Novel Silanol-Containing Polymers and Their Blends

ABSTRACT

Novel 4-vinylphenyldimethylsilanol polymer (PVPDMS) and co-polymers (ST-VPDMS) were synthesized by the oxyfunctionalization re- action of the silane. The reaction was found to proceed efficiently and quantitatively. Miscibility studies indicated that about 4 molpercnt; of 4-vin- ylphenyldimethylsilanol (VPDMS) functional group in the copolymer could achieve miscibility with poly(n-butyl methacrylate) (PBMA) and poly(N-vinylpyrrolidone) (PVPr). However, for copolymers containingmore than 34 molpercnt; VPDMS, their blends with PBMA were immiscible. The observed miscibility window of ST-VPDMS/PBMA blends was as- cribed to the competition between the self-association of dimethylsilanol groups and intermolecular hydrogen bonding of dimethylsilanol groups with the carbonyl groups of PBMA. A comparison of the efficiency of the miscibility enhancement and the miscibility windows of VPDMS, p-(hexafluoro-2-isopropyl) styrene (HFPS), and phenolic-containing polymers was made in terms of such competition. The glass transition behavior of the miscible blends involving VPDMS and HFPS-containing styrene copolymers with PBMA were analyzed by the Schneider equation.     

Complexity behind CO2 capture on NH2-MIL-53(Al)

Some Metal Organic Frameworks (MOFs) show excellent performance in extracting carbon dioxide from different gas mixtures. The origin of their enhanced separation ability is not clear yet. Herein, we present a combined experimental and theoretical study of the amino-functionalized MIL-53(Al) to elucidate the mechanism behind its unusual high efficiency in CO(2) capture. Spectroscopic and DFT studies point out only an indirect role of amine moieties. In contrast to other amino-functionalized CO(2) sorbents, no chemical bond between CO(2) and the NH(2) groups of the structure is formed. We demonstrate that the functionalization modulates the "breathing" behavior of the material, that is, the flexibility of the framework and its capacity to alter the structure upon the introduction of specific adsorbates. The absence of strong chemical interactions with CO(2) is of high importance for the overall performance of the adsorbent, since full regeneration can be achieved within minutes under very mild conditions, demonstrating the high potential of this type of adsorbents for PSA like systems.     

The use of phospholipid modified column for the determination of lipophilic properties in high performance liquid chromatography

A new chromatographic stationary phase obtained by coating a reversed phase amide column with phosphatidylcholine based liposomes solution to yield a phospholipid modified column (PLM). The modification is achieved by the dynamic coating method which recycles the coating solution through the column in a closed loop for a period of 24 h. The chromatographic properties of the new column have changed significantly as compared to the original amide column due to the phospholipid coating. A good correlation was observed between n-octanol/water logP values and the logarithm of the retention factor obtained on the PLM column for a large number of solutes. In addition the PLM column was characterized using the linear solvation energy relationship (LSER). The values of the LSER system constants for the PLM column were calculated and were found to be very close to those of the n-octanol/water extraction system thus suggesting that the PLM column can be used for the estimation of n-octanol/water partition coefficient and serve as a possible alternative to the shake-flask method for lipophilicity determination. In addition, the results suggest that the PLM column can provide an alternative to other phospholipid-based column such as the IAM and the DPC columns.     

Sheet-beam geometry for in vivo fluorescent x-ray computed tomography: proof-of-concept experiment in molecular imaging

We propose a fluorescent x-ray computed tomography method using an array of detectors with an incident sheet beam, aimed at providing molecular imaging with high sensitivity and good spatial resolution. In this study, we prove the feasibility of this concept and investigate its imaging properties, including spatial and contrast resolutions and quantitativeness, by imaging an acrylic phantom and a normal mouse brain using a preliminary imaging system with monochromatic synchrotron x rays.     

Discrete angle rotations of Bi nanoparticles embedded in a Ga matrix

Spontaneous instabilities of nanoparticles are known to be influenced by the temperature, and strongly depend on the particle size. However, it is not clear what is the role of the surrounding material that is in contact with the particle. Here we report on the difference between spontaneous rotations of Bi nanoparticles embedded in amorphous SiO and those embedded in liquid Ga. The phenomenon was studied quantitatively by time resolved transmission electron microscopy using Fourier Transform analysis of highresolution electron microscopy images. While rotations of Bi nanoparticles embedded in amorphous SiO occur by all angles, the rotations of Bi nanoparticles embedded in liquid Ga occur by discrete angles. Our results point quantitatively, for the first time, to the role and importance of the contacting surrounding surface during the rotation of nanoparticles.     

