Self‐healing of poly(propylene oxide)‐polybenzoxazine thermosets by photoinduced coumarine dimerization

In this work, a self‐healing strategy for poly(propylene oxide)s bearing coumarine‐benzoxazine units (PPO‐CouBenz)s based on light induced coumarine dimerization reactions is described. Four different types of poly(propylene oxide) amines with molecular weights ranging from 440 to 5000 Da were reacted with formaldehyde and 4‐methyl‐7‐hydroxycoumarin to yield desired (PPO‐CouBenz)s. The crosslinked polymer films were prepared by solvent casting of various compositions of PPO‐CouBenzs in chloroform followed by thermal ring opening reaction of benzoxazine groups at 210–240 °C. Thermal curing and thermal stability of the initial PPOs and final products were investigated. Using allyl benzoxazine in the formulation, it was demonstrated that the toughness of the films was improved. Photoinduced healing of coumarin‐based cured PPO‐CouBenz polymer films was investigated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2911–2918     

Novel C2-symmetric macrocycles bearing diamide-diester groups: synthesis and enantiomeric recognition for primary alkyl ammonium salts

We synthesized a series of novel macrocycles with diamide-diester groups (S,S)-1, (S,S)-2, (S,S)-3, and (R,R)-1, derived from dimethyloxalate and amino alcohols by high dilution technique, and evaluated enantiomeric recognition properties of these macrocycles toward primary alkyl ammonium salts by 1H NMR titration. Taking into account the host employed, important differences were observed in the Ka values of (R)-Am and (S)-Am for (S,S)-1 and (R,R)-1 hosts, KS/KR = 5.55 and KR/KS = 3.65, Delta Delta Go = 0.43 and -0.32 kJ mol-1, respectively. There seems a general tendency for the host to include the guests with the same absolute configuration.     

Omni-composites: a new strategy for forming bulk nanostructured materials

This work describes a new route for producing bulk materials from extremely high loading levels of inorganic nanoparticles, approaching 80%, while maintaining optical transparency. More specifically, LaF3 nanoparticles with trifluorovinyl ether (TFVE) ligands were synthesized. Because a single nanoparticle will have many functional ligands attached to its surface, the nanoparticles themselves act as cross-linkers, without the need for a matrix phase for the composite, promoting homogeneity and reduced optical scattering. In order to distinguish these new types of composites from traditional nanocomposites, they are referred to here as "omni"-composites because the material is composed entirely (Lat. omnino) of composite nanoparticles.     

Thermodynamic properties of a photon gas confined in hypothetical arbitrary-shaped perfectly reflecting nano-scale geometries

In nano scale, thermodynamic properties of gases show difference from those in macro scales. One of the reasons of this difference is the quantum size effects (QSE), which become significant when compared with the thermal de Broglie wavelength of particles to the characteristic length of the system. In this study, thermodynamic behavior of a photon gas confined in a nanoscale domain is examined in terms of QSE. It is obtained that due to quantum size effects the global thermodynamic properties of a photon gas confined in a nano scale domain are different than those in macro scale. The matter of QSE on thermodynamics of substances at micro/nano scale is relatively a new research area and the new findings might lead to significant new applications.     

Influence of alkyl chain length on phosphate self-assembled monolayers

A series of alkyl phosphates with alkyl chain lengths ranging from C10 to C18 have been synthesized. Self-assembled monolayers (SAMs) of these molecules were prepared on titanium oxide surfaces by immersion of the substrates in alkyl phosphate solutions of 0.5 mM concentration in n-heptane/isopropanol. The SAMs were characterized by means of dynamic water contact angle (dCA) measurements, variable-angle spectroscopic ellipsometry (VASE), X-ray photoelectron spectroscopy (XPS), and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS). A higher degree of order and packing density within the monolayers was found for alkyl phosphates with alkyl chain lengths exceeding 15 carbon atoms. This is reflected in a lower dCA hysteresis, as well as a film thickness measured by VASE and XPS close to the expected values for SAMs with an average alkyl chain tilt angle of 30 degrees to the surface normal. Additionally a shift of the symmetric and antisymmetric C-H stretching modes in the PM-IRRAS spectra to lower wave numbers was observed. These findings imply a higher two-dimensional crystallinity of the films derived from alkyl phosphates with a longer alkyl chain length.     

