Photopolymerization studies of alkyl and aryl ester derivatives of ethyl α-hydroxymethylacrylate

Several new benzoate ester derivatives of ethyl α-hydroxymethylacrylate were synthesized using phase transfer catalysis and found to display unexpectedly rapid photopolymerization; i.e., from 2 to 8 times faster than MMA. New derivatives described here include the 4-fluoro-, 4-trifluoromethyl-, 4-methyl-, 2-hydroxy-, 4-nitro-, 4-methoxy-, 4-cyano-, and 3,4,5-trimethoxybenzoate esters along with the parent benzoate ester. Relative reactivities of these monomers in photopolymerizations were compared with those of the nonaromatic formate, acetate, hexanoate, and stearate derivatives. Reactivities of the nonaromatic ester derivatives increased with the length of the side chain while for the more reactive aromatic esters, rates increased in the order 4-methyl-, 4-fluoro- and benzoate < 4-trifluoromethyl- and 2-hydroxy- < 4-cyano- < 4-methoxy- < 3,4,5-trimethoxybenzoate. T_gs of the benzoate polymers ranged from 125°C for the 4-fluoro to 163°C for the 4-cyanobenzoate while those of the alkyl ester derivatives ranged from 15 to 78°C. Number average molecular weights of photoinitiated polymers (ca 10,000–20,000) were lower than those found for bulk and solution polymers (20,000—708,000) consistent with higher radical concentrations from photoinitiation. These materials greatly expand the number of candidates available for rapid photocure in thin film and coating applications, especially because their physical properties are those of linear rather than highly crosslinked structures formed from multifunctional systems. © 1996 John Wiley & Sons, Inc.     

Influence of oxygen pressure of ZnO/glass substrate produced by pulsed filtered cathodic vacuum arc deposition

The effects of oxygen pressure on the structural and optical properties of high quality transparent conductive ZnO thin films were studied in detail. ZnO thin films were prepared by pulsed filtered cathodic vacuum arc deposition system under various oxygen pressures on glass substrate at room temperature. With increasing oxygen pressure, the structure and optical properties of films change. The structural and optical properties of the ZnO thin films were investigated using X-ray diffraction, transmittance spectrometry, refractive index, oscillator parameters, energy band gap and Urbach tail. The films show c-axis oriented (0 0 2) hexagonal wurtize crystal structure. It has been found that the grain size of ZnO thin films increases from 16.9 to 22.6 nm with the increase of oxygen pressure from 3.8×10⁻⁴ to 6.9×10⁻⁴ Torr and the crystallinity is enhanced. Average transmittance is about 90% in the visible region of the ZnO thin films. From optical transmittance spectra of ZnO films, the absorption edge shifts towards the taller wavelength with an increase in oxygen pressure. The energy band gap decreases from 3.31 to 3.20 eV with an increase in oxygen pressure. The packing density investigation shows in ZnO films high packing densities (above 0.78) can be obtained.     

Structure–reactivity relationships of alkyl α‐hydroxymethacrylate derivatives

A series of alkyl α‐hydroxymethacrylate derivatives with various secondary functionalities (ether, ester, carbonate, and carbamate) and terminal groups (alkyl, cyano, oxetane, cyclic carbonate, phenyl and morpholine) were synthesized to investigate the effect of intermolecular interactions, H‐bonding, π–π interactions, and dipole moment on monomer reactivity. All of the monomers except one ester and one ether derivative are novel. The polymerization rates, determined by using photo‐DSC, showed the average trend (aromatic carbamate > hydroxyl > ester > carbonate ～ aliphatic carbamate ～ ether), with several exceptions due to the differences in terminal groups. There is a correlation between the chemical shift differences of the double bond carbons, the calculated dipole moments, and the reactivities only for nonhydrogen bonded monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Potentiometric Studies on Complexation of Cu(II) Ion with Methyl/Nitro-Substituted 1,10-Phenanthrolines and Selected Amino Acids

Protonation constants of methyl/nitro substituted 1,10-phenanthrolines {(m/n-sphen): 4-methyl-phenanthroline (4-mphen), 5-methyl-1,10-phenanthroline (5-mphen), 4,7-dimethyl-1,10-phenanthroline (dmphen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10-phenanthroline (5-nphen)] and the amino acids (aa) l-tyrosine (tyr) and glycine (gly), and their corresponding binary and ternary stability constants with Cu(II), were determined in aqueous 0.1 mol·L^?1 KCl ionic media at 298.15 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. The species distribution diagrams were obtained using the “SPE” software package under the experimental conditions described. The order of stability of the ternary complexes in terms of the primary ligands is [Cu(tmphen)(aa)]⁺ > [Cu(dmphen)(aa)]⁺ > [Cu(4-mphen)(aa)]⁺ > [Cu(5-mphen)(aa)]⁺ > [Cu(5-nphen)(aa)]⁺. The stability constants of the ternary complexes decrease in the following order: [Cu(m/n-sphen)(gly)]⁺ > [Cu(m/n-sphen)(tyr)]⁺, which is identical to the sequence found for the binary complexes of Cu(II) with gly and tyr.     

