A resonance Raman spectroscopic study of the protonation of Disperse Orange 25 in solution and adsorbed on oxide surfaces

The protonation of Disperse Orange 25 (DO25) in aqueous solution, and upon adsorption on oxide surfaces, was studied by resonance Raman (RR) spectroscopy. The neutral and protonated forms of DO25 were modelled by DFT calculations of the isolated molecules in the gas phase at the B3‐LYP/DZ level, enabling calculation of the vibrational spectra of these species, together with vibrational assignments. RR spectra show that DO25 is physisorbed on the SiO₂ surface, but its adsorption on SiO₂ Al₂O₃ or H‐mordenite results in protonation. This observation indicates the presence of Brønsted acidic sites on these oxide surfaces with pK_a values ⩽2.5. RR studies of the adsorption of DO25 can therefore provide useful information on the nature of surface acidity on oxides, which is complementary to that obtained from other probe molecules. Copyright © 2007 John Wiley & Sons, Ltd.     

Morphology of InN nanorods using spectroscopic Raman imaging

We report the vibrational properties of vertical and oblique InN nanorods (NRs) grown by molecular beam epitaxy (MBE). Surface optical (SO) Raman mode at 561 cm⁻¹, belonging to E₁ symmetry [SO(E₁)], is identified along with symmetry allowed Raman modes of E₂(low), E₂(high), and E₁(LO) at 87, 489, and 589 cm⁻¹, respectively, corresponding to wurtzite InN phase. Usually, SO phonon modes arise due to breakdown of translational symmetry of surface potential at surface defects, which are attributed by the surface roughness. Intensity distribution of E₁(LO) and SO(E₁) phonon modes over a specified area have been analysed using Raman area mapping with an optical resolution of 400 nm. Imaging with E₁(LO) phonon mode, originating from the bulk of the sample, distinguishes the vertical NRs alone. We are able to resolve NR morphologies in both vertical and oblique cases with additional Raman mapping analysis of SO(E₁) phonon mode, emerging from the surface irregularities, which are confined to the tip of MBE grown NRs. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface potential variation of gold nanoparticles by organic vapors revealed by Raman scattering of 1,4‐phenylenediisocyanide

The NC stretching frequency in the potential‐dependent surface‐enhanced Raman scattering spectrum of 1,4‐phenylenediisocyanide (1,4‐PDI) is very sensitive to the electrode potential, and much the same peak shift is observed when an Au nanoparticle with mean diameter from 16 to 90 nm attached to 1,4‐PDI‐adsorbed gold nanogap system is exposed solely to organic vapors. This leads us to conclude that the surface potential of Au nanoparticles should change by as much as +0.57 and −0.34 V, respectively, in the presence of CCl₄ and NH₃ because of their respective electron‐withdrawing and electron‐donating properties, regardless of the size of Au nanoparticles in the gold nanogap system. Copyright © 2012 John Wiley & Sons, Ltd.     

Assessment of membrane potential using confocal microspectrofluorimetry

Some slow potentiometric dyes, e.g., 3,3-dipropylthiacarbocyanine and tetramethylrhodamine methyl ester, exhibit fluorescence spectral changes on redistributing from aqueous medium to cells. This effect has been used for spectroscopic discrimination of the emissions from free and bound dyes in cells. Such a discrimination can, in principle, allow for the assessment of cell membrane potential in individual cells, using the Nernst equation applied to the ratio of free dye fluorescence intensities inside and outside of the cell.     

3D-assembled Ag nanowires for use in plasmon-enhanced spectroscopic sensors

Surface plasmon-enhanced spectroscopic sensors for fluorescence and Raman spectroscopy use high-density metallic nanostructures to strongly enhance the light–matter interaction. In this contribution, we will review the processes by which three-dimensional (3D) multilayered Ag nanowires assemble from one-dimensional Ag nanowires and their plasmon-enhanced sensing applications, giving emphasis to the physical mechanism underlying the plasmon-enhanced spectroscopy. In particular, we discuss the practical aspects of 3D porous and flexible plasmonic platforms used for spectroscopic sensing applications. Combining a portable spectrometer with a low-cost but highly sensitive and flexible plasmonic substrate is potentially useful for on-site chemical analysis in the contexts of environmental monitoring, food safety, forensic science, and point-of-care healthcare medical diagnostics.     

