New SERS feature of β‐carotene: consequences for quantitative SERS analysis

While recording SERS spectra of pure β‐carotene at sub‐micromole concentrations for reference purpose, we discovered an unusual spectral response never reported before. In pre‐resonance conditions with the 532‐nm line, SERS of β‐carotene with AgNPs exhibits among the strong υ(CC) mode at 1512 cm⁻¹ unshifted from normal Raman spectrum, additional strong bands at 1649, 1575 and 1387 cm⁻¹ as well as other medium bands not observed in the Raman spectrum of the crystalline powder. Such behavior is explained in terms of selection rules relaxation upon cyclohexene terminal rings of the β‐carotene interaction with the NP surface. AFM images of the SERS system suggested dimers and trimers clustering of the nanoparticles with adsorbed β‐carotene. In light of the new SERS feature the consequences in correct interpretation of the SERS imaging from complex biosystems containing carotenoids are discussed. Relative intensity ratio of the β‐carotene band at 1512 cm⁻¹ and water against concentration allowed a reliable SERS calibration curve for 50 to 500 nmol l⁻¹ concentration range and provided quantitative SERS assessment of the carotenoid content in the sea urchin (Paracentrotus lividus) gonads extracts. Copyright © 2015 John Wiley & Sons, Ltd.     

Stimulated Raman scattering influenced by concentration,fluorescence profile and bandwidth of β‐carotene in liquid‐core optical fiber

We demonstrated stimulated Raman scattering (SRS) of carbon disulfide (CS₂) influenced by β‐carotene in a liquid‐core optical fiber (LCOF). Owing to the double fluorescence characteristics and large third‐order optical nonlinearity of β‐carotene, the high‐order Stokes lines, such as the seventh‐order Stokes line of CS₂, can be observed at a relatively low input‐laser power. The thresholds of Stokes lines lowered with the addition of the carotenoid when the concentration of solution was within 10⁻¹² and 10⁻⁷ mol/L; the threshold increments and intensities of Stokes lines were correlative with the fluorescence profile of β‐carotene: when the fluorescence intensity of the wavenumber region on the spectrum was high, the Stokes line intensity was also high and its threshold increment was small, and vice versa. These results are expected to be worthy of the applications on the tunable laser and the seeding laser. Copyright © 2009 John Wiley & Sons, Ltd.     

Applying the method of Coherent Anti‐stokes Raman microscopy for imaging of carotenoids in microalgae and cyanobacteria

Coherent anti‐stokes Raman scattering microscopy (CARS) was applied to visualize carotenoids in microalgae and cyanobacteria. Nonlinear light–matter interaction utilized in CARS microscopy inevitably induces a number of competing nonlinear processes, such as multiphoton excitation fluorescence. Microalgae and cyanobacteria being an intrinsically well‐fluorescent object generates a strong two‐photon‐excitation fluorescence (TPEF) signal which should be effectively suppressed during the CARS experiment. Using an energetically balanced duel‐wavelength excitation scheme and spectral purification of detecting signal, the TPEF was completely blocked providing a possibility to probe microalgae and cyanobacteria in a fingerprint region of the CARS spectrum. Microspectroscopy experiments were carried out with three species ‐ cyanobacteria Nostoc Commune, Nostoc sp. and Chlorella sp. Distinct bands obtained in CARS spectra of such species were assigned to carotenoids and were taken as spectral markers in the imaging experiment. CARS imaging known as a chemical selective and label‐free technique allows non‐invasion monitoring of accumulation and movement of chemical compound at the subcellular level. Obtained high‐resolution images of carotenoid distribution in algae and cyanobacteria clearly demonstrate the potential of CARS microscopy for spatially resolved analysis of the natural products stored in the microalgae and cyanobacteria cell. Copyright © 2013 John Wiley & Sons, Ltd.     

On the use of β‐carotene as a probe for solvent polarizability

The solvatochromism of β‐carotene confirms its high sensitivity not only to the polarizability of the medium, but is also contaminated by additional solute/solvent interactions due to its dipolarity and acidity, as well as to changes in its molecular structure in some solvents. A thermochromic analysis of β‐carotene dissolved in 2‐methylbutane and 1‐chlorobutane (ClB) revealed the influence of the solvent dipolarity on its UV/Vis‐spectroscopy behavior in these solvents. Applying Abe's method to the solvent‐induced shift of the first Vis absorption band of β‐carotene in ClB revealed that the electronic excitation substantially increases its polarizability and its dipole moment. Other experimental evidence also confirms that β‐carotene is not a suitable polarizability probe of the medium. Copyright © 2013 John Wiley & Sons, Ltd.     

