Molecular dynamics of tert-butyl chloride confined in CPG studied by NMR

The molecular dynamics of tert-butyl chloride (TBC) confined to Controlled Pore Glass matrices of 25 and 7.5 nm were investigated by measuring NMR linewidths, lineshapes, and 1H and 2H spin--lattice relaxation times. The behaviour of confined TBC can be explained assuming that the guest molecules form two distinct phases; the surface-affected phase, composed of molecules located at the pore surface, and the bulk-like phase located at the centre of the pores. The bulk-like component of confined TBC, at the temperatures corresponding to the phase III, is characterized by two dynamically different subphases.     

Proton relaxation NMR study of polycrystalline progesterone.

Polycrystalline progesterone (4-pregnene-3,20-dione, C21H30O2) has been investigated by proton NMR methods between 80 and 350 K. A reduction in dipolar second moment is ascribed to methyl group reorientation. Minima in the spin-lattice relaxation time found in measurements at five frequencies from 7 to 200 MHz are attributed to reorientation of two of the three methyl groups in each molecule, characterized by activation energy Ea = 10.9 +/- 0.8 kJ/mol and tau o = (2.3 +/- 0.2) x 10(-13) s. Additional relaxation at lower temperatures is attributed to reorientation of the third methyl group with Ea approximately 3.4 kJ/mol. Measurements were also made of relaxation in the rotating frame.     

High homogeneity B(1) 30.2 MHz Nuclear Magnetic Resonance Probe for off-resonance relaxation times measurements

This paper reports on design and construction of a double coil high-homogeneity ensuring Nuclear Magnetic Resonance Probe for off-resonance relaxation time measurements. NMR off-resonance experiments pose unique technical problems. Long irradiation can overheat the sample, dephase the spins because of B(1) field inhomogeneity and degrade the signal received by requiring the receiver bandwidth to be broader than that needed for normal experiment. The probe proposed solves these problems by introducing a separate off-resonance irradiation coil which is larger than the receiver coil and is wound up on the dewar tube that separates it from the receiver coil thus also thermally protects the sample from overheating. Large size of the irradiation coil also improves the field homogeneity because as a ratio of the sample diameter to the magnet (coil) diameter increases, the field inhomogeneity also increases (Blümich et al., 2008) [1]. The small receiver coil offers maximization of the filling factor and a high signal to the noise ratio.     

Local mobility in grafted polydimethylsiloxane melts

Spin–lattice relaxation time constants, T₁, were studied for low-molecular-weight linear and grafted polydimethylsiloxane over a wide temperature and frequency range. Quantitative evaluations of proton T₁ measurements indicated two relaxation processes: anisotropic rotation of methyl groups around the Si–C bond (low temperature process) and motions of the PDMS side-chains connected with the glass transition (high temperature process). Additional analyses of the T₁ relaxation dispersion profiles revealed specific local segment fluctuation times, which are characteristic of the coherent motions in the grafted polymer chains.     

Novel method to determine the actual surface area of a laser-nanotextured sensor

The actual surface area of a gold-coated conductive layer over the laser nano-textured surface of sapphire is determined using an electrochemical cyclic voltammetry. The method is down scaled to measure the sensing surface area of 200 × 200 μm² on a laser-ablated ripple sensor used for surface-enhanced Raman spectroscopy/scattering (SERS). Ripple SERS sensors made on different substrates of high refractive index materials such as GaP, diamond, SiC, and Al₂O₃ make a versatile sensing platform with the detection of analyte (here a thiophenol) down to 10 nM concentrations. Direct measurement of the surface area provides a powerful tool to investigate roughness, porosity, and morphology of coatings used for SERS or other light harvesting surfaces such as solar cells. Novelty of the proposed method is in the use of cathodic peak of surface passivation–activation cycle for calculation of surface charge. The method enables high-accuracy surface area measurements from as small as 0.01 mm² pads up to functional solar cells.     

Solid state H NMR study of molecular dynamics and domain sizes in PBT with the fullerene derivates: Decylamine-C60 and tetracyanoethylene oxide-C60

The solid-state ¹H NMR on-resonance and off-resonance techniques have been performed to study molecular dynamics and domain sizes in heterogenous nanocomposites based on poly(butylene terephthalate) and nanoparticles C₆₀ modified by n-decylamine (DA) or tetracyanoethylene oxide (TCNEO), respectively. The spin-lattice off-resonance relaxation times in the rotating frame T_1ρ^off as well as the second moment M₂ of the absorption line were analysed as a function of temperature. To determine the size of heterogeneities and characterize the morphology of the nanocomposites, the ¹H NMR spin-diffusion experiment designed by Goldman-Shen [1,2] was performed. The results from the measurements allow us to investigate the spin-diffusion phenomenon and relaxation behavior of the new nanocomposites.     

Molecular Dynamics and Structure of Poly(Methyl Methacrylate) Chains Grafted from Barium Titanate Nanoparticles

Core−shell nanocomposites comprising barium titanate, BaTiO₃ (BTO), and poly(methyl methacrylate) (PMMA) chains grafted from its surface with varied grafting densities were prepared. BTO nanocrystals are high-k inorganic materials, and the obtained nanocomposites exhibit enhanced dielectric permittivity, as compared to neat PMMA, and a relatively low level of loss tangent in a wide range of frequencies. The impact of the molecular dynamics, structure, and interactions of the BTO surface on the polymer chains was investigated. The nanocomposites were characterized by broadband dielectric and vibrational spectroscopies (IR and Raman), transmission electron microscopy, differential scanning calorimetry, and nuclear magnetic resonance. The presence of ceramic nanoparticles in core–shell composites slowed down the segmental dynamic of PMMA chains, increased glass transition temperature, and concurrently increased the thermal stability of the organic part. It was also evidenced that, in addition to segmental dynamics, local β relaxation was affected. The grafting density influenced the self-organization and interactions within the PMMA phase, affecting the organization on a smaller size scale of polymeric chains. This was explained by the interaction of the exposed surface of nanoparticles with polymer chains.     

Study of nucleation induced structure modification in isotactic polypropylene by DMTA and solid state NMR

Isotactic polypropylene (iPP) modified by heterogeneous nucleation and molten state drawing was investigated using the DMTA and NMR methods. The nucleation was realized by specific α and β nucleating agents, 1,3,2,4-bis(3,4-dimetylobenzylideno) sorbitol (Millad 3988, Miliken) leading to the creation of the α phase, and N,N′-dicyklohexylo-2,6-naftaleno dikarboxy amid (NJ100) as the β phase promoter. The processing induced modification was performed by molten state drawing during an extrusion in the range between the die exit and the calibration unit. An increase of the glass transition temperature of iPP was found to be drawing independent for the β-nucleated samples, and dependent in the case of the α-iPP. Changes in the macromolecular mobility, depending on the α/β iPP structure and molten state drawing, was found by NMR lineshape and second moment measurements.