Quantitative analysis of ezetimibe in human plasma by gas chromatography‐mass spectrometry

A new, specific and sensitive GC‐MS method with electron impact ionization technique was developed for quantitative analysis of ezetimibe (EZE) in human plasma. Prior to GC analysis, EZE was derivatized with N‐methyl‐N‐trimethylsilyl‐trifluoroacetamide (MSTFA), which is a trimethyl silylating reagent. The derivatization reaction was optimized and parameters such as catalyst, derivatization time, temperature, solvent and the volume of silylating reagent were investigated. Trimethylsilyl ether derivative of EZE was determined in selected ion monitoring (SIM, mass‐to‐charge ratio (m/z): 326) mode. The method was validated with respect to LOD and LOQ, precision, accuracy, linearity, specificity, stability, and recovery. The LOQ and LOD were found as 15 and 10 ng/mL, respectively. The linearity of the method ranged from 15 to 250 ng/mL. The correlation coefficient of the calibration curve was 0.9977 ± 0.0004 (± S.E.M.). The intra‐ and inter‐day precisions (RSD) were less than 6% and accuracies (bias) for intra‐ and inter‐day accuracy were found between –4.04 and 9.71% at four different concentration levels (15, 40, 100, 250 ng/mL). The proposed method was successfully applied to real human plasma samples for determination of total EZE.     

Photoinitiated Free Radical Polymerization Using Benzoxazines as Hydrogen Donors

Summary: Free radical polymerization of methyl methacrylate (MMA) is initiated upon irradiation at λ > 350 nm in CH₂Cl₂ that contains benzoxazine (P‐a) and one of the following photosensitizers: benzophenone (BP), thioxanthone (TX), 2‐chlorothioxanthone (CTX), 2‐isopropyl thioxanthone (ITX), and camphorquinone (CQ). The postulated mechanism is based on the intermolecular reaction of the excited photosensitizer with the tertiary amino moiety of the ground state P‐a and a subsequent hydrogen abstraction reaction. The resulting aminoalkyl radicals initiate the polymerization. The incorporation of P‐a groups into polymers is demonstrated by spectroscopic methods. The possibility of deep curing using the described photoinitiating system followed by the thermal ring opening of the incorporated P‐a groups is also demonstrated.

Schematic of the photoinitiated free radical polymerization using benzoxazines as hydrogen donors.     

Conformable variational iteration method,conformable fractional reduced differential transform method and conformable homotopy analysis method for non-linear fractional partial differential equations

In this paper, we introduce conformable variational iteration method (C-VIM), conformable fractional reduced differential transform method (CFRDTM) and conformable homotopy analysis method (C-HAM). Between these methods, the C-VIM is introduced for the first time for fractional partial differential equations (FPDEs). These methods are new versions of well-known VIM, RDTM and HAM. In addition, above-mentioned techniques are based on new defined conformable fractional derivative to solve linear and non-linear conformable FPDEs. Firstly, we present some basic definitions and general algorithm for proposal methods to solve linear and non-linear FPDEs. Secondly, to understand better, the presented new methods are supported by some examples. Finally, the obtained results are illustrated by the aid of graphics and the tables. The applications show that these new techniques C-VIM, CFRDTM and C-HAM are extremely reliable and highly accurate and it provides a significant improvement in solving linear and non-linear FPDEs.     

Spectroscopic characterization of environmentally relevant C10-chloroterpenes from a photochemically modified toxaphene standard

Twenty-five pure environmentally relevant toxaphene components have been isolated from photochemically modified technical toxaphene by means of a combination of column chromatography on silica gel and preparative high resolution liquid chromatography. These compounds are 6 chlorinated camphenes (1–3, 5, 7, and 11) and 19 chlorinated bornanes (4, 6, 8–10, 12–16, 18–24, 26, and 27 according to Table 1). Two further chlorobornanes (17 and 25) have been isolated from a highly chlorinated mixture obtained by the excess chlorination of 2-exo,10-dichlorobornane. The structural elucidation of the isolated compounds has been carried out with spectroscopical methods.