Radical polymerization inside living cells.

Polymerization reactions conducted inside cells must be compatible with the complex intracellular environment, which contains numerous molecules and functional groups that could potentially prevent or quench polymerization reactions. Here we report a strategy for directly synthesizing unnatural polymers in cells through free radical photopolymerization using a number of biocompatible acrylic and methacrylic monomers. This offers a platform to manipulate, track and control cellular behaviour by the in cellulo generation of macromolecules that have the ability to alter cellular motility, label cells by the generation of fluorescent polymers for long-term tracking studies, as well as generate a variety of nanostructures within cells. It is remarkable that free radical polymerization chemistry can take place within such complex cellular environments. This demonstration opens up a multitude of new possibilities for how chemists can modulate cellular function and behaviour and for understanding cellular behaviour in response to the generation of free radicals.

Enhanced osteogenic activity of phosphorylated polyetheretherketone via surface-initiated grafting polymerization of vinylphosphonic acid.

Polyetheretherketone (PEEK) is considered to be a prime candidate with the potential to replace biomedical metallic materials as an orthopedic and dental implant on account of its elastic modulus similar to that of human cortical bone. Unfortunately, its biomedical application is impeded by the bioinert surface property and inferior osteogenic activity. In this work, phosphate groups were incorporated onto the PEEK surface through a single-step UV-initiated graft polymerization of vinylphosphonic acid. Diffuse reflectance Fourier transform infrared spectroscopy (DRFTIR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) revealed that phosphate groups were successfully introduced onto the PEEK surface without apparently altering its surface topographical feature and roughness. Water contact angle measurements diclosed the increasing hydrophilia after surface phosphonation. In vitro cell adhesion, spreading, proliferation, alkaline phosphatase activity, extracellular matrix mineralization, and real-time PCR analyses showed enhanced adhesion, spreading, proliferation and osteogenic differentiation of MC3T3-E1 osteoblast on the surface-phosphorylated PEEK. An in vivo biological evaluation in the rabbit tibiae proximal defect model by means of a histological analysis confirmed that the surface-phosphorylated PEEK had improved bone-implant contact. The obtained results indicate that enhanced osteogenic activity to surface-phosphorylated PEEK, which gives positive information of its potential applications in orthopedic and dental implants.

Thiol-ene click chemistry towards easy microarraying of half-antibodies.

A UV light-induced thiol-ene coupling reaction (TEC) between half-antibodies (hIgG) and vinyl functionalized glass surfaces was run for biosensing in the microarray format. The accomplished performance improved that obtained with whole antibodies.

An efficient enzymatic modification of cordycepin in ionic liquids under ultrasonic irradiation.

A comparative study of the immobilized Candida antarctica lipase B (Novozym 435)-catalyzed acylation of cordycepin with vinyl acetate in ionic liquids (ILs) under ultrasonic irradiation and shaking was conducted. The application of ultrasonic irradiation instead of shaking during acylation resulted in an enhanced reaction rate and a higher level of substrate conversion. Among the various ILs examined, 1-butyl-3-methylimidazolium tetrafluorobrate ([C4MIm][BF4]) was the best medium for the reaction because it produced the highest substrate conversion. In [C4MIm][BF4], the optimal ultrasonic power, water activity, and reaction temperature were 120 W, 0.33, and 50 °C, respectively. The acylation of cordycepin in [C4MIm][BF4] proved to be regioselective under both conditions: the C5'-OH was acylated. Novozym 435 exhibited a much higher operational stability in [C4MIm][BF4], and 58.0% of its original activity was maintained after ten reuse cycles under ultrasonic irradiation. Compared with the cordycepin, the rate of adenosine deaminase-catalyzed deamination was greatly reduced when the 5'-OH was substituted by acetyl group. These results demonstrated that the combined application of ultrasonic irradiation and IL as a medium was an efficient approach for the enzymatic modification of cordycepin.

Kinetics and products of the gas-phase reactions of divinyl sulfoxide with OH and NO3 radicals and O3.

