Preparation of hydrophilic poly(vinylidene fluoride) membrane by in-situ grafting of N-vinyl pyrrolidone via a reactive vapor induced phase separation procedure

Increasing hydrophilicity of hydrophobic membrane is one of the strategies to improve its antifouling performance. Herein we report a procedure of reactive-vapor induced phase separation to prepare an N-vinyl pyrrolidone (NVP) modified poly(vinylidene fluoride) (PVDF) membrane to improve its hydrophilicity. PVDF solution containing NVP monomer was cast in ammonia water vapor atmosphere to prepare the modified membrane. During the process, PVDF was dehydrofluorinated by the reactive vapor of ammonia water to generate double bond of FC═CH, and then NVP was grafted. The degree of grafting modification and the microstructure evolution of the membrane were studied by adjusting the amount of NVP addition. A possible mechanism of membrane formation from crystallization gelling to non-crystallization gelling has been proposed to understand the morphology change from nodular sphere to bi-continuous microstructure with fibril matrix. It has been found that rising the degree of modification has changed the polymorph of PVDF from β to α crystalline phase, as well as turned the hydrophobic PVDF membrane into hydrophilic. Moreover, the modified membrane displayed obvious reduction in bovine serum albumin adsorption, suggesting improvement in anti-fouling performance. Therefore, our work provides an easy strategy to prepare hydrophilic PVDF membrane, which may have promising potential applications.     

Sulfuryl Fluoride Mediated Synthesis of Amides and Amidines from Ketoximes via Beckmann Rearrangement

A metal-free and redox-neutral method for Beckmann rearrangement employing inexpensive and readily available SO₂F₂ gas is described. The reported transformation proceeds at ambient temperature and is compatible with a wide range of sterically and electronically diverse aromatic, heteroaromatic, aliphatic and lignin-like oximes providing amides in good to excellent yields. The reaction proceeds through the formation of an imidoyl fluoride intermediate that can also be used for the synthesis of amidines.     

Dependence of dielectric,ferroelectric, and piezoelectric properties on crystalline properties of p(VDF‐co‐TrFE) copolymers

Thermal processing at various temperatures has been used to fabricate poly(vinylidene fluoride‐co‐trifluoroethylene) [P(VDF‐co‐TrFE)] films with varied crystalline properties in an attempt to improve their piezoelectric properties. Although the dielectric constant of the films annealed at higher temperature is smaller than that of cooled and quenched ones, it has been shown that the annealed films possess larger crystallinity and stacked lamellar crystal grain size. The ferroelectric domains deriving from crystal region in all the samples are effectively improved by hot polarization. As a result, the remnant polarizations (P_r) and coercive electric field (E_c) of the corresponding films are improved at a low frequency due to the response of dipoles in crystal phase, and the largest piezoelectric constant in the longitudinal thickness mode (d₃₃=?25 pC/N) is obtained in an annealed copolymer film. The results illustrate improving the crystal structure of P(VDF‐co‐TrFE) is an effective way to realize high electromechanical properties, which provides broadly applied scenery for this kind of copolymer in piezoelectric components. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Improving waterproof/breathable performance of electrospun poly(vinylidene fluoride) fibrous membranes by thermo‐pressing

Facing the ever‐increasing demand for waterproof/breathable materials, a rapid and efficient fabrication method of these functional materials with excellent performance as well as robust mechanical properties remains challenging. Herein, a simple and scalable strategy referred to as thermo‐pressing is introduced to improve the waterproof/breathable performance and mechanical properties of electrospun PVDF fibrous membranes. The synergistic effect of temperature and pressure acted on the electrospun PVDF membranes on the fiber morphology and crystal structure was investigated, which can be able to effectively enhance waterproof performance and mechanical properties, endowing the as‐prepared membranes with a modest breathability. The membranes thermo‐pressed at 150 °C with a pressure of 8.27 MPa exhibit robust tensile strength of 40.65 MPa, which is superior to those of the previous reports (below 32.8 MPa). Notably, the optimized membranes enable to show a high hydrostatic pressure of 102 kPa, good WVTR of 10.87 kg m⁻² d⁻¹ and excellent abrasion resistance, which implies that the thermo‐pressing is an efficient and facile way to steer the fiber morphology and crystal structure of electrospun membranes to improve their application performance. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 36–45     

Color centers in irradiated MgF2

Abstract

Color centers in rutile-structured MgF₂ single crystals irradiated at 20K/360K by reactor neutrons are investigated spectroscopically at LNT. Four different types of the F-F vacancy bond in MgF₂ are possibly identified to the observed absorption bands as due to the F₂ centers; instead of previous assignments, the 300nm band to the F₂(D_2h), the 325nm band to the F₂(C₁), the 355nm band to the F₂(C_2v), and the 400nm band to the F₂(C_2h) centers.     

Preliminary study on singlet oxygen production using CeF3:Tb3+@SiO2-PpIX

Luminescent properties and singlet oxygen production using CeF₃:Tb³⁺-based nanoparticles modified with SiO₂ and protoporphyrin IX (PpIX) were studied. CeF₃:Tb³⁺ nanopowder was prepared via sol–gel route, with subsequent surface coating by SiO₂ layer and the conjugation with photosensitive PpIX molecules. Radioluminescence spectra suggest an energy transfer from Ce³⁺ to Tb³⁺ ions and from Tb³⁺ to molecules of PpIX photosensitizer. The energy transfer was confirmed by photoluminescence decay curves. Singlet oxygen production was detected using a reaction of ¹O₂ with 3’-(p-aminophenyl) fluorescein (APF) chemical probe after X-Ray excitation. Qualitative changes in time resolved photoluminescence spectra in the region of 520 nm indicate ¹O₂ generation. Studied nanocomposites may be good candidates for the application in X-ray induced photodynamic therapy.     

One-Pot,Fluoride-Promoted Wittig Reaction

A one-pot, fluoride-promoted Wittig reaction was developed. The reactions of ethyl α-bromoacetate with aliphatic, aromatic, and heteroaromatic aldehydes in the presence of tri-n-butylphosphine and tetrabutylammonium fluoride produced α,β-unsaturated esters in good to excellent yields and E-stereoselectivity. Under the same conditions, reactions of ethyl α-bromopropionate, α-bromo acetonitrile, and α-bromoacetophenone with aliphatic and aromatic aldehydes in the presence of tri-n-butylphosphine and tetrabutylammonium fluoride produced the expected α,β-unsaturated derivatives in good E-stereoselectivity. The protocol was extended to semistabilized ylides and applied to the synthesis of some combretastatin analogs.