Thioxanthonation of fluorenone: Visible photoinitiator for radical polymerization

Thioxanthonation of fluorenone resulted in a new visible light initiator namely, indeno [1,2‐b]thioxanthene‐7,13‐dione (TX–FN). The detailed photophysical properties of the singlet and the triplet excited states of TX–FN are reported using steady‐state absorption, fluorescence, and phosphorescence, as well as laser flash photolysis techniques. Photoinitiated polymerization of MMA with TX–FN and CQ has been investigated in the presence and absence of a co‐initiator (MDEA). Additionally, Photo‐DSC studies were performed both in mono‐ and multiacrylate systems with TX–FN and parent compounds TX and FN. The obtained results were compared for formulations consisting of CQ. At low initiator concentrations, the conversions were lower than those obtained with TX–FN. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1012–1019     

Revisiting the crystallization of poly(2‐alkyl‐2‐oxazoline)s

Poly(2‐alkyl‐2‐oxazoline)s (PAOx) exhibit different crystallization behavior depending on the length of the alkyl side chain. PAOx having methyl, ethyl, or propyl side chains do not show any bulk crystallization. Crystallization in the heating cycle, that is, cold crystallization, is observed for PAOx with butyl and pentyl side chains. For PAOx with longer alkyl side chains crystallization occurs in the cooling cycle. The different crystallization behavior is attributed to the different polymer chain mobility in line with the glass transition temperature (T_g) dependency on alkyl side chain length. The decrease in chain mobility with decreasing alkyl side chain length hinders the relaxation of the polymer backbone to the thermodynamic equilibrium crystalline structure. Double melting behavior is observed for PButOx and PiPropOx which is explained by the melt‐recrystallization mechanism. Isothermal crystallization experiments of PButOx between 60 and 90 °C and PiPropOx between 90 and 150 °C show that PAOx can crystallize in bulk when enough time is given. The decrease of T_g and the corresponding increase in chain mobility at T > T_g with increasing alkyl side chain length can be attributed to an increasing distance between the polymer backbones and thus decreasing average strength of amide dipole interactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 721–729     

Reactions of ortho-substituted α,α-dibromoacetophenones with nucleophiles: first examples of combined carbophilic and bromophilic attack on C-Br bonds

An efficient method for the formation of α-carbonyl-monosubstituted acetophenones from ortho-methoxy- and ortho-hydroxy-α,α-dibromoacetophenones and a range of selected nucleophiles, occurring via a carbophilic substitution/bromophilic substitution/protonation cascade process, is described. In turn, the preparation of α,α-dibromoacetophenones, isolated in high yields, relies on the neighboring group participation of the ortho-substituents in the starting ortho-substituted acetophenones.     

Polarized absorption spectra of highly oriented two-dimensional aggregates of tetrachlorobenzimidazolocarbocyanine in thin films

Reaching a control on the mesoscopic morphology and internal molecular arrangement of cyanine aggregates is an important step for realization of devices with tailor-made optical properties. Despite a wealth of research, understanding of the relationship between molecular organization, excitonic states and dynamics of aggregates is still preliminary. To this end, we have employed polarized absorption spectroscopy to investigate the relationship between internal molecular organization and excitonic states of J-aggregates in 1,1′,3,3′tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine (TTBC) thin films in poly-vinyl alcohol (PVA). Angular dependence of the UV–vis spectra has been measured at 11 different orientations between the electric field polarization and the macroscopic alignment axis. Aggregate spectral response consisted of an asymmetrically split Davydov pair of bands exhibiting opposite polarization: an H-band (505 nm, Lorentzian-like, polarized along the macroscopic film axis) and a J-band (594 nm, one-dimensional J-aggregate like band shape, polarized perpendicular to the macroscopic film axis). The polarized absorption observations were found to be consistent with a herringbone model for which the internal molecular arrangement, the excited state structure and dynamics have recently been detailed by us upon interpretation of isotropic absorption data in ionic aqueous solution.     