Using relative rate methods, rate constants for the gas-phase reactions of divinyl sulfoxide [CH 2CHS(O)CHCH 2; DVSO] with NO 3 radicals and O 3 have been measured at 296 +/- 2 K, and rate constants for the reaction with OH radicals have been measured over the temperature range of 277-349 K. Rate constants obtained for the NO 3 radical and O 3 reactions at 296 +/- 2 K were (6.1 +/- 1.4) x 10 (-16) and (4.3 +/- 1.0) x 10 (-19) cm (3) molecule (-1) s (-1), respectively. For the OH radical reaction, the temperature-dependent rate expression obtained was k = 4.17 x 10 (-12)e ((858 +/- 141)/ T ) cm (3) molecule (-1) s (-1) with a 298 K rate constant of (7.43 +/- 0.71) x 10 (-11) cm (3) molecule (-1) s (-1), where, in all cases, the errors are two standard deviations and do not include the uncertainties in the rate constants for the reference compounds. Divinyl sulfone was observed as a minor product of both the OH radical and NO 3 radical reactions at 296 +/- 2 K. Using in situ Fourier transform infrared spectroscopy, CO, CO 2, SO 2, HCHO, and divinyl sulfone were observed as products of the OH radical reaction, with molar formation yields of 35 +/- 11, 2.2 +/- 0.8, 33 +/- 4, 54 +/- 6, and 5.4 +/- 0.8%, respectively, in air. For the experimental conditions employed, aerosol formation from the OH radical-initiated reaction of DVSO in the presence of NO was minor, being approximately 1.5%. The data obtained here for DVSO are compared with literature data for the corresponding reactions of dimethyl sulfoxide.

Ultrafast reversible photo-cross-linking reaction: toward in situ DNA manipulation.

We describe a novel ultrafast reversible DNA interstrand photo-cross-linking reaction via 3-cyanovinylcarbazole nucleoside ( (CNV)K). Oligodeoxynucleotide (ODN) containing (CNV)K can be photo-cross-linked by irradiation at 366 nm for 1 s, and the photo-cross-linked ODN can be split by irradiation at 312 nm for 60 s.

Water absorption and desorption from the dipole ordered polymer poly(methylvinylidene cyanide).

From thermal desorption studies, we find evidence that absorbed water in the bulk of poly(methylvinylidene cyanide) is more weakly bound than is the case for copolymer films of poly(vinylidenefluoride-trifluoroethylene). Ultraviolet laser enhanced thermal desorption of absorbed water exhibits little light polarization dependence for poly(methylvinylidene cyanide) in contrast to absorbed water in copolymer films of poly(vinylidenefluoride-trifluoroethylene). The implications of these differences are discussed.

Ultraviolet photochemistry of trichlorovinylsilane and allyltrichlorosilane: vinyl radical (HCCH2) and allyl radical (H2CCHCH2) production in 193 nm photolysis.

The absolute gas phase ultraviolet absorption spectra of trichlorovinylsilane and allyltrichlorosilane have been measured from 191 to 220 nm. Over this region the absorption spectra of both species are broad and relatively featureless, and their cross sections increase with decreasing wavelength. The electronic transitions of trichlorovinylsilane were calculated by ab initio quantum chemical methods and the observed absorption bands assigned to the A(1)A''<-- X[combining tilde](1)A'' transition. The maximum absorption cross section in the region, at 191 nm, is sigma = (8.50 +/- 0.06) x 10(-18) cm(2) for trichlorovinylsilane and sigma = (2.10 +/- 0.02) x 10(-17) cm(2) for allyltrichlorosilane. The vinyl radical and the allyl radical are formed promptly from the 193 nm photolysis of their respective trichlorosilane precursors. By comparison of the transient visible absorption and the 1315 nm I atom absorption from 266 nm photolysis of vinyl iodide and allyl iodide, the absorption cross sections at 404 nm of vinyl radical ((2.9 +/- 0.4) x 10(-19) cm(2)) and allyl radical ((3.6 +/- 0.8) x 10(-19) cm(2)) were derived. These cross sections are in significant disagreement with literature values derived from kinetic modeling of allyl or vinyl radical self-reactions. Using these cross sections, the vinyl radical yield from trichlorovinylsilane was determined to be phi = (0.9 +/- 0.2) per 193 nm photon absorbed, and the allyl radical yield from allyltrichlorosilane phi = (0.7 +/- 0.2) per 193 nm photon absorbed.

Photochemical generation of six- and five-membered cyclic vinyl cations.

