Multipole modes and spin features in the Raman spectrum of nanoscopic quantum rings

We present a systematic study of ground state and spectroscopic properties of many-electron nanoscopic quantum rings. Addition energies at zero magnetic field (B) and electrochemical potentials as a function of B are given for a ring hosting up to 24 electrons. We find discontinuities in the excitation energies of multipole spin and charge density modes, and a coupling between the charge and spin density responses that allow to identify the formation of ferromagnetic ground states in narrow magnetic field regions. These effects can be observed in Raman experiments, and are related to the fractional Aharonov-Bohm oscillations of the energy and of the persistent current in the ring

Photoluminescence studies on RF plasma-polymerized thin films

Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.

Microwave exfoliated reduced graphene oxide epoxy nanocomposites for high performance applications

Graphene has captured the attention of scientific community due to recently emerging high performance applications. Hence, studying its reinforcing effects on epoxy resin is a significant step. In this study, microwave exfoliated reduced graphene oxide (MERGO) was prepared from natural graphite for subsequent fabrication of epoxy nanocomposites using triethylenetetramine (TETA) as a curing agent via insitu polymerization. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), C13 NMR spectroscopy, X-ray photoelectron spectroscopy (XPS) and ultravioletevisible (UVevis) spectroscopy were employed to confirm the simultaneous reduction and exfoliation of graphene oxide. The reinforcing effect of MERGO on epoxy resin was explored by investigating its static mechanical properties and dynamic mechanical analysis (DMA) at MERGO loadings of 0 to 0.5 phr. The micro-structure of epoxy/MERGO nanocomposites was investigated using scanning electron microscope (SEM), transmission electron microscope (TEM) and XRD techniques. The present work reports an enhancement of 32%, 103% and 85% in tensile, impact and flexural strength respectively of epoxy by the addition of even 0.25 phr MERGO. At this loading elastic and flexural moduli also increased by 10% and 65%, respectively. Single-edge-notch three-point-Bending (SEN-TPB) fracture toughness (KIC) measurements were carried out where a 63% increase was observed by the introduction of 0.25 phr MERGO. The interfacial interactions brought about by graphene also benefited the dynamic mechanical properties to a large extent in the form of a significant enhancement in storage modulus and slightly improved glass transition temperature. Considerable improvements were also detected in dielectric properties. The epoxy nanocomposite also attained an ac conductivity of 10 5 S/m and a remarkable increase in dielectric constant. The simple and cost effective way of graphene synthesis for the fabrication of epoxy/MERGO nanocomposites may be extended to the preparation of other MERGO based polymer nanocomposites. This remarkable class of materials has thrown open enormous opportunities for developing conductive adhesives and in microelectronics

Determination of yield and quality parameters of energy crops applying laboratory and field spectroscopy

A real-time analysis of renewable energy sources, such as arable crops, is of great importance with regard to an optimised process management, since aspects of ecology and biodiversity are considered in crop production in order to provide a sustainable energy supply by biomass. This study was undertaken to explore the potential of spectroscopic measurement procedures for the prediction of potassium (K), chloride (Cl), and phosphate (P), of dry matter (DM) yield, metabolisable energy (ME), ash and crude fibre contents (ash, CF), crude lipid (EE), nitrate free extracts (NfE) as well as of crude protein (CP) and nitrogen (N), respectively in pretreated samples and undisturbed crops. Three experiments were conducted, one in a laboratory using near infrared reflectance spectroscopy (NIRS) and two field spectroscopic experiments. Laboratory NIRS measurements were conducted to evaluate to what extent a prediction of quality parameters is possible examining press cakes characterised by a wide heterogeneity of their parent material. 210 samples were analysed subsequent to a mechanical dehydration using a screw press. Press cakes serve as solid fuel for thermal conversion. Field spectroscopic measurements were carried out with regard to further technical development using different field grown crops. A one year lasting experiment over a binary mixture of grass and red clover examined the impact of different degrees of sky cover on prediction accuracies of distinct plant parameters. Furthermore, an artificial light source was used in order to evaluate to what extent such a light source is able to minimise cloud effects on prediction accuracies. A three years lasting experiment with maize was conducted in order to evaluate the potential of off-nadir measurements inside a canopy to predict different quality parameters in total biomass and DM yield using one sensor for a potential on-the-go application. This approach implements a measurement of the plants in 50 cm segments, since a sensor adjusted sideways is not able to record the entire plant height. Calibration results obtained by nadir top-of-canopy reflectance measurements were compared to calibration results obtained by off-nadir measurements. Results of all experiments approve the applicability of spectroscopic measurements for the prediction of distinct biophysical and biochemical parameters in the laboratory and under field conditions, respectively. The estimation of parameters could be conducted to a great extent with high accuracy. An enhanced basis of calibration for the laboratory study and the first field experiment (grass/clover-mixture) yields in improved robustness of calibration models and allows for an extended application of spectroscopic measurement techniques, even under varying conditions. Furthermore, off-nadir measurements inside a canopy yield in higher prediction accuracies, particularly for crops characterised by distinct height increment as observed for maize.