The influence of pH and anions on the adsorption mechanism of rifampicin on silver colloids

The influence of pH and anions on the adsorption mechanism of rifampicin on colloidal silver nanoparticles has been analysed by electronic absorption, resonance Raman (RR) and surface‐enhanced resonance Raman spectroscopy (SERRS). Rifampicin is a widely used antibiotic with a zwitterionic nature. SERRS spectra of rifampicin adsorbed on silver sols, prepared using hydroxylamine hydrochloride as reducing agent, undergo dramatic changes upon lowering the pH. The spectral form changes progressively from that characteristic of chemisorbed rifampicin (at pH > 7) to one very similar to the rifampicin RR spectrum (at lower pH), indicative of a modification of the adsorption mechanism on the surface of the Ag nanoparticles. The RR‐type SERRS spectrum is proposed to result from formation of an ion pair between rifampicin and Cl⁻ anions, which, deriving from the colloid preparation, are adsorbed on the Ag surface. The addition of anions to the hydroxylamine hydrochloride sol facilitates conversion from the chemisorbed to ion pair form and leads to an order of magnitude increase in the SERRS signal. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of potential functions on stochastic resonance

In this paper, the effects of a bistable potential function U(x)=-ax²/2+b|x|^2γ/(2γ) on stochastic resonance (SR) is discussed. We investigate the effects of index γ on the performance of the SR system with fixed parameters a and b, and with fixed potential barriers, respectively. To measure the performance of the SR system in the presence of an aperiodic input, the bit error rate is employed, as is commonly used in binary communications. The numerical simulations strongly support the theoretical results. The goal of this investigation is to explore the effects of the shape of potential functions on SR and give a guidance of nonlinear systems in the application of information processing.     

Absolute Raman intensity measurements and determination of the vibrational second hyperpolarizability of adamantyl endcapped polyynes

Linear sp‐carbon polyynes are ideal molecules for the direct investigation of the physical properties of one‐dimensional conjugated systems. Traditionally, the main obstacle to the study of these systems has been their instability under normal laboratory conditions. Thanks to improved chemical syntheses, a broadened range of polyynes is now available for study, including the hydrocarbon series endcapped with adamantyl groups, Ad[n]. In this work, the quantitative Raman spectroscopic analysis is reported for each member of this homologous series. The Raman scattering intensities corresponding to the major features of the polyyne segment (i.e., the effective conjugation coordinate or Я lines) are then used to evaluate the nonlinear optical (NLO) behavior via determination of the vibrational contribution to the second hyperpolarizability (γ_vib). This study shows that γ_vib values as a function of length are of the same order of magnitude as those arising from the electronic contribution to the molecular second hyperpolarizability, γ_ele, as reported for triisopropylsilyl polyynes, TIPS[n], using the differential optical Kerr effect technique. The nonlinear response for Ad[n] polyynes, supported by the analogous response for TIPS[n] polyynes, confirms that linear sp‐carbon molecules have large second hyperpolarizabilities that show a power‐law increase in γ‐values versus length that is larger than other known π‐conjugated systems, such as polyenes. Furthermore, the NLO response of polyynes versus length approaches the theoretical limit described by Kuzyk more closely than other conjugated organic oligomers. Copyright © 2012 John Wiley & Sons, Ltd.     

The effect of anti-hydrogen bond on Fermi resonance: A Raman spectroscopic study of the Fermi doublet ν1—ν12 of liquid pyridine

The effects of anti-hydrogen bond on the ν₁—ν₁₂ Fermi resonance (FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of Fermi coupling coefficient W of the ring breathing mode ν ₁ and triangle mode ν ₁₂ of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the ν₁—ν₁₂ Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν₁—ν₁₂ FR of pyridine. According to the mechanism of the formation of anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν₁—ν₁₂ FR of pyridine is given.     