The photochemical solvolyses of 4-tert-butylcyclohex-1-enyl(phenyl)iodonium tetrafluoroborate (1) and cyclopent-1-enyl(phenyl)iodonium tetrafluoroborate (2) in methanol yield vinylic ethers and vinylic cycloalkenyliodobenzenes and cycloalkenylbenzene, which are the trapping products of the geometrically destabilized C6-ring and C5-ring vinyl cation with the solvent and with the leaving group iodobenzene. Iodonium salt 2 also yields an allylic ether and allylic cyclopentenyliodobenzenes and cyclopentenylbenzene, which are the trapping products of the C5-ring allylic cation produced from the C5-ring vinyl cation by a hydride shift in a typical carbocationic rearrangement.

Volume contraction in photocured dental resins: the shrinkage-conversion relationship revisited.

UNLABELLED: Polymerization shrinkage and degree of conversion (DC) of resin composites are closely related manifestations of the same process. Ideal dental composite would show an optimal degree of conversion and minimal polymerization shrinkage. These seem to be antagonistic goals, as increased monomer conversion invariably leads to high polymerization shrinkage values. OBJECTIVES: This paper aims at accurately determining the polymerization volume contraction of experimental neat resins and to link it to the number of actual vinyl double bonds converted in single ones instead of, as generally done, to the degree of conversion. METHODS: Different mixtures of Bis-GMA/TEGDMA (traditionally used monomers) were analyzed. Contraction of the polymers was determined by pycnometry and the use of a density column. DC was determined by the use of Raman spectrometry. RESULTS: An univocal relationship has been found between the volume contraction and the actual number of vinyl double bonds converted into single ones. A contraction value of 20.39 cm3/mole (of converted C=C) was deduced from 27 measurements. SIGNIFICANCE: This relationship helps in finding solutions to the polymerization shrinkage problem. A reduction of the polymerization shrinkage due to the chemical reaction may obviously be expected from the addition of molecules allowing a decrease in the number of double bonds converted per unit volume of resin matrix, while maintaining the degree of conversion (of Bis-GMA and TEGDMA) and thus the mechanical properties. Further research will be directed at this objective.

Interphase structure-property relationships in thermoset dimethacrylate nanocomposites.

OBJECTIVES: The aim of this research was to better understand the relationships between interphase composition and the resultant mechanical properties of thermoset methacrylate nanocomposites, ultimately for the purpose of improving the properties of dental restorative materials through manipulation of the interphase. METHODS: Silica nanoparticles were silanized with three different silanes and blends of those silanes to generate six different interphase compositions. The silanes varied in their relative polarity, flexibility, and reactivity towards photo-polymerization. Composites containing 60% by mass of the silanized fillers were prepared and analyzed for uncured paste handling characteristics, vinyl conversion, biaxial flexure strength (BFS), modulus, and Knoop hardness. RESULTS: Dual silanization of the fillers improved the handling characteristics of the uncured composite pastes compared to those containing fillers silanized with 3-methacryloxypropyltrimethoxysilane. To obtain high BFS, functional groups reactive in free radical polymerization were needed in the composite interphase, but a high concentration of those groups was not necessary. Moduli were highest for composites with interphases that contained styrylethyltrimethoxysilane, a reactive aromatic silane. The hardness values of the composites with reactive interphases were all comparable. Methacrylate conversion was only modestly influenced by silane interphase composition. SIGNIFICANCE: This study suggests that dual silanization is a practical method for improving the handling characteristics of uncured dental restorative nanocomposites while maintaining or improving the mechanical properties of the cured composites.

The photophysical properties of a julolidene-based molecular rotor.

The photophysical properties of 9-dicyanovinyljulolidine are sensitive to solvent viscosity but are little affected by changes in polarity. In fluid solution, the lifetime of the first-excited singlet state is very short and triplet state formation cannot be detected by laser flash photolysis. Decay of the excited singlet state is strongly activated and weak phosphorescence can be observed in a glassy matrix at 77 K. Temperature dependent 1H NMR studies indicate that the molecule undergoes slow internal rotation in solution, for which the activation energy has a value of ca. 35 kJ mol(-1). This process is unlikely to account for the poor fluorescence quantum yield found in fluid solution. Instead, it is considered that the target compound undergoes rapid rotation around the dicyanovinyl double bond from the excited singlet state. The rate of rotation depends weakly on the viscosity of the solvent in a range of linear alcohols at room temperature. This might represent the fact that the rotor is relatively small and can pack into cavities in the solvent structure. In glycerol, the rate of rotation is more sensitive to viscosity effects but a quite complex temperature dependence is observed in ethanol. Here, the rate is almost activationless in a glassy matrix and in fluid solution at high temperature but strongly activated at intermediate temperatures.

