Spectroscopic characterization of alkali-metal exchanged natrolites

Synchrotron infrared (IR) and micro-Raman spectroscopic studies have been performed on zeolite natrolites as a function of the non-framework composition at ambient conditions. This establishes the spectroscopic characterization of the ion-exchanged natrolites in the alkali-metal series both in the as-prepared hydrated (M-NAT-hyd, M = Li, Na, K, Rb, and Cs) and some stable dehydrated forms (M-NAT-deh, M = Rb and Cs). The former series exhibits non-framework cation-size dependent opening of the helical channels to span ca. 21° range in terms of the chain rotation angle, ? (or ca. 45° range in terms of the chain bridging angle, T-O2-T). For these hydrated phases, both IR and Raman spectra reveal that the degree of the red-shifts in the frequencies of the helical 8-ring channel as well as the 4-ring unit is proportional to the ionic radius of the non-framework cations. Linear fits to the data show negative slopes of -55.7 from Raman and -18.3 from IR in the 8-ring frequencies and ionic radius relationship. The spectroscopic data are also used to identify the modes of the dehydration-induced "collapse" of the helical 8-ring channels as observed in the stable anhydrous Rb-NAT-deh and Cs-NAT-deh. In addition, we demonstrate that the spectroscopic data in the hydrated series can be used to distinguish different water arrangements along the helical channels based on the frequency shifts in the H-O-H bending band and the changes in the O-H stretching vibration modes.

Spectroscopic and computational characterizations of alkaline-earth- and heavy-metal-exchanged natrolites

Synchrotron infrared (IR) and micro-Raman spectra of natrolites containing alkaline-earth ions (Ca2+, Sr2+, and Ba2+) and heavy metals (Cd2+, Pb2+, and Ag+) as extra-framework cations (EFCs) were measured under ambient conditions. Complementing our previous spectroscopic investigations of natrolites with monovalent alkali metal (Li+, Na+, K+, Rb +, and Cs+) EFCs, we establish a correlation between the redshifts of the frequencies of the 4-ring and helical 8-ring units and the size of the EFCs in natrolite. Through ab initio calculations we have derived structural models of Ca2+- and Ag+-exchanged natrolites with hydrogen atoms, and found that the frequency shifts in the H - O - H bending mode and the differences in the O - H stretching vibration modes can be correlated with the orientations of the water molecules along the natrolite channel. Assuming that the members of a solid solution series behave as an ideal mixture, we will be able to use spectroscopy to probe compositions. Deviation from ideal behavior might indicate the occurrence of phase separation on various length scales. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio calculations, Raman and NMR investigation of the plastic crystal di-methyl pyrrolidinium iodide

Above 110 °C the symmetric di-methyl-pyrrolidinium iodide salt forms a plastic crystal phase of interest in the area of new electrolyte materials. In this study ab initio calculations of this material has been conducted in order to assign the vibrational spectra. Raman spectroscopy measurements on the solid salt as well as on the salt dissolved in different solvents has been performed and these have been compared to the theoretical spectra. Furthermore, Raman spectra as a function of temperature have been recorded to investigate possible changes in inter-ionic interaction and/or structure through the phase transition. 1H NMR linewidth measurements as a function of temperature showed a large decrease in linewidth above 100 °C, attributed here to an increase in mobility in agreement with a previously reported phase transition at ~110 °C.

NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN

We report spectroscopic results from investigations of a novel solid polymeric fast-ion-conductor based on poly(acrylonitrile), (PAN, of repeat unit [CH₂CH(CN)]_n), and the salt LiCF₃SO3 . From NMR studies of the temperature and concentration dependencies of ⁷Li- and ^lH-NMR linewidths, we conclude that significant ionic motion occurs at temperatures close to the glass transition temperature of these polymer-in-salt electrolytes, in accordance with a recent report on the ionic conductivity. In the dilute salt-in-polymer regime, however, ionic motion appears mainly to be confined to local salt-rich domains, as determined from the dramatic composition dependence of the ionic conductivity. FT-Raman spectroscopy is used to directly probe the local chemical anionic environment, as well as the Li⁺–PAN interaction. The characteristic δ_s(CF₃) mode of the CF₃SO₃⁻ anion at _~750–780 cm^−l shows that the ionic substructure is highly complex. Notably, no spectroscopic evidence of free anions is found even at relatively salt-depleted compositions (e.g. N:Li_~60–10:1). A strong Li⁺–PAN interaction is manifested as a pronounced shift of the characteristic polymer C=N stretching mode, found at _~2244 cm^−l in pure PAN, to _~2275 cm^−l for Li⁺-coordinated C=N moieties. Our proton-NMR data suggest that upon complexation of PAN with LiCF3 SO₃, the glass transition occurs at progressively lower temperatures.

