Temperature-dependent hydrogen-bond geometry in liquid water

We have determined the hydrogen-bond geometry in liquid water from 0 to 80 degrees C by combining measurements of the proton magnetic shielding tensor with ab initio density functional calculations. The resulting moments of the distributions of hydrogen-bond length and angle are direct measures of thermal disorder in the hydrogen-bond network. These moments, and the distribution functions that can be reconstructed from them, impose quantitative constraints on structural models of liquid water.     

High-Resolution Infrared Spectrum of CD(3)CN: Analysis of the Interacting nu(3) and nu(6) Bands and Evaluation of the A(0) Constant

The infrared spectrum in the range 900-1230 cm(-1) including the fundamental bands nu(3) and nu(6) of CD(3)CN has been studied. The resolution attained was 0.0025 cm(-1) in the measurement on the Bruker 120 HR Fourier spectrometer in Oulu. About 4000 lines were assigned in the nu(6) band. For the weak nu(3) band, which has not been observed earlier directly, we were able to assign 206 lines in three subbands K=8-10. These lines become detectable due to the strong nu(3)/nu(6) Coriolis resonance. There is also an l(1,-2) resonance between nu(3) and nu(6), which made it possible to obtain a value 2.647721(50) cm(-1) for the axial rotational constant A(0), when D(0)(K) from force field calculations was applied. Different types of resonances with the overtone 3nu(8) and the combinations nu(4)+nu(8) and nu(7)+nu(8) were observed. A fit with a standard deviation of 0.0019 cm(-1) was attained by using a model of 10 different resonances. Copyright 2001 Academic Press.     

Reduction of water wettability of nanofibrillated cellulose by adsorption of cationic surfactants

Adsorption isotherms of single and double chain cationic surfactants with different chain length (cetyltrimethyl-, didodecyl- and dihexadecyl ammonium bromide) onto cellulose nanofibrils were determined. Nanofibrillated cellulose, also known as microfibrillated cellulose (MFC), with varying contents of carboxyl groups (different surface charge) was prepared by TEMPO-mediated oxidation followed by mechanical fibrillation. The fibril charge was characterized by potentiometric and conductometric titration. Surfactant adsorption was verified by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS). Wetting and adhesion of water onto fibril films was determined by contact angle measurements. Small aggregates (admicelles) of surfactant were shown to form on the nanofibril surfaces, well below critical micelle concentrations. The results demonstrate the possibility of using cationic surfactants to systematically control the degree of water wettability of cellulose nanofibrils.     

Structure of nanofibrillated cellulose layers at the o/w interface

The nature of layers formed by cellulose nanofibrils that had been surface modified (hydrophobized) at the oil/water (o/w) interface was investigated. The aim of the study was to clarify the mechanism underlying the excellent ability of these nanoparticles to stabilize emulsions. Layers of hydrophobized nanofibrillated cellulose spread at the o/w interface were deposited on glass slides by the Langmuir-Blodgett deposition technique. Overall evaluation of layer structures was performed by image analysis based on a Quadtree decomposition of images obtained from a flatbed scanner. A more detailed characterization of the layer structures was performed by Atomic Force Microscopy (AFM), and Field-Emission Scanning Electron Microscopy (FE-SEM). The results show that nanofibrils that were able to stabilize emulsions occur as single, dispersed fibrils or form large, network-like aggregates at the o/w interface. Fibrils that were insufficiently hydrophobized and therefore did not stabilize emulsions were only partially deposited and formed small, compact aggregates. We conclude that it is likely that the network formation is the main mechanism by which the fibrils prevent coalescence of emulsion droplets.     

Analysis of the ν1 band of CH3I

The rotational structure of the infrared band ν₁ of CH₃I has been studied at a resolution of 0.04 cm^?1 using a grating spectrometer. In the analysis including 470 lines a resonance, explained to be caused by ν₂ + 2ν₆^±2, has been taken into account. The molecular constants derived include, e.g., α₁^A = 0.051129(14) cm^?1 and α₁^B = 0.0983(9) × 10^?3 cm^?1.     

SERS‐based detection of barcoded gold nanoparticle assemblies from within animal tissue

We have explored the potential of deep Raman spectroscopy, specifically surface‐enhanced spatially offset Raman spectroscopy (SESORS), for non‐invasive detection from within animal tissue, by employing SERS‐barcoded nanoparticle (NP) assemblies as the diagnostic agent. This concept has been experimentally verified in a clinically‐relevant backscattered Raman system with an excitation line of 785 nm under ex vivo conditions. We have shown that our SORS system, with a fixed offset of 2–3 mm, offered sensitive probing of injected 2‐quinolinethiol‐barcoded NP assemblies through animal tissue containing both protein and lipid. In comparison with that of non‐aggregated SERS‐barcoded gold NPs, we have demonstrated that the tailored SERS‐barcoded aggregated NP assemblies have significantly higher detection sensitivity. We report that these NP assemblies can be readily detected at depths of 7–8 mm from within animal proteinaceous tissue with high signal‐to‐noise ratio. In addition, they could also be detected from beneath 1–2 mm of animal tissue with high lipid content, which generally poses a challenge because of high absorption of lipids in the near‐infrared region. We have also shown that the signal intensity and signal‐to‐noise ratio at a particular depth is a function of the SERS tag concentration used and that our SORS system has a 2‐quinolinethiol detection limit of 10⁻⁶ M. Higher detection depths may possibly be obtained with optimization of the NP assemblies, along with improvements in the instrumentation. Such NP assemblies offer prospects for in vivo, non‐invasive detection of tumours along with scope for incorporation of drugs and their targeted and controlled release at tumour sites. These diagnostic agents combined with drug delivery systems could serve as a ‘theranostic agent’, an integration of diagnostics and therapeutics into a single platform. Copyright © 2013 John Wiley & Sons, Ltd.     