Ultrafast excited state dynamics controlling photochemical isomerization of N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium coordinated to a {Re-1(CO)(3)(2,2 '-bipyridine)} chromophore

Two Multifunctional photoactive complexes [Re(Cl)(CO)(3)-(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+) = N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy = 2,2'-bipyridine) were synthesized. characterized. and their redox and photonic properties were investigated by cyclic voltammetry: ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions: and time-resolved resonance Raman spectroscopy. The first reduction step of either complex Occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans -> cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3) -> MeDpe(+) (MLCT)-M-3 (MLCT = metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximate to 42 (73%) and approximate to 430ps (27%). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3) -> MeDpe(+) and Re(CO)(3) -> bpy (MLCT)-M-3 states, from which a MeDpe(+) localized intraligand 3 pi pi* excited state ((IL)-I-3) is populated with lifetimes of approximate to 0.6 and approximate to 10 ps, respectively. The 3IL state undergoes a approximate to 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle Structural variations. The complex [Re(MeDpe+)(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.

Novel lanthanide luminescent materials based on complexes of 3-hydroxypicolinic acid and silica nanoparticles

New lanthanide complexes of 3-hydroxypicolinic acid (HpicOH) were prepared: [Ln(H2O)(picOH)(2)(mu-HpicO)].3H(2)O (Ln = Eu, Tb, Er). The complexes were characterized using photoluminescence, infrared, Raman, and H-1 NMR spectroscopy, and elemental analysis. The crystal structure of [Eu(H2O)(picOH)(2)(mu-HpicO)] . 3H(2)O 1 was determined by X-ray diffraction. Compound 1 crystallizes in a monoclinic system with space group P2(1)/c and cell parameters a = 9.105(13) Angstrom, b = 18.796(25) Angstrom, and c = 13.531(17) Angstrom, and beta = 104.86(1) deg. The 3-hydroxypicolinate ligands coordinate through both N,O- or O,O- chelation to the lanthanide ions, as shown by X-ray and spectroscopic results. Photoluminescence measurements were performed for the Eu(III) and Tb(III) complexes; the Eu(III) complex was investigated in more detail. The Eu(III) compound is highly luminescent and acts as a photoactive center in nanocomposite materials whose host matrixes are silica nanoparticles.

Lanthanide complexes of 2-hydroxynicotinic acid: synthesis, luminescence properties and the crystal structures of [Ln(HnicO)(2)(mu-HnicO)(H2O)] center dot nH(2)O (Ln = Tb, Eu)

New lanthanide complexes of 2-hydroxynicotinic acid (H(2)nicO) [Ln(HnicO)(2)(mu-HnicO)(H2O)] (.) nH(2)O (Ln = Eu, Gd, Tb, Er, Tm) were prepared. The crystal structures of the [Tb(HnicO)(2)(g-HnicO)(H2O)] (.) 1.75H(2)O(1) and [Eu(HniCO)(2)(mu-HnicO)(H2O)] (.) 1.25H(2)O (2) complexes were determined by X-ray diffraction. The 2-hydroxynicotinate ligand coordinates through O,O-chelation to the lanthanide(III) ions as shown by X-ray diffraction and the infrared, Raman and NMR spectroscopy results. Photoluminescence measurements were performed for the Eu(III) and Tb(III) complexes. Lifetimes of 0.592 +/- 0.007 and 0.113 +/- 0.002 ms were determined for the Eu3+ and Tb3+ emitting states D-5(0) and D-5(4), respectively. A value around 30% was found for the D-5(0) quantum efficiency. The energy transfer mechanisms between the lanthanide ions and the ligands are discussed and compared with those observed in similar complexes involving the 3-hydroxypicolinate ligand based on the luminescence of the respective Gd3+-based complexes. (C) 2003 Published by Elsevier Ltd.

Polymer-mediated disruption of drug crystallinity

Ibuprofen (IB), a BCS Class II compound, is a highly crystalline substance with poor solubility properties. Here we report on the disruption of this crystalline structure upon intimate contact with the polymeric carrier cross-linked polyvinylpyrrolidone (PVP-CL) facilitated by low energy simple mixing. Whilst strong molecular interactions between APIs and carriers within delivery systems would be expected on melting or through solvent depositions, this is not the case with less energetic mixing. Simple mixing of the two compounds resulted in a significant decrease in the differential scanning calorimetry (DSC) melting enthalpy for IB, indicating that approximately 30% of the crystalline content was disordered. This structural change was confirmed by broadening and intensity diminution of characteristic IB X-ray powder diffractometry (PXRD) peaks. Unexpectedly, the crystalline content of the drug continued to decrease upon storage under ambient conditions. The molecular environment of the mixture was further investigated using Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectroscopy. These data suggest that the primary interaction between these components of the physical mix is hydrogen bonding, with a secondary mechanism involving electrostatic/hydrophobic interactions through the IB benzene ring. Such interactions and subsequent loss of crystallinity could confer a dissolution rate advantage for IB. (C) 2006 Elsevier B.V. All rights reserved.