In-situ confocal Raman monitoring of evaporation process during protein crystallization

We have introduced an in-situ Raman monitoring technique to investigate the crystallization process inside protein drops. In addition to a conventional vapour-diffusion process, a novel procedure which actively stimulates the evaporation from a protein drop during crystallization was also evaluated, with lysozyme as a model protein. In contrast to the conventional vapour-diffusion condition, the evaporation-stimulated growth of crystals was initiated in a simple dehydration scheme and completed within a significantly shorter time. To gain an understanding of crystallization behaviours under the conditions with and without such evaporation stimulation, confocal Raman spectroscopy combined with linear regression analysis was used to monitor both lysozyme and HEPES buffer concentrations in real time. The confocal measurements having a high spatial resolution and good linear response revealed areas of local inhomogeneity in protein concentration when the crystallization started. The acquired concentration profiles indicated that (1)ÿthe evaporation-stimulated crystallization proceeded with protein concentrations lower than those under conventional vapour diffusion, and (2)ÿcrystals under the evaporation-stimulated condition were noticeable within an early stage of crystallization before the protein concentration approached its maximum value. The HEPES concentration profiles, on the other hand, increased steadily towards the end of the process regardless of the conditions used for crystallization. In particular, the observed local inhomogeneities specific to protein distribution suggested an accumulation mechanism of protein molecules that initiates the nucleation of crystals.

Pressure-induced structural transitions in MOO3·xH2O (x = 1/2, 2) molybdenum trioxide hydrates : a raman study

The high-pressure behaviors of M_OO₃·1/2H₂O and M_OO₃·2H₂O have been investigated by Raman spectroscopy in a diamond anvil cell up to 31.3 and 30.3 GPa, respectively. In the pressure range up to around 30 GPa, both M_OO₃·1/2H₂O and M_OO₃·2H₂O undergo two reversible structural phase transitions. We observed a subtle structural transition due to O−H···O hydrogen bond in M_OO₃·1/2H₂O at 3.3 GPa. We found a soft mode phase transition in M_OO₃·2H₂O at 6.6 GPa. At higher pressures, a frequency discontinuity shift and appearance of new peaks occurred in both M_OO₃·1/2H₂O and M_OO₃·2H₂O, indicating that the second phase transition is a first-order transition. The frequency redshift of the O−H stretching bands of M_OO₃·1/2H₂O and M_OO₃·2H₂O are believed to be related to the enhancement of the O−H···O weak hydrogen bonds under high pressures.

High-pressure spectroscopic study of hydrous and anhydrous Cs-exchanged natrolites

Structural phase transitions in hydrous Cs-exchanged natrolite (Cs-NAT-hyd) and anhydrous Cs-exchanged natrolite (Cs-NAT-anh) have been investigated as a function of pressure and temperature using micro-Raman scattering and synchrotron infrared (IR) spectroscopy with pure water as the penetrating pressure medium. The spectroscopic results indicate that Cs-NAT-hyd undergoes a reversible phase transition around 4.72 GPa accompanied by the discontinuous frequency shifts of the breathing vibrational modes of the four-ring and helical eight-ring units of the natrolite framework. On the other hand, we observe that Cs-NAT-anh becomes rehydrated at 0.76 GPa after heating to 100 °C and then transforms into two distinctive phases at 2.24 and 3.41 GPa after temperature treatments at 165 and 180 °C, respectively. Both of these high-pressure phases are characterized by the absence of the helical eight-ring breathing modes, which suggests the collapse of the natrolite channel and formation of dense high-pressure polymorphs. Together with the fact that these high-pressure phases are recoverable to ambient conditions, our results imply a novel means for radionuclide storage utilizing pressure and a porous material.

Spectroscopic study of the effects of pressure media on high-pressure phase transitions in natrolite

Structural phase transitions in natrolite have been investigated as a function of pressure and different hydrostatic media using micro-Raman scattering and synchrotron infrared (IR) spectroscopy. Natrolite undergoes two reversible phase transitions at 0.86 and 1.53 GPa under pure water pressure medium. These phase transitions are characterized by the changes in the vibrational frequencies of four- and eight-membered rings related to the variations in the bridging T−O−T angles and the geometry of the elliptical eight-ring channels under pressure. Concomitant to the changes in the framework vibrational modes, the number of the O−H stretching vibrational modes of natrolite changes as a result of the rearrangements of the hydrogen bonds in the channels caused by a successive increase in the hydration level under hydrostatic pressure. Similar phase transitions were also observed at relatively higher pressures (1.13 and 1.59 GPa) under alcohol−water pressure medium. Furthermore, no phase transition was found up to 2.52 GPa if a lower volume ratio of the alcohol−water to natrolite was employed. This indicates that the water content in the pressure media plays a crucial role in triggering the pressure-induced phase transitions in natrolite. In addition, the average of the mode Grüneisen parameters is calculated to be about 0.6, while the thermodynamic Grüneisen parameter is found to be 1.33. This might be attributed to the contrast in the rigidity between the TO4 tetrahedral primary building units and other flexible secondary building units in the natrolite framework upon compression and subsequent water insertion.