Carbon-based materials applied to the development of chemically modified sensors: Trends to environmental applications**

Nowadays, carbon-based materials applied to the development of chemically modified sensors have been highlighted once they can generate methods with high sensitivity, stability, conductivity, accuracy and low cost. Hence, these sensors have been used in environmental monitoring in aneco-friendlyy, sensitive, fast, efficient, inexpensive and robust way. In this review, firstly we described about carbon-based materials and their derivatives, followed by the chemically modified carbon-based sensors manufacturing overview and their applications in environmental analytical chemistry related to inorganic and organic compounds determinations. Future perspectives on trends of the carbon-based materials applications in the sensor modifications are also described.     

A Deep-Blue-Emitting Heteroatom-Doped MR-TADF Nonacene for High-Performance Organic Light-Emitting Diodes**

We present a p- and n-doped nonacene compound, NOBNacene, that represents a rare example of a linearly extended ladder-type multiresonant thermally activated delayed fluorescence (MR-TADF) emitter. This compound shows efficient narrow deep blue emission, with a λ_PL of 410 nm, full width at half maximum, FWHM, of 38 nm, photoluminescence quantum yield, Φ_PL of 71 %, and a delayed lifetime, τ_d of 1.18 ms in 1.5 wt % TSPO1 thin film. The organic light-emitting diode (OLED) using this compound as the emitter shows a comparable electroluminescence spectrum peaked at 409 nm (FWHM=37 nm) and a maximum external quantum efficiency (EQE_max) of 8.5 % at Commission Internationale de l’Éclairage (CIE) coordinates of (0.173, 0.055). The EQE_max values were increased to 11.2 % at 3 wt % doping of the emitter within the emissive layer of the device. At this concentration, the electroluminescence spectrum broadened slightly, leading to CIE coordinates of (0.176, 0.068).     

Recent Developments in Kramers’ Theory of Reaction Rates

In this short review, we provide an update of recent developments in Kramers’ theory of reaction rates. After a brief introduction stressing the importance of this theory initially developed for chemical reactions, we briefly present the main theoretical formalism starting from the generalized Langevin equation and continue by showing the main points of the modern Pollak, Grabert and Hänggi theory. Kramers’ theory is then sketched for quantum and classical surface diffusion. As an illustration the surface diffusion of Na atoms on a Cu(110) surface is discussed showing escape rates, jump distributions and diffusion coefficients as a function of reduced friction. Finally, some very recent applications of turnover theory to different fields such as nanoparticle levitation, microcavity polariton dynamics and simulation of reaction in liquids are presented. We end with several open problems and future challenges faced up by Kramers turnover theory.     

Visible Light-Mediated Cyclisation Reaction for the Synthesis of Highly-Substituted Tetrahydroquinolines and Quinolines

Condensation of 2-vinylanilines and conjugated aldehydes followed by an efficient light-mediated cyclisation selectively yields either substituted tetrahydroquinolines with typically high dr, or in the presence of an iridium photocatalyst the synthesis of quinoline derivatives is demonstrated. These atom economical processes require mild conditions, with the substrate scope demonstrating excellent site selectivity and functional group tolerance, including azaarene-bearing substrates. A thorough experimental mechanistic investigation explores multiple pathways and the key role that imine and iminium intermediates play in the absorption of visible light to generate reactive excited states. The synthetic utility of the reactions is demonstrated on gram scale quantities in both batch and flow, alongside further manipulation of the medicinally relevant products.     

Acylphosphonamidates and α-hydroxyiminophosphonamidates. Synthesis of N-acylphosphordiamidates by Beckmann rearrangement. Crystal structure of (E)-α-hydroxyiminobenzyl-1-pyrrolidinylphosphinate

Reaction of methyl benzoylphosphonochloridate (3) with a secondary or primary series of amines yielded methyl benzoylphosphonamidates, 4a-e. The latter compounds reacted with hydroxylamine to yield a-hydroxyiminobenzylphosphonamidates (5a-e), largely as (E)-isomers. The structure of methyl (E)-a-hydroxyimino-benzyl-1-pyrrolidinylphosphinate (5b) was determined by single-crystal X-ray crystallography. Heating oximes 5a-e in boiling toluene caused them to undergo Beckmann rearrangement to N-benzoylphosphordiamidates 6a-e. © 1996 John Wiley & Sons, Inc.