GC Investigation of the Solubility Parameters of Water-Soluble Homopolymers and Double-Hydrophilic Diblock Copolymers

Solubility parameters of water-soluble 2-(diethylamino)ethyl methacrylate (DEA) homopolymer and [2-(diethylamino)ethyl methacrylate]-[2-(dimethylamino) ethyl methacrylate] (DEA–DMA) diblock copolymer were analyzed by inverse gas chromatography and values were compared to the solubility parameters of 2-(dimethylamino) ethyl methacrylate (DMA) homopolymer. Sorption thermodynamic parameters of some aliphatic, alicyclic and aromatic hydrocarbons, weight fraction activity coefficients, Flory–Huggins interaction parameters and solubility parameters for both hydrocarbons and polymers were calculated. It was observed that sorption thermodynamic parameters on (co)polymers depend on the molecular structures of hydrocarbons. Evaluating both the calculated values of the weight fraction activity coefficients and Flory–Huggins interaction parameters, the solving ability of the hydrocarbons for DEA, DMA homopolymers and DEA–DMA diblock copolymer decreased in the following sequence: aromatic > alicyclic > aliphatic hydrocarbons.     

High temperature pyrolysis of poly(phenylene vinylene)s with poly(ε-caprolactone) or polystyrene side chains

Journal of Thermal Analysis and Calorimetry - High temperature pyrolysis studies of poly(phenylene vinylene)s PPVs with lateral substituents poly(ε-caprolactone) (PPV–PCL) or...     

Thioxanthone based water-soluble photoinitiators for acrylamide photopolymerization

The two water-soluble thioxanthone-based 2-(carboxymethoxy) thioxanthone, 1A and 2-thioxanthone-thioacetic acid sodium salts, 2A were synthesized and characterized by spectroscopic methods. The quantum yield for fluorescence emission (φ_f) in water was found to be 0.50 for 1A and 0.05 for 2A. The long phosphorescence lifetime, that is 201 and 114 ms in a matrix at 77 K for 1A and 2A, respectively, indicates a π-π∗ nature of the lowest triplet state. The triplet lifetimes were determined by laser flash photolysis as 12 and 12.6 μs for 1A and 2A. Polymerization of acrylamide (AAm) was initiated by both initiators in water. Decarboxylation of initiators was achieved during 20 min of irradiation. It was found that 2A initiated polymerization of AAm in water more efficiently than 1A.     

Spectrophotometric determination of bisoprolol in pharmaceutical preparations by charge transfer reactions

A simple, rapid and sensitive method for the spectrophotometric determination, of bisoprolol was developed. The proposed methods were based on the charge-transfer reactions of bisoprolol, as n-electron donor, with 7,7,8,8-tetracyanoqumodimethane (TCNQ) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as ??-acceptors to give highly colored complexes. The proposed methods were validated according to the ICH guidelines with respect to linearity, limit of detection, limit of quantification, accuracy, precision, recovery and specificity. Beer??s law is obeyed over the concentration ranges of 10?C60 and 10?C80 ??g/mL bisoprolol with TCNQ and DDQ, respectively. The proposed methods were successfully applied to the assay of bisoprolol in pharmaceutical preparations.     

Spectrofluorimetric Determination of Aliskiren in Tablets and Spiked Human Plasma through Derivatization with Dansyl Chloride

A simple and sensitive method has been developed and validated for the determination of aliskiren (ALS) in its dosage forms and spiked plasma. The method was based on the reaction of the drug with dansyl chloride in the presence of bicarbonate solution of pH 10.5 to give a highly fluorescent derivative which was measured at 501 nm with excitition at 378 nm in dichloromethane. Different experimental parameters affecting the development of the method and stability were carefully studied and optimized. The calibration curves were linear over the concentration ranges of 100–700 and 50–150 ng/mL for standard solution and plasma, respectively. The limits of detection were 27.52 ng/mL in standard solution, 4.91 ng/mL in plasma. The developed method was successfully applied to the analysis the drug in the commercial tablets and spiked plasma samples. The mean recovery of ALS from tablets and plasma was 100.10 and 97.81%, respectively. A proposal of the reaction pathway was presented.