High-pressure structural transitions of Sc2O3 by X-ray diffraction, raman spectra, and ab initio calculations

The high-pressure behavior of scandium oxide (Sc₂O₃) has been investigated by angle-dispersive synchrotron powder X-ray diffraction and Raman spectroscopy techniques in a diamond anvil cell up to 46.2 and 42 GPa, respectively. An irreversible structural transformation of Sc₂O₃ from the cubic phase to a monoclinic high-pressure phase was observed at 36 GPa. Subsequent ab initio calculations for Sc₂O₃ predicted the phase transition from the cubic to monoclinic phase but at a much lower pressure. The same calculations predicted a second phase transition at 77 GPa from the monoclinic to hexagonal phase.

Synthesis and characterization of surface-enhanced Raman-scattered gold nanoparticles

In this paper, we report a simple, rapid, and robust method to synthesize surface-enhanced Raman-scattered gold nanoparticles (GNPs) based on green chemistry. Vitis vinifera L. extract was used to synthesize noncytotoxic Raman-active GNPs. These GNPs were characterized by ultraviolet-visible spectroscopy, dynamic light-scattering, Fourier-transform infrared (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The characteristic surface plasmon-resonance band at ~528 nm is indicative of spherical particles, and this was confirmed by TEM. The N–H and C–O stretches in FTIR spectroscopy indicated the presence of protein molecules. The predominant XRD plane at (111) and (200) indicated the crystalline nature and purity of GNPs. GNPs were stable in the buffers used for biological studies, and exhibited no cytotoxicity in noncancerous MIO-M1 (Müller glial) and MDA-MB-453 (breast cancer) cell lines. The GNPs exhibited Raman spectral peaks at 570, 788, and 1,102 cm-1. These new GNPs have potential applications in cancer diagnosis, therapy, and ultrasensitive biomarker detection.

Development and evaluation of a raman flow cell for monitoring continuous flow reactions

We show how in-line Raman spectroscopy can be used to monitor both reactant and product concentrations for a heterogeneously catalysed Suzuki cross reaction operating in continuous flow. The flow system consisted of an HPLC pump to drive a homogeneous mixture of the reactants (4-bromobenzonitrile, phenylboronic acid, and potassium carbonate) through an oven heated (80°C) palladium catalyst immobilised on a silica monolith. A custom built PTFE in-line flow cell with a quartz window enabled the coupling of an Ocean Optics Raman spectrometer probe to monitor both the reactants and product (4-cyanobiphenyl). Calibration was based on obtaining multivariate spectral data in the range 1530 cm–1 and 1640 cm–1 and using partial least-squares regression (PLSR) to obtain a calibration model which was validated using gas chromatography–mass spectrometry (GCMS) analysis. In-line Raman monitoring of the reactant and product concentrations enable (i) determination of reaction kinetic information such as the empirical rate law and associated rate constant and (ii) optimisation of either the product conversion (61 % at 0.02 mL min–1 generating 17 g h–1) or product yield (14 % at 0.24 mL min–1 generating 53 g h–1).

Graphene oxide decorated diatom silica particles as new nano-hybrids: Towards smart natural drug microcarriers

Herein, we demonstrate the fabrication of a novel nano-hybrid material based on diatom silica microparticles from diatomaceous earth (DE) and graphene oxide (GO). Two different approaches for the fabrication of nano-hybrids were used, including covalent coupling of GO sheets onto the diatom surface and electrostatic attachment. Covalent attachment was carried out through a facile amine coupling strategy via activation of carboxyl groups on GO, followed by covalent attachment to amine terminal groups of 3-aminopropyl-triethoxysilane (APTES) functionalized DE particles. Electrostatic attachment of GO (i.e. negatively charged) was carried out on positively charged APTES functionalized DE particles. The GO decorated DE nano-hybrids prepared with both the fabrication processes were extensively characterized by SEM, TEM, FTIR, and Raman spectroscopy to confirm the new chemical composition and structure. The application of the GO-DE nano-hybrid as a smart pH sensitive micro-drug carrier at pH 7.4 and pH 3.5 was demonstrated using a model drug, indomethacin (IMC). Finally, the drug release data were fitted to zero-order and Korsmeyer-Peppas models to understand the mechanism of drug release. This journal is © The Royal Society of Chemistry.

Temperature-dependent Raman spectra of bamboo-like boron nitride nanotubes

Phonon properties of boron nitride nanotubes (BNNTs) were investigated using Raman spectroscopy at different temperatures and new sp3- bonded BN vibrations were identified. The Raman peak of the E2g mode of BNNTs is found to be downshifted and broadened compared to that of hexagonal BN at the same temperature. By increasing the temperature, the energy of the E2g mode and the sp3-bonding mode are downshifted, with the temperature coefficients being -0.010 and -0.069cm-1/K, respectively. We attribute this downshifting to anharmonic effects as well as the elongation of the B-N bond in BNNT structures with increasing temperature. © 2014 The Japan Society of Applied Physics.