Preparation of CF3-containing 1,3-di- and 1,1,3-trisubstituted allenes

Novel synthetic pathway to access trifluoromethylated allenes with 1,3-di- as well as 1,1,3-trisubstitution patterns was developed from a variety of 4,4,4-trifluorobut-2-yn-1-ols which were then transformed into the corresponding vinylic iodides in highly regio- and stereospecific manners, and zinc-mediated beta-elimination after trifluoroacetylation of the hydroxyl group eventually realized the formation of the target molecules in good to excellent overall yields in facile and short steps.     

Poly(ethylene oxide) thin films produced by electrospray deposition: morphology control and additive effects of alcohols on nanostructure

Nanostructured thin films were prepared by electrospray deposition (ESD) from poly(ethylene oxide) (PEO) aqueous solution. The surface morphologies of the deposited films were observed using scanning electron microscopy (SEM). The SEM images revealed the correlations between the morphologies and the ESD conditions. By changing the applied voltage and solution properties such as viscosity, surface tension, conductivity, and molecular weight, PEO thin films with diverse nanostructures--from nanospheres to nanofibers--were fabricated. It was also revealed that the addition of alcohols to polymer solution, which enables simultaneously changing the viscosity, the surface tension, and the conductivity, enhanced the formation of the fibrous structure. These results indicate that the ESD method is potentially a useful option for producing nanoengineered polymer surface.     

Infrared spectroscopic investigation of poly(2-methoxyethyl vinyl ether) during thermosensitive phase separation in water

Hydration changes of poly(2-methoxyethyl vinyl ether) (PMOVE) synthesized via living cationic polymerization have been investigated during a temperature-responsive phase separation in water by using infrared spectroscopy. An aqueous PMOVE solution has lower critical solution temperatures (LCSTs) of 66 degrees C in H2O and 65 degrees C in D2O at approximately 15 wt %. During phase separation, the C-H stretching (nu(C-H)) bands of PMOVE shift downward (red shift). In particular, the IR band assigned to the antisymmetric stretching vibration of the terminal methyl groups exhibits a remarkably large red shift by 16 cm-1. The band also exhibits a red shift with increasing polymer concentration at T < Tp. Density functional theory (DFT) calculations of the models of hydrated PMOVE indicate that the shift is due mainly to the breaking of hydrogen bonds (H-bonds) between the oxygen of the methoxy groups and water and partially to the breaking of the CH...O H-bond to them.     

Thermoelectric power of quasi-one-dimensional Nb3X4 with X=S, Se andTe

The thermoelectric power of linear chain synthetic metals Nb₃X₄ (with X=S, Se and Te) was measured from 5 to 300 K. The thermopower is negative indicating a dominant transport by electrons. Common to three compounds, in lower temperature regions the thermopower rises linearly with temperature but soon saturates. With respect to Nb₃S₄ and Nb₃Se₄ we have found no special anomaly of the thermopower except for a little higher magnitude.With respect to Nb₃Te₄ anomalies in the thermopower vs temperature appear at about 80 and 20 K which are explained in terms of the charge- density-wave phase transition from the simultaneous measurement of the resistivity and the observation of the electron diffraction patterns.     

Chronopotentiometry study of a cation-exchange membrane in the presence of cationic surfactant in membrane surface vicinity

In this study, the effect of cationic surfactant (benzalkonium chloride) on the transport of KCl through a sulfonated styrene-divinyl benzene cation-exchange membrane was investigated. The presence of benzalkonium chloride as the cationic surfactant, which interacts with the sulfonic groups on membrane surface, has to disturb the transport of K⁺ ions and directly gives responses in its chronopotentiogram. The electrodialysis of the cationic surfactant solution showed an irreversible monotonous increase of the total system potential due to the fouling phenomena. However, a small amount of cationic surfactant in the membrane surface vicinity was observed to give a fluctuating chronopotentiogram at the high current density. This fluctuation is started by a steep increase and followed by the decrease of potential, which finally relaxed to reach a steady state. This potential fluctuation is proposed to be the response of a structural transformation of surfactant micelles on the membrane surface under perturbation of the externally applied electric field, which is discussed and examined qualitatively in this report.     

How the geometrical model for plant cell wall formation enables the production of a random texture

Cellulose synthase (CESA) molecules are the building blocks and catalytic centers of the CESA complex. The study of mutants in Arabidopsis has led to insight into the structure of these nanomachines. Inside the plasma membrane, the CESA molecules are arranged in complexes, which, apart from the CESA molecules proper, contain other, mostly unidentified, proteins. We developed a theory in which CESA density, together with distance between cellulose microfibrils (CMFs) being deposited and cell geometry, determines wall texture. We have shown earlier how this theory is able to explain the production of axial, helical, helicoid and crossed-polylamellate textures. In the present article we extend this theory to random wall textures.     

