosilymethyl)-organophosphine Chalkogenides Apart from the usual GRIGNARD method the preparation of compounds with the atom group is also possible in the way citated above. In the case [X = S] [R = me] twofold silylation occurs under the same conditions. Further metalation of C? H-bond is investigated.     

Chemical Modification of Chitosan, 17

The Michael reaction of chitosan with acrylic acid was carried out successfully, even in water alone as the reaction medium. As a consequence of its good solubility in water, the reaction product, N‐carboxyethylchitosan, showed excellent biodegradable properties with standard activated sludge.

     

Application of Poly(3‐hexylthiophene) Functionalized with an Anchoring Group in Dye‐sensitized Solar Cells

A series of three poly(3‐hexylthiophene) functionalized either with a cyanoacetic acid (CA) or a rhodanine‐3‐acetic acid anchoring groups were synthesized and characterized. The TiO₂ based dye‐sensitized solar cells have been fabricated and performances were tested. We show that shorter chain length (15 thiophene units) linked to CA binding group gives good performances as J_sc, V_oc, FF and η(%) were 6.93(mA · cm⁻²), 0.65(V), 0.67 and 3.02%, respectively. A maximum IPCE of ≈50% at 500 nm was recorded with a liquid electrolyte, under AM 1.5 simulated solar irradiance.

     

On‐Chip Alginate Microencapsulation of Functional Cells

We report the use of a PTFE‐based microfluidic device for the encapsulation of living, therapeutically‐active cells within monodisperse alginate microspheres. We present a novel microfluidic platform and a flexible experimental method for the production of alginate microspheres. Cell lines HEK293, U‐2 OS and PC12 were separately encapsulated using this method, with minimal loss of cell viability.

     

[2, 3] Sigmatropic Rearrangements on Lithiation of Some Allyl Sulfides. Preliminary communication

In five cases, [2,3] sigmatropic rearrangement of the type has been observed.     

Synthesis and Characterization of β‐Cyclodextrin Based Functional Monomers and its Copolymers with N‐isopropylacrylamide

Two novel monovinyl β‐cyclodextrin (β‐CD) monomers are synthesized. Their chemical compositions are characterized by means of element analysis, NMR and FT‐IR spectroscopy. The results show that the synthesis techniques used are convenient and efficient. Using N‐isopropylacrylamide as a comonomer, two novel linear copolymers can also be synthesized.

Synthesis route of monovinyl β‐CD monomers.     

Deformation of methylenecyclopropane in solution: NMR study in the nematic phase at 240 and 400 MHz

The NMR spectrum of methylenecyclopropane oriented in two nematic phases has been measured at 240 and 400 MHz. Ratios of the proton-proton distances have been obtained. These values are compared with those deduced from the structure of the molecule in the gaseous state; they suggest an increase of the ethylenic angle in the nematic phase.     

Multiscale Modeling of Branch Length in Butyl Acrylate Solution Polymerization

Branch lengths resulting from both backbiting and intermolecular chain transfer to polymer are examined for the solution polymerization of butyl acrylate, using a rate‐equation model and ordinary differential equations. Backbiting is allowed to generate branches of varying length, according to a cumulative distribution function obtained from a lattice kinetic Monte Carlo simulation. About 8% of the branches produced by backbiting are 10 mers or longer. In contrast to common assumptions about the origins of short‐chain and long‐chain branches, the model indicates that nearly all of the long‐chain branches may be produced by backbiting, rather than intermolecular chain transfer to polymer.

     

Studies on synthesis and kinetics of thermodecomposition of the nickel(Ⅱ) compounds with Schiff base derived from amino acids

Monoaqua salicylaldehyde-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp1) and monoaqua o-vanillin-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp2) were synthesized. The composition and structures of these two compounds were analyzed. Their thermal stability and non-isothermal kinetics were also investigated by use of TG and DTG curves. The possible reaction mechanisms in their first steps of thermal decomposition reactions were deduced by means of integral and differential methods. Thermodecomposition kinetic equations of the compounds are as follows:Cp1: da/At = A . exp(-E/RT) . 3/2(1 - a)4/3 . [1/(1 - a)1/3 -1]-1 Cp2 : da/At = A . exp(-E/RT) . (1 - a)     

Effect of gegen ion in cationic polymerization and copolymerization of trioxane

p-Chlorophenyldiazonium hexafluorophosphate has been reported to be a superior catalyst for cationic polymerization and copolymerization of trioxane as compared to boron trifluoride dibutyl etherate (BF₃·Bu₂O)¹. In the present investigation the effect of anions derived from elements in Group VA, AsF and SbF, has been ascertained. It has been concluded that p-chlorophenyldiazonium hexafluoroarsenate is also a superior catalyst to boron trifluoride dibutyletherate (BF₃·Bu₂O), while p-chlorophenyl-diazonium hexafluoroantimonate is inferior. Copolymers with the highest polymer yield (>95%) and molecular weight (intrinsic viscosity = 4 to 5) were obtained with Simple dependences on catalyst concentration have been observed to hold for a wide catalyst concentration range ([M]/[C]) = (1 to 20) × 10⁵: For the same relationships hold. However, the polymer yield (75%) and molecular weights (intrinsic viscosity ?1) are considerably lower while the extent of chain transfer is higher. Furthermore, the polymerization proceeds with explosive violence. The quantitative aspects resulting from polymerization, for the most part, can be interpreted in terms of the extent of dissociation of the propagating ions.