Raman spectroscopic determination of the acidity constants of salicylaldoxime in aqueous solution

A sensitive and efficient method for the determination of acidity constants of salicylaldoxime (SALO) (2‐hydroxybenzaldehyde oxime), using both Raman spectroscopic and potentiometric methods, at 30 °C in 50% (wt/wt) of ethanol–water mixture and at the constant ionic strength I = 0.1 M is proposed. The effect of pH on the Raman spectra has also been studied. The Raman spectroscopic technique allows the identification of compounds in different molecular and molecular ionic structures. The limit of detection (LOD) was determined to be 0.05 mol dm⁻³ for SALO by means of Raman peak area. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic study of ceramic Sr2Bi4Ti5O18

Raman spectra of ceramic Sr2Bi4Ti5O18 （SBTi5） are reported to consist of four different Raman bands. Temperature-dependent spectra reveal the relationship between the lattice vibration and the material＇s structure. There appears a relatively large change in structure of the material at about 273K, The anharmonic potential of the material has a great influence on its phonon mode full width at half maximum （FWHM）, which can be expressed by a function of temperature. Theoretical fittings of the FWHMs for the two modes at around 312 cm^-1 and 464cm^-1 indicate that the latter phonon mode is more anharmonic than the former one.     

BH分子基态和激发态解析势能函数和光谱性质

运用多参考组态相互作用的方法和Dunning’s相关调和基函数并含扩散基的大基组aug-cc-pV5Z,获得了BH分子基态（X¹Σ⁺）和6个电子激发态（a³П, A¹П, B¹Σ⁺, b³Σ⁺, b³ 关键词： 势能曲线 解析势能函数 多参考组态相互作用方法 光谱常数     

Negative Temperature of Inner Horizon and Planck Absolute Entropy of a Kerr-Newman Black Hole

Considering the contribution of both the outer and inner horizons, the Hamilton-Jacobi method is applied to a Kerr-Newman black hole and a negative temperature of the inner horizon is obtained. Under the negative temperature inside the black hole, the thermodynamics of the two horizons is studied, and the new Bekenstein-Smarr formula is given. The entropies of the inner and outer horizons are all positive. The new entropy expression of the black hole satisfies the Nernst Theorem and can be regarded as the Planck absolute entropy.     

A resonance Raman spectroscopic investigation into the effects of fixation and dehydration on heme environment of hemoglobin

The effects of fixation and dehydration procedures on heme environment inside human erythrocytes were examined using resonance Raman spectroscopy. The resonance Raman spectroscopic data along with far‐infrared spectra show that hemoglobin in air‐dried red blood cells and those fixed in the precipitating fixatives, methanol and acetone, changes to hemichrome, a low‐spin component in which the sixth coordination site of the iron is occupied by the imidazole group of the distal histidine. The cross‐linking fixatives, formaldehyde and glutaraldehyde, maintain hemoglobin in its native conformational state (oxyhemoglobin) as evidenced by the appearance of the oxygen ligand marker bands along with the skeletal sensitive modes. However, polymerization with cross‐linking fixatives increases the auto‐oxidation kinetics of hemoglobin and gradually oxidizes it to the met state. Moreover, the dehydration of a red blood cell under N₂ results in a change of oxyhemoglobin to a six coordinate low‐spin Fe^II derivative of hemoglobin, hemochrome. Copyright © 2009 John Wiley & Sons, Ltd.     

Analytical analysis of surface potential for grooved-gate MOSFET

The improvement of the characteristics of grooved-gate MOSFETs compared to the planar devices is attributed to the corner effect of the surface potential along the channel. In this paper we propose an analytical model of the surface potential distribution based on the solution of two-dimensional Poisson equation in cylindrical coordinates utilizing the cylinder approximation and the structure parameters such as the concave corner $\theta _0 $. The relationship between the minimum surface potential and the structure parameters is theoretically analysed. Results confirm that the bigger the concave corner, the more obvious the corner effect. The corner effect increases the threshold voltage of the grooved-gate MOSFETs, so the better is the short channel effect (SCE) immunity.     