Control of diameter,morphology, and structure of PVDF nanofiber fabricated by electrospray deposition

Poly(vinylidene fluoride) (PVDF) nanofibers were prepared by electrospray deposition (ESD). To control the diameter, morphology, and structure of PVDF nanofibers, some parameters were investigated, such as polymer concentration, nozzle‐to‐ground collector distance, feeding rate of the polymer solution, and applied voltage. The fabricated fiber was 80–700 nm in diameter. The increase in the polymer concentration caused an increase in the polymer viscosity and fiber diameter. At low polymer concentration (5 wt %), polymer nanoparticles were formed. An increase in applied voltage will increase the fiber diameter. Variation in the nozzle‐to‐ground collector distance did not result in significant changes in the fiber diameter. Increase in the feeding rate of the polymer solution decreased the fiber diameter. Differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) measurements showed that the melting point and total crystallinity were decreased. Fourier transform infrared spectroscopy (FTIR) measurement revealed that ESD process induced the formation of the oriented β‐phase PVDF structures. It was also demonstrated that the addition of hydrofluorocarbon solvent to polymer solution remarkably enhanced the formation of β‐phase crystalline structure of PVDF nanofiber. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 779–786, 2006     

Discrimination of conventional and organic white cabbage from a long-term field trial study using untargeted LC-MS-based metabolomics

The influence of organic and conventional farming practices on the content of single nutrients in plants is disputed in the scientific literature. Here, large-scale untargeted LC-MS-based metabolomics was used to compare the composition of white cabbage from organic and conventional agriculture, measuring 1,600 compounds. Cabbage was sampled in 2 years from one conventional and two organic farming systems in a rigidly controlled long-term field trial in Denmark. Using Orthogonal Projection to Latent Structures–Discriminant Analysis (OPLS-DA), we found that the production system leaves a significant (p?=?0.013) imprint in the white cabbage metabolome that is retained between production years. We externally validated this finding by predicting the production system of samples from one year using a classification model built on samples from the other year, with a correct classification in 83 % of cases. Thus, it was concluded that the investigated conventional and organic management practices have a systematic impact on the metabolome of white cabbage. This emphasizes the potential of untargeted metabolomics for authenticity testing of organic plant products.     

Fluorescence Energy Transfer Study of Interstrand DNA Cross-linking Caused by Rigid Bisintercalator

The intermolecular cross-linking of DNA with a rigid bisintercalator, 1,4-bis(( N -methylquinolinium-4-yl)vinyl)benzene (pMQVB) has been studied using fluorescence resonance energy transfer (FRET), fluorescence anisotropy measurements, and dynamic fluorescence microscopy. Short DNA duplexes, single-labeled with fluorescein (donor) and x-rhodamine (acceptor), were used as energy transfer partners. Due to the quenching effect of pMQVB on the emission of both fluorescein and x-rhodamine, the energy transfer was monitored using the corrected Stern-Volmer plots. The cross-linking ability of pMQVB depended on the ligand structure; the planar E , E isomer cross-linked DNA contrary to the non-planar E , Z isomer. Dynamic fluorescence microscopy observation also demonstrated the ability of pMQVB to cross-link large T4 DNA molecules.     

Incorporation of glucose oxidase into Langmuir-Blodgett films based on Prussian blue applied to amperometric glucose biosensor

Glucose oxidase (GOx) was immobilized in the organic-inorganic Langmuir-Bldogett (LB) films consisting of octadecyltrimethylammonium (ODTA) and nanosized Prussian blue (PB) clusters. The amperometric glucose biosensors based on the LB films were fabricated and tested. It was found that the sensors exhibited a clear response current under an applied voltage of 0.0 V (vs Ag/AgCl). The linearity of current density versus glucose concentration was confirmed below 15 mmol/L concentration. This is the first observation of biosensor function of the hybrid organic-inorganic LB films. The successful preparation of glucose sensors operating at the very low potential indicates that the adsorbed PB clusters in the LB films act as an electrocatalyst for the electrochemical reduction of hydrogen peroxide, which is the final product of the enzymatic reaction sequence. The observed low potential applicability is estimated to inhibit the responses of interferants such as ascorbic acid, uric acid, and acetominophen. It was also found that an electrostatic interaction between positively charged ODTA+ and the adsorbed species of both GOx and PB provided a stabilized adsorption state in the LB films. Such stable immobilization contributes to the steady amperometric response current observed in the present ODTA/PB/GOx LB films.