Real-time optical reconstruction of the diffused 3D object using phase information calculated by Continuous Wavelet Transform

We propose the real time optical reconstruction of a three-dimensional (3D) object from a digitally recorded hologram. Phase distribution of the recorded hologram is numerically calculated by 1-dimensional Continuous Wavelet Transform (1D-CWT) for digital reconstruction with phase only information. Also, the phase distribution of 1D-CWT transferred to the spatial light modulator (SLM) is used to obtain optically reconstructed image. It is observed that an efficient real-time analysis can be achieved, if phase of 1D-CWT is used. In the same time, optically reconstructed 3D objects obtained by only phase information are about three times brighter than bleached hologram intensity's. So the minimum power loss can be obtained. Numerical and experimental results are presented.     

Urea dimethacrylates functionalized with bisphosphonate/bisphosphonic acid for improved dental materials

Incorporation of bisphosphonate/bisphosphonic acid groups in dental monomer structures should increase interaction of these monomers with dental tissue as these groups have strong affinity for hydroxyapatite. Therefore, new urea dimethacrylates functionalized with bisphosphonate (1a, 1b) and bisphosphonic acid (2a, 2b) groups are synthesized and evaluated for dental applications. Monomers 1a and 1b are synthesized from 2‐isocyanatoethyl methacrylate (IEM) and two bisphosphonated amines (BPA1 and BPA2), prepared as reported elsewhere. Selective dealkylation of the bisphosphonate ester groups of 1a and 1b using trimethylsilyl bromide (TMSBr) gives monomers (2a and 2b) with bisphosphonic acid functionality. X‐ray diffractometer (XRD), Raman spectroscopy, and X‐ray photoelectron spectroscopy (XPS) analyses of monomer‐treated HAP particles show that 2a induces formation of stable monomer‐calcium salts, similar to 10‐methacryloyloxydecyl dihydrogen phosphate (MDP), with higher chemical interaction than 2b. The photopolymerization studies indicate good copolymerizability with commercial dental monomers. In vitro studies on NIH 3T3 mouse embryonic fibroblast cells have clearly shown that the tested monomers (1b and 2b) are not toxic according to the MTT standards. All these properties make these monomers suitable as biocompatible cross‐linkers/adhesives for dental applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3195–3204     

Multiarm star triblock terpolymers via sequential double click reactions

Multiarm star triblock terpolymers were obtained by using two different click reactions sequentially: Cu(I) catalyzed azide–alkyne and Diels–Alder. The synthetic strategy is described as follows: (poly(methyl methacrylate))_n‐(polystyrene)_m‐poly(divinyl benzene)) ((PMMA)_n‐(PS)_m‐polyDVB) multiarm star diblock copolymer was first obtained from an azide–alkyne click reaction of (alkyne‐PS)_m‐polyDVB multiarm star polymer with α‐anthracene‐ω‐azide PMMA (anth‐PMMA‐N₃), followed by a Diels–Alder click reaction of the anthracene groups at the star periphery with α‐maleimide poly (tert‐butyl acrylate) (PtBA‐MI) or α‐maleimide poly(ethylene glycol) (PEG‐MI) leading to target (PtBA)_k‐(PMMA)_n‐(PS)_m‐polyDVB and (PEG)_p‐(PMMA)_n‐(PS)_m‐polyDVB multiarm star triblock terpolymers. The hydrodynamic diameter of individual multiarm star triblock terpolymers were measured by dynamic light scattering (DLS) to be ～24–27 nm in consistent with the atomic force microscopy (AFM) images on silicon substrates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1557–1564, 2010     

Synthesis,characterization, crystal structure,and antimicrobial studies of 2-morpholinoethyl-substituted benzimidazolium salts and their silver(I)-N-heterocyclic carbene complexes

Research on Chemical Intermediates - This article describes synthesis of N-morpholinoethylbenzimidazole (1), 2-morpholinoethyl-substituted benzimidazolium salts (NHC precursors, 2a–c), and...     

Solvatochromic rotaxane molecular shuttles

A strongly fluorescent bistable rotaxane is described in which the relative position of the macrocyclic ring with respect to a solvatochromic fluorophore gives a strong response in the spectral domain.