Solvatochromism of 2‐(N,N‐dimethylamino)‐7‐nitrofluorene and the natural dye β‐carotene: application for the determination of solvent dipolarity and polarizability

The effects of solvents on chemical phenomena (rate and equilibrium constants, spectroscopic transitions, etc.) are conveniently described by solvation free‐energy relationships that take into account solvent acidity, basicity and dipolarity/polarizability. The latter can be separated into its components by manipulating the UV–vis spectra of two solvatochromic probes, 2‐(N,N‐dimethylamino)‐7‐nitrofluorene (DMANF) and a di‐(tert‐butyl)‐tetramethyl docosanonaen probe (ttbP9) whose synthesis is laborious and expensive. Recently, we have shown that the natural dye β‐carotene can be conveniently employed instead of ttbP9 for the determination of solvent polarizability (SP) of 76 molecular solvents and four ionic liquids. In the present work, we report the polarizabilities of further 24 solvents. Based on the solvatochromism of β‐carotene and DMANF, we have calculated solvent dipolarity (SD) for 103 protic and aprotic molecular solvents, and ionic liquids. The dependence of SD and SP on the number of carbon atoms in the acyl‐ or alkyl group of several homologous series (alcohols; 2‐alkoxyethanols; carboxylic acid‐ anhydrides, and esters, ionic liquids) is calculated and briefly discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

Two‐beam multiplexed CARS based on a broadband oscillator

A two‐beam multiplexed coherent anti‐Stokes Raman scattering (CARS) microscopy setup is demonstrated by using a broadband (BB) Ti:sapphire oscillator without using any specialty fibres. A well‐defined spectral structure of the source leads to a delay‐sensitive CARS measurement in two‐colour CARS and also provides an efficient means of obtaining three‐colour CARS signals combined with the dispersion compensation of the BB pulse. Our result implies that the background suppression is limited by the onset of the spurious signals caused by the different CARS process, qualitatively differing from what is typically observed in the CARS microscopy. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of ultrasound and blanching pretreatments on polyacetylene and carotenoid content of hot air and freeze dried carrot discs

The effect of ultrasound and blanching pretreatments on polyacetylene (falcarinol, falcarindiol and falcarindiol-3-acetate) and carotenoid compounds of hot air and freeze dried carrot discs was investigated. Ultrasound pretreatment followed by hot air drying (UPHD) at the highest amplitude and treatment time investigated resulted in higher retention of polyacetylenes and carotenoids in dried carrot discs than blanching followed by hot air drying. Freeze dried samples had a higher retention of polyacetylene and carotenoid compounds compared to hot air dried samples. Color parameters were strongly correlated with carotenoids (p<0.05). This study shows that ultrasound pretreatment is a potential alternative to conventional blanching treatment in the drying of carrots.     

Spectroscopic and structural investigations of α‐, β‐, and γ‐AlH3 phases

With its reputation as a high‐energy density fuel, aluminum hydride (AlH₃) has received renewed attention as a material that is particularly suitable, not only for hydrogen storage but also for rocket propulsion. While the various phases of AlH₃ have been investigated theoretically, there is a shortage of experimental studies corroborating the theoretical findings. In response to this, we present here an investigation of these compounds based primarily on two research areas in which there is the greatest scarcity of information in the literature, namely Raman and infrared (IR) absorption analysis. To the authors' knowledge, this is the first report of experimental far‐IR absorption results on these compounds. Two different samples prepared by broadly similar ethereal reactions of AlCl₃ with LiAlH₄ were analyzed. Both Raman and IR absorption measurements indicate that one sample is purely γ‐AlH₃ and that the other is a mixture of α‐, β‐, and γ‐AlH₃ phases. X‐ray diffraction confirms the spectroscopic findings, most notably for the β‐AlH₃ phase, for which optical spectroscopic data are reported here for the first time. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopy of the transition of α‐gallium oxyhydroxide to β‐gallium oxide nanorods