Synthesis of cationic beta-vinyl substituted meso-tetraphenylporphyrins and their in vitro activity against herpes simplex virus type 1.

An easy route to cationic beta-vinyl substituted meso-tetraphenylporphyrin derivatives is described. Two novel compounds were tested in vitro for their antiviral photoactivity against herpes simplex virus type 1. One of these compounds exhibited a significant activity, reaching 99% of virus inactivation after 15 min of photoactivation.

Synthesis and complexing properties of [2.n](2,6)pyridinocrownophanes.

[2.n](2,6)Pyridinocrownophanes (3a-e) were efficiently prepared by intramolecular [2 + 2] photocycloaddition of vinylpyridine derivatives under irradiation using a 400-W high-pressure mercury lamp through a Pyrex filter. They were of cis-configuration with respect to the cyclobutane ring, which was proven by the specific methine proton NMR resonances at delta 3.98-4.08. From ESI-MS analysis 3a-e were found to form 1:1 complexes with Ag+ cation. In a liquid-liquid extraction, 3 showed the highest affinity toward Ag+ cation among several heavy metal nitrates. In this series, 3c possessing four ethereal oxygen atoms was found to show the highest Ag+ affinity, according to the liquid-liquid extraction and determination of stability constant with the cation. The photoreactivity of precursor vinylpyridines is discussed by the predictor gamma(r(c)) proposed by Caldwell.

Volumetric contraction and methacrylate conversion in photo-polymerized amorphous calcium phosphate/methacrylate composites.

Because of its relatively high solubility in aqueous media and its rapid transformation to hydroxyapatite, amorphous calcium phosphate (ACP) has been utilized as the filler phase of resin-based bioactive composites that have remineralization potential. The objectives of this study were to determine how various methacrylate resins and various types of ACP fillers affect acrylic vinyl conversion and polymerization shrinkage (PS). Several types of photo-crosslinkable resin systems were prepared and admixed with a mass fraction of 40% of either unhybridized, silica- or zirconia-hybridized ACP. After visible light-activated photo-polymerization ACP composites were assessed by near infrared spectroscopy for degree of vinyl conversion and by mercury dilatometry for PS. It was found for these composites that vinyl conversion was independent of filler type but strongly dependent on the type and composition of the resin phase. PS, on the other hand, showed more complex dependence both on the resin type and composition and, in some cases, on the type of ACP. In order to obtain ACP/methacrylate-based composites with maximal vinyl conversion, resin type and composition are of primary importance. However, in order to minimize volume contraction on polymerization it appears necessary to consider both the resin and filler type of these bioactive composites.

Chlorin-type photosensitizers photochemically derived from vinyl porphyrins.

The reaction of singlet oxygen with four vinyl-substituted dicarboxylic porphyrins, vinyldeuteroporphyrin (VD), ethylvinyldeuteroporphyrin (EVD), hydroxyethylvinyldeuteroporphyrin (HVD) and protoporphyrin (PP) in organic solutions is investigated. The main products, the "hydroxyaldehyde" chlorin-type derivatives, are formed with a concentration-dependent photochemical quantum yield that reaches a maximum of 7.4 +/- 1.6 x 10(-3). However, owing to the high turnover of singlet-oxygen production, these chlorin-type compounds are easily prepared photochemically with a chemical yield of 70% and little side product formation. In chemical ionization mass spectrometry, these compounds display an unusual fragmentation with a loss of 16 mass units. This is attributed to the loss of the oxygen bound to the saturated carbon of the modified pyrrole unit. All these compounds sensitize the formation of singlet oxygen with a yield around 0.8. They interact with singlet oxygen with rate constants of 5 x 10(6)-9 x 10(6) M-1 s-1, lower than those measured for vinyl porphyrins. These data are likely to help in the characterization of photoproducts of vinyl porphyrins relevant to photodynamic therapy (PP, HVD). As exemplified with VD and EVD, they also point out the reaction of singlet oxygen as an efficient route to chlorin-type photosensitizers.