Aluminium nanohole arrays enhanced resonance Raman scattering spectra in the near ultraviolet region

Aluminium nanohole arrays with fixed diameter were fabricated by focused ion beam and the periodicities were turned.Aluminium nanohole arrays enhanced resonance Raman scattering spectra in the near ultraviolet region were studied experimentally and theoretically,which revealed that the SERRS enhancement factor was as high as 6 orders.     

Fast spectroscopic imaging strategies for potential applications in fMRI

Technical aspects of two general fast spectroscopic imaging (SI) strategies, one based on gradient echo trains and the other on spin echo trains, are reviewed within the context of potential applications in the field of functional magnetic resonance imaging (fMRI). Fast spectroscopic imaging of water may prove useful for identifying mechanisms underlying the blood oxygenation level dependence (BOLD) of the water signal during brain activation studies. Reasonably rapid mapping of changes in proton signals from brain metabolites, like lactate, creatine or even neurotransmitter associated metabolites like GABA, is substantially more challenging but technically feasible particularly as higher field strengths become available. Fast spectroscopic methods directed towards the ³¹P signals from phosphocreatine (PCr) and adenosine tri-phosphates (ATP) are also technically feasible and may prove useful for studying cerebral energetics within fMRI contexts.     

Raman spectroscopic probing of plant material using SERS

We report surface‐enhanced Raman studies on intact plant material using onion layers as a biological target, and silver nanoaggregates and silver island films as enhancing plasmonic structures. Surface‐enhanced Raman scattering (SERS) enhancement allows the detection of strong Raman signatures of chemical constituents of the surface of the onion layer such as cellulose, proteins, and flavonols. Because of long‐time incubation, SERS sensors can access the extracellular space in the inner of the layer. The location of silver nanoparticles inside the onion layer has been monitored by the SERS images collected from chemicals present in the onion and/or reporter molecules attached to the nanoparticles. Our studies show a competitive adsorption of intrinsic bio molecules of the onion layer and reporter molecules. Different spectra from different places of the layer indicate the complex heterogeneous chemical structure of the plant material. The pH‐sensitive reporter molecule para mercapto benzoic acid attached to the nanoparticles allows us to infer pH values inside the extracellular matrix of the onion layer. Copyright © 2015 John Wiley & Sons, Ltd.     

Physical properties of nanofluid suspension of ferromagnetic graphite with high Zeta potential

We report on the magnetic properties and stability of nanofluid ferromagnetic graphite (NFMG) studied through the measurements of its magnetization hysteresis curves, Raman spectrum and the so-called Zeta potential. The obtained results suggest a robust ferromagnetic behavior of NFMG even at room temperature along with a good stability of the dispersed solution (with Zeta potential around 41.3 mV) and a good reactivity between magnetic graphite and CTAB type cationic surfactant.     

Study of second-order nonlinear hyperpolarisability of all-trans-β-carotene in solutions by linear spectroscopic technique

This paper demonstrates the second-order nonlinear hyperpolarisability \gamma of all-trans-β-carotene in different solvents by linear spectroscopic technique that is based on resonance Raman scattering and UV--VIS (Ultraviolet-visible) absorption spectroscopy. Owing to the two-level model well describing the link that exists between the resonance Raman scattering and stimulated Raman scattering, the stimulated Raman polarisability α_{\rm R} can be calculated through the two-photon resonance system. The value of \gamma of all-trans-β-carotene in carbon bisulfide solution is 6.435\times 10^{-33} esu (1~esu of resistance =8.98755\times10^{11}~\Omega) that is close to the true value, because the solution of all-trans-β-carotene in carbon bisulfide satisfies the rigid resonance Raman scattering condition. This method is expected to be worthy of applications to measure the second-order nonlinear hyperpolarisability of a conjugate organic molecule.