The thermo‐Raman spectra of synthesised α‐gallium oxyhydroxide nanorod prove that the transition of α‐gallium oxyhydroxide to β‐gallium oxide nanorods occurs above 350 °C but below 400 °C. Scanning electron microscopy proves that the morphology of the α‐gallium oxyhydroxide nanorods is retained upon calcination to β‐gallium oxide. X‐ray diffraction patterns show that the nanorods are α‐gallium oxyhydroxide converting upon calcination to β‐gallium oxide. Intense Raman bands are observed at 190, 262, 275, 430, 520, 605, and 695 cm⁻¹, which undergo a red shift of ∼5 cm⁻¹ upon heating to 350 °C. Upon thermal treatment above 350 °C, the Raman spectrum shows a significantly different pattern. Raman bands are observed at 155, 212, 280, 430, 570, and 685 cm⁻¹. The thermo‐Raman spectra are in harmony with the TG and DTG patterns, which show that the reaction of α‐gallium oxyhydroxide to β‐gallium oxide occurs at 365 °C. Copyright © 2008 John Wiley & Sons, Ltd.     

Fiber‐based light sources for biomedical applications of coherent anti‐Stokes Raman scattering microscopy

During the past decade coherent anti‐Stokes Raman scattering (CARS) microscopy has evolved to one of the most powerful imaging techniques in the biomedical sciences, enabling the label‐free visualization of the chemical composition of tissue in vivo in real time. While the acquisition of high‐contrast images of single cells up to large tissue sections enables a wide range of medical applications from routine diagnostics to surgical guidance, to date CARS imaging is employed in fundamental research only, essentially because the synchronized multiple wavelength pulsed laser sources required for CARS microscopy are large, expensive and require regular maintenance. Laser sources based on optical fibers can overcome these limitations combining highest efficiency and peak powers with an excellent spatial beam profile and thermal stability. In this review we summarize the different fiber‐based approaches for laser sources dedicated to coherent Raman imaging, in particular active fiber technology and passive fiber‐based frequency conversion processes, i.e. supercontinuum generation, soliton self‐frequency shift and four‐wave mixing. We re‐evaluate the ideal laser parameters for CARS imaging and discuss the suitability of different laser concepts for turn‐key operation required for routine application in clinics.

     

Phase‐locking of two independent degenerate coherent anti‐Stokes Raman scattering processes: concept,proposed all‐optical implementation,and potential applications

A novel approach toward phase‐locking of two independently produced yet energetically degenerate coherent anti‐Stokes Raman scattering (CARS) processes is put forward. The proposed all‐optical implementation involves a modified Mach–Zehnder interferometer, which is utilized to transfer phase coherence from three totally uncorrelated laser beams into two degenerate CARS beams that are produced in two distinct Raman active samples. Such a CARS interferometer based on coherent phase transport allows explicit measurement and control of phase differences between the two phase‐locked degenerate CARS processes, and hence may find applications in pertinent research fields such as CARS spectroscopy (tomography) as well as quantum information processing and transfer. Copyright © 2011 John Wiley & Sons, Ltd.     

A Combined Experimental and Theoretical Study on the Formation of Ag Filaments on β‐Ag2MoO4 Induced by Electron Irradiation

A combined experimental and theoretical study is presented to understand the novel observed nucleation and early evolution of Ag filaments on β‐Ag₂MoO₄ crystals, driven by an accelerated electron beam from an electronic microscope under high vacuum. The growth process, chemical composition, and the element distribution in these filaments are analyzed in depth at the nanoscale level using field‐emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM) with energy‐dispersive spectroscopy (EDS) characterization. To complement experimental results, chemical stability, structural and electronic aspects have been studied systematically using first‐principles electronic structure theory within a quantum theory of atoms in molecules (QTAIM) framework. The Ag nucleation and formation on β‐Ag₂MoO₄ are a result of structural and electronic changes of the AgO₄ tetrahedral cluster as a constituent building block of β‐Ag₂MoO₄, consistent with Ag metallic formation. The formation of Ag filament transforms the β‐Ag₂MoO₄ semiconductor from n‐ to p‐type concomitant with the appearance of Ag defects.     