Stiffness contribution of cellulose nanofibrils to composite materials

Nanocomposites, reinforced by different types of cellulose fibrils, have gained increased interest the last years due to the promising mechanical properties. There is a lack of knowledge about the mechanical properties of the cellulose fibrils, and their contribution to the often claimed potential of the impressive mechanical performance of the nanocomposites. This paper investigates the contribution from different types of cellulose nanofibril to the overall elastic properties of composites. A multiscale model is proposed, that allows back-calculation of the elastic properties of the fibril from the macroscopic elastic properties of the composites. The different types of fibrils used were nanofibrillated cellulose from wood, bacterial cellulose nano-whiskers and microcrystalline cellulose. Based on the overall properties of the composite with an unaged polylactide matrix, the effective longitudinal Young’s modulus of the fibrils was estimated to 65 GPa for the nanofibrillated cellulose, 61 GPa for the nano whiskers and only 38 GPa for the microcrystalline cellulose. The ranking and absolute values are in accordance with other studies on nanoscale morphology and stiffness estimates. Electron microscopy revealed that in the melt-processed cellulose nanofibril reinforced thermoplastics, the fibrils tended to agglomerate and form micrometer scale platelets, effectively forming a microcomposite and not a nanocomposite. This dispersion effect has to be addressed when developing models describing the structure–property relations for cellulose nanofibril composites.     

Highly dispersed palladium nanoparticles on mesocellular foam: an efficient and recyclable heterogeneous catalyst for alcohol oxidation

Palladium nanoparticles immobilized on amino-functionalized mesocellular foam constitute an efficient catalyst for the aerobic oxidation of primary and secondary alcohols to their corresponding carbonyl compounds in high to excellent yields. An exceptionally high TON of 365?000 was reached for the oxidation of 1-phenylethanol under solvent-free reaction conditions. The catalyst can be recycled many times with retained activity as shown by the identical rate curves of the first and fifth runs.     

Electrochemical synthesis of gold and protein gradients on particle surfaces

A straightforward, versatile approach to the production of protein gradients on planar and spherical particle surfaces is described. The method is based on the spatially controlled oxidation of thiolated surfaces by Au(III) ions generated via the electrochemical oxidation of a gold electrode in a phosphate-buffered saline solution (10 mM PBS, pH 7.2, 150 mM NaCl). Because the gold electrode is in direct contact with the thiolated surfaces, the released Au(III) ions, which are present as Au(III) chloride complexes, give rise to the formation of a surface gradient of Au(I)-thiolate complexes depending on the local redox potential given by the local Au(III) concentration. As is shown on the basis of the use of X-ray photoelectron spectroscopy and fluorescently labeled proteins, the Au(I)-thiolate complexes can subsequently be functionalized with thiolated proteins, yielding surface density protein gradients on micrometer-sized nonconducting polymer beads as well as linear Au(I)-thiolate gradients on planar silicon surfaces.     

Proton magnetic shielding tensor in liquid water

The nuclear magnetic shielding tensor is a sensitive probe of the local electronic environment, providing information about molecular structure and intermolecular interactions. The magnetic shielding tensor of the water proton has been determined in hexagonal ice, but in liquid water, where the tensor is isotropically averaged by rapid molecular tumbling, only the trace of the tensor has been measured. We report here the first determination of the proton shielding anisotropy in liquid water, which, when combined with chemical shift data, yields the principal shielding components parallel (sigma(parallel)) and perpendicular (sigma(perpendicular)) to the O-H bond. We obtained the shielding anisotropy sigma(parallel)-sigma(perpendicular) by measuring the proton spin relaxation rate as a function of magnetic induction field in a water sample where dipole-dipole couplings are suppressed by H/D isotope dilution. The temperature dependence of the shielding components, determined from 0 to 80 degrees C, reflects vibrational averaging over a distribution of instantaneous hydrogen-bond geometries in the liquid and thus contains unique information about the temperature-dependent structure of liquid water. The temperature dependence of the shielding anisotropy is found to be 4 times stronger than that of the isotropic shielding. We analyze the liquid water shielding components in the light of previous NMR and theoretical results for vapor and ice. We show that a simple two-state model of water structure fails to give a consistent interpretation of the shielding data and we argue that a more detailed analysis is needed that quantitatively relates the shielding components to hydrogen bond geometry.