Structures of Pd(CN)2and Pt(CN)2: intrinsically nanocrystalline materials?

Analysis and modeling of X-ray and neutron Bragg and total diffraction data show that the compounds referred to in the literature as “Pd(CN)2”and“Pt(CN)2” are nanocrystalline materials containing of small sheets of vertex-sharing square-planar M(CN)4 units, layered in a disordered manner with an intersheet separation of 3.44 A at 300 K. The small size of the crystallites means that the sheets’ edges form a significant fraction of each material. The Pd(CN)2 nanocrystallites studied using total neutron diffraction are terminated by water and the Pt(CN)2 nanocrystallites by ammonia, in place of half of the terminal cyanide groups, thus maintaining charge neutrality. The neutron samples contain sheets of approximate dimensions 30 A x 30 A. For sheets of the size we describe, our structural models predict compositions of Pd(CN)2-xH2O and Pt(CN)2-yNH3 (x = y = 0.29). These values are in good agreement with those obtained from total neutron diffraction and thermal analysis, and are also supported by infrared and Raman spectroscopy measurements. It is also possible to prepare related compounds Pd(CN)2-pNH3 and Pt(CN)2-qH2O, in which the terminating groups are exchanged. Additional samples showing sheet sizes in the range 10 A x 10 A (y = 0.67) to 80 A x 80 A (p = q = 0.12), as determined by X-ray diffraction, have been prepared. The related mixed-metal phase, Pd1/2Pt1/2(CN)2-qH2O(q = 0.50), is also nanocrystalline (sheet size 15 A x 15 A). In all cases, the interiors of the sheets are isostructural with those found in Ni(CN)2. Removal of the final traces of water or ammonia by heating results in decomposition of the compounds to Pd and Pt metal, or in the case of the mixed-metal cyanide, the alloy, Pd1/2Pt1/2, making it impossible to prepare the simple cyanides, Pd(CN)2, Pt(CN)2 or Pd1/2Pt1/2(CN)2, by this method.

Multi-responsive hydrogels based on N-isopropylacrylamide and sodium alginate

Hydrogels consisting of sodium alginate and N-isopropylacrylamide covalently crosslinked with N,N′-methylenebisacrylamide were prepared. The mixed-interpenetrated networks obtained were characterized using elemental analysis, Fourier transform infrared and Raman spectroscopy, swelling measurements and environmental scanning electron microscopy. The thermo- and pH-responsive properties of these hydrogels were evidenced by their swelling behaviour, which depended also on the amount of crosslinking agent and hydrogel composition.

Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

Pressure-induced electrical and structural anomalies in Pb(1-x)Ca(x)TiO(3) thin films grown at various oxygen pressures by chemical solution route

Lead calcium titanate (Pb(1-x)Ca(x)TiO(3) or PCT) thin films have been thermally treated under different oxygen pressures, 10, 40 and 80 bar, by using the so-called chemical solution deposition method. The structural, morphological, dielectric and ferroelectric properties were characterized by x-ray diffraction, FT-infrared and Raman spectroscopy, atomic force microscopy and polarization-electric-field hysteresis loop measurements. By annealing at a controlled pressure of around 10 and 40 bar, well-crystallized PCT thin films were successfully prepared. For the sample submitted to 80 bar, the x-ray diffraction, Fourier transformed-infrared and Raman data indicated deviation from the tetragonal symmetry. The most interesting feature in the Raman spectra is the occurrence of intense vibrational modes at frequencies of around 747 and 820 cm(-1), whose presence depends strongly on the amount of the pyrochlore phase. In addition, the Raman spectrum indicates the presence of symmetry-breaking disorder, which would be expected for an amorphous (disorder) and mixed pyrochlore-perovskite phase. During the high-pressure annealing process, the crystallinity and the grain size of the annealed film decreased. This process effectively suppressed both the dielectric and ferroelectric behaviour. Ferroelectric hysteresis loop measurements performed on these PCT films exhibited a clear decrease in the remanent polarization with increasing oxygen pressure.

Structural, Electronic, and Vibrational Properties of Amino-adamantane and Rimantadine Isomers

We performed a first principles total energy investigation on the structural, electronic, and vibrational propel ties of adamantane molecules, functionalized with amine and ethanamine groups. We computed the vibrational signatures of amantadine and rimanadine isomers with the functional groups bonded to clinic:ill carbon sites By comparing Out results with recent infrared and Raman spectroscopic data, we discuss the possible presence of different isomers in experimental samples.