Time‐resolved investigation of the ν1 ro‐vibrational Raman band of H2CO with fs‐CARS

The technique of femtosecond time‐resolved coherent anti‐Stokes scattering (fs‐CARS) is used to investigate the strongly perturbed ν₁ ro‐vibrational Raman band of formaldehyde (H₂CO). The time‐dependent signal is simulated using a ‘Watson‐’Hamiltonian in A‐type reduction and Raman theory for asymmetric rotors. The results are compared with the experimental data. The fs‐CARS method measures the evolution of the polarization in a molecular ensemble via superposition of many states and is sensitive to spectral irregularities or line shifts of the involved transitions. ‘Coriolis’ interactions play a major role in the analysis of the ν₁ band of formaldehyde. We successfully simulate the fs‐CARS transient signal from the ν₁ band of formaldehyde including a model for multiple ‘Coriolis’ interactions, without the necessity of describing the complete interaction between all the vibrational levels. ‘Coriolis’ coupling coefficients and energy shifts are derived from the experiment by a least‐square fit. The results are discussed and compared to literature values. Copyright © 2006 John Wiley & Sons, Ltd.     

Vibrational spectroscopy and DFT calculations of di‐amino acid peptides: α‐ and β‐N‐acetyl‐L‐Asp‐L‐Glu in the solid state

Experimental vibrational spectroscopic studies and density functional theory (DFT) calculations of the di‐amino acid peptide derivatives α‐ and β‐N‐acetyl‐L‐Asp‐L‐Glu have been undertaken. Raman and infrared spectra have been recorded for samples in the solid state. DFT simulations were conducted using the B3‐LYP correlation functional and the cc‐pVDZ basis set to determine energy minimized/geometry optimized structures (based on a single isolated molecule in the gaseous state). Normal coordinate calculations have provided vibrational assignments for fundamental modes, including their potential energy distributions. Significant differences are observed between α‐ and β‐N‐acetyl‐L‐Asp‐L‐Glu both in the computed structures and in the vibrational spectra. The combination of experimental and calculated spectra provide an insight into the structural and vibrational spectroscopic properties of di‐amino acid peptide derivatives. Copyright © 2009 John Wiley & Sons, Ltd.     

Chemical imaging of glucose by CARS microscopy

Glucose is one of the most fundamental molecules within life and bioengineering sciences. Present understanding of its role in cellular and bioengineering processes relies primarily on invasive, large‐scale biochemical analysis, providing no spatial information on glucose pools or fluxes. This work identifies an emerging microscopy technique based on coherent anti‐Stokes Raman scattering (CARS), which fulfills the need of quantitative imaging of glucose at the single‐cell level with submicrometer resolution. No sample preparation with reporter molecules is required, ensuring that the low‐weight metabolite is studied under natural conditions. The potential of CARS microscopy is illustrated by quantitatively mapping glucose fluxes and distributions in a microfluidic bioreactor and in lipid‐bilayer vesicles, the latter as a model for glucose transmembrane transport. Furthermore, the metabolic response to a glucose pulse was monitored in living yeast cells. This study signifies a new era within CARS microscopy for its use of monitoring carbohydrates, in particular glucose which is one of the most abundant molecules in nature. Copyright © 2010 John Wiley & Sons, Ltd.     

X‐ray spectromicroscopy in soil and environmental sciences

X‐ray microscopy is capable of imaging particles in the nanometer size range directly with sub‐micrometer spatial resolution and can be combined with high spectral resolution for spectromicroscopy studies. Two types of microscopes are common in X‐ray microscopy: the transmission X‐ray microscope and the scanning transmission X‐ray microscope; their set‐ups are explained in this paper. While the former takes high‐resolution images from an object with exposure times of seconds or faster, the latter is very well suited as an analytical instrument for spectromicroscopy. The morphology of clusters or particles from soil and sediment samples has been visualized using a transmission X‐ray microscope. Images are shown from a cryo‐tomography experiment based on X‐ray microscopy images to obtain information about the three‐dimensional structure of clusters of humic substances. The analysis of a stack of images taken with a scanning transmission X‐ray microscope to combine morphology and chemistry within a soil sample is shown. X‐ray fluorescence is a method ideally applicable to the study of elemental distributions and binding states of elements even on a trace level using X‐ray energies above 1 keV.     

