Crystallization of polymers

In the past 35 years, the emphasis of the activities has been doing and stimulating of fundamental research; managing research toward improvement and development of polymer systems and industrial applications of polymers; and providing analytical support by utilization and development of characterization techniques and methods. Throughout, the research activities concerned the study of molecular structure, crystallization and melting, morphology, and thermal properties of polymeric systems, and to study and understand the relations between these topics. With respect to Thermal Analysis & Calorimetry (TA&C), quantitative research has been realized in the field of crystallization of polymers of which a choice of recent work is discussed.     

The origin of the conformational preference of N,N'-diaryl-N,N'-dimethyl ureas

Poly aromatic ureas and poly aromatic amides are important classes of foldamers-oligomers with well defined conformations. We have explored the origins of the conformational preference of some N,N'-diaryl-N,N'-dimethyl ureas by a combination of NMR spectroscopy and electronic structure calculations using both a recently developed density functional (M06-2X) and a DFT approach (DFT-D) having empirical corrections for dispersive interactions. We have validated the DFT-D approach for structures of this type using high level wavefunction calculations, (CCSD(T)), of the unsubstituted N,N'-diphenyl-N,N'-dimethyl urea. For the N,N'-diaryl-N,N'-dimethyl ureas we have identified a number of 'endo' conformers (i.e. having an E,E geometrical conformation about the two urea C-N bonds), both π- and tert-butyl-stacked, as well as 'exo' structures (having a Z geometrical conformation about at least one of the C-N bonds), and have computed the relative energies of these conformers as well as the barriers for their interconversion. We find that the relative energies of the 'endo' structures closely follow the relative values of the dispersive interactions. The calculations have allowed us to associate different conformers with the various peaks in the NMR spectra, which point to relatively small differences in energy between the conformers. Somewhat larger energy differences are predicted by the two computational approaches, with the M06-2X functional performing the better of the two. It is suggested that the continuum model employed may not be sufficiently accurate to reflect the solvation of the various conformers.     

Fractionation and characterization of gold nanoparticles in aqueous solution: asymmetric-flow field flow fractionation with MALS, DLS, and UV–Vis detection

Asymmetrical-flow field flow fractionation (AFFF) separates constituents based on hydrodynamic size and is emerging as a powerful tool for obtaining high-resolution information on the size, molecular weight, composition, and stability of nanoscale particles in liquid media. We employ a customized AFFF system combining on-line detectors for multi-angle light scattering, dynamic light scattering, and UV–Vis absorption. Our objective is to develop optimized measurement protocols for the characterization of gold nanoparticles (GNPs), which are widely utilized in biomedical research and other nanotechnology applications. Experimental conditions have been optimized by controlling key parameters, including injection volume and solids concentration, mobile phase composition, membrane type and pore size, and ratio of channel-to-cross-flow rates. Individual citrate-stabilized GNP components (nominally 10, 20, 30, 40, and 60 nm) and GNPs functionalized with polyethylene glycol were separated from multicomponent GNP mixtures by AFFF and subsequently characterized. We discuss the effects due to variations in measurement parameters and GNP surface modification on observed retention, recovery, and peak resolution.     

Laser optoacoustic spectroscopy of gold nanorods within a highly scattering medium

We describe a spectroscopic comparative analysis based on the optoacoustic technique over the wavelength range from 410nm to 1000nm using a Q-switched Nd:YAG pumped optical parametric oscillator tunable source on a gold nanostructure solution located within a highly scattering medium. The advantages of this method over standard spectroscopy techniques are the possibility to localize and monitor the spectroscopic response of absorbing materials located within turbid media. The operation is confirmed using a comparative analysis with the spectroscopic results obtained from a reference measurement scheme, based on a highly sensitive collimated optical transmission setup in parallel and under the same experimental conditions as the optoacoustic technique.     

Electronic speckle-pattern interferometer using holographic optical elements for vibration measurements

We report a simple, compact electronic speckle-pattern interferometer (ESPI) incorporating holographic optical elements (HOEs) for the study of out-of-plane vibration. Reflection and transmission HOEs provide reference and object beams in the interferometer. The alignment difficulties with conventional ESPI systems are minimized using HOEs. The time-average ESPI subtraction method is used to generate the fringe pattern and remove background speckle noise by introducing a phase shift between consecutive images. The amplitude and phase maps are obtained using path-difference modulation.     

Dependence of Er:Yb-codoped 1.5 μm amplifier on wavelength-tuned auxiliary seed signal at 1 μm wavelength

We report on experiments performed with a cladding-pumped single-mode Er:Yb-codoped single-frequency fiber amplifier simultaneously seeded by a distributed-feedback diode at 1556 nm and a tunable external-cavity diode laser emitting at a wavelength of about 1 μm wavelength. The influence of the output wavelength of the external-cavity laser on amplification and reabsorption behavior of the Yb emission as well as the amplifier performance at a wavelength of 1556 nm is examined experimentally.     

Vacancy diffusion in Cu Σ = 9 [110] twist grain boundary

Both the formation energy and the diffusive activation energy of a single vacancy migrating in the first four atomic layers intra- and inter-layer near Cu Σ = 9 [110] twist GB have been investigated by using the MAEAM. The formation of the vacancy is favorable on the first layer (1L) near the GB plane and is spontaneous on sites ‘2’–‘5’ especially ‘2’ and ‘4’. The effects of the GB on the intra- as well as inter-layer migration are mainly for 1L–1L as well as for 1L–1L′, 2L–1L and 3L–1L related to the 1L, respectively. Furthermore, the vacancy in 1L is favorable to migrate in 1L (intra-layer) or through GB plane to 1L′, the one in either 2L or 3L is favorable to migrate to 1L. So the vacancy tends to converge to the first layer near the GB plane.     

Crystal chemistry of three new monodimensional fluorometalates templated with ethylenediamine

Three new monodimensional hybrid metal (Ti, In, Al) fluorides are synthesized with ethylenediamine (en) as a templating agent in solvothermal conditions assisted by microwave heating. All structures involve inorganic chains built up from TiO₂F₄ octahedra connected by two opposite O²⁻ vertices in [H₂en]·(TiOF₄) (I), from InF₆(H₂O) pentagonal bipyramids linked by F–F edges in [H₂en]·(InF₄(H₂O))₂·H₂O (II) and from (Al₇F₃₀)⁹⁻ polyanions sharing two opposite AlF₆ octahedra in [H₂en]₃·(Al₆F₂₄) (III). I is tetragonal, P4/ncc, a = 12.761(3) Å, c = 8.041(3) Å; II is orthorhombic, F2dd, a = 6.904(5) Å, b = 16.559(5) Å, c = 19.777(4) Å and III is monoclinic, P2₁/n, a = 9.387(2) Å, b = 6.710(2) Å, c = 21.513(6) Å, β = 97.18(3)°.     

Are Allenes with Zwitterionic Character Still Allenes? Of Course!

The true ground state of 1 is a matter of debate, but for clarity and convenience the allene resonance form 1 a , is the most appropriate. The arguments for aromaticity made by Christl and Engels are shown to be incorrect.

     

Robust Supramolecular Network on Ag(111): Hydrogen‐Bond Enhancement through Partial Alcohol Dehydrogenation

Alcohol oxidation and self‐assembly: the in situ oxidation of hydroxyl functional groups to quinone groups promotes the formation of enhanced hydrogen bonds and allows reorganization of the resulting supramolecular self‐assemblies, which evolve from a weakly bound dense phase to a strongly bound nanoporous open structure (see picture).