SERS detection of polychlorinated biphenyls using β‐cyclodextrin functionalized gold nanoparticles on agriculture land soil

A highly sensitive surface‐enhanced Raman scattering (SERS) platform for the selective trace analysis of persistent organic pollutant (POP) such as polychlorinated biphenyl (PCBs) was reported based on β‐CD modified gold nanoparticles (AuNPs) with the real environmental sample of polluted soil. The synthesized gold nanoparticles were characterized using UV–vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) and transmission electron microscopy (TEM). In polluted soil the presentation of PCB is confirmed by using GC‐MS. It is further verified and confirmed by using SERS. When the contaminated soil was added to the system, the binding of soil with β‐CD resulted in the aggregation of AuNPs, and excellent Raman signal was obtained which can reflect the isomers of polychlorinated biphenyls. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of the structural order of all‐trans‐β‐carotene on the Raman scattering cross section at low concentrations

Using the technique of liquid‐core optical fiber (LCOF), we measured the Raman scattering cross sections (RSCSs) of the carbon–carbon (C C) stretching vibrational modes of all‐trans‐β‐carotene in carbon disulfide (CS₂) at concentrations ranging from 10⁻⁶ to 10⁻¹¹ M . It was found that the RSCSs of all‐trans‐β‐carotene were extremely high with decreasing concentration, and the absolute RSCS of C stretching modes of all‐trans‐β‐carotene reached the value of 2.6 × 10⁻²⁰ cm² molecule⁻¹ Sr⁻¹ at 8 × 10⁻¹¹ M , which is larger than at 8 × 10⁻⁶ Mby 4 orders of magnitude. A theoretical interpretation of the anomalous experimental results is given, which introduces a qualitative nonlinear model of coherent weakly damped electron‐lattice vibrations in structural order of all‐trans‐β‐carotene. Copyright © 2010 John Wiley & Sons, Ltd.     

Interaction of water‐soluble triphenylphosphines with β‐cyclodextrin: a quantum chemistry study

The interaction of β‐cyclodextrin (β‐CD) with meta‐trisulfonated triphenylphosphine derivatives bearing one or two methyl (or methoxy) groups on the aromatic rings has been investigated by PM3 calculations. The results show that phosphine molecules interact with β‐CD having either an unsubstituted sulfophenyl group or a substituted sulfophenyl group at the para and/or meta‐position. The presence of one methyl or methoxy group in the ortho‐position on each aromatic ring prevents the formation of an inclusion complex between meta‐trisulfonated triphenylphosphine derivatives and β‐CD. The deeply included phosphines in the β‐CD cavity show significant van der Waals interactions with β‐CD. These interactions are at the origin of the high association constants between these molecules and β‐CD. Phosphines exhibiting small association constants interact with β‐CD by forming H‐bonds and weak (or null) van der Waals interactions. Copyright © 2011 John Wiley & Sons, Ltd.     

Kinetics and mechanisms of gas‐phase decarbonylation of α‐methyl‐trans‐cinamaldehyde and E‐2‐methyl‐2‐pentenal under homogeneous catalysis of hydrogen chloride

The kinetics of the gas‐phase elimination of α‐methyl‐trans‐cinamaldehyde catalyzed by HCl in the temperature range of 399.0–438.7 °C, and the pressure range of 38–165 Torr is a homogeneous, molecular, pseudo first‐order process and undergoing a parallel reaction to produce via (A) α‐methylstyrene and CO gas and via (B) β‐methylstyrene and CO gas. The decomposition of substrate E‐2‐methyl‐2‐pentenal was performed in the temperature range of 370.0–410.0 °C and the pressure range of 44–150 Torr also undergoing a molecular, pseudo first‐order reaction gives E‐2‐pentene and CO gas. These reactions were carried out in a static system seasoned reactions vessels and in the presence of toluene free radical inhibitor. The rate coefficients are given by the following Arrhenius expressions:

• Products formation from α‐methyl‐trans‐cinamaldehyde
• α‐methylstyrene :
• β‐methylstyrene :
• Products formation from E‐2‐methyl‐2‐pentenal
• E‐2‐pentene :

The kinetic and thermodynamic parameters for the thermal decomposition of α‐methyl‐trans‐cinamaldehyde suggest that via (A) proceeds through a bicyclic transition state type of mechanism to yield α‐methylstyrene and carbon monoxide, whereas via (B) through a five‐membered cyclic transition state to give β‐methylstyrene and carbon monoxide. However, the elimination of E‐2‐methyl‐2‐pentenal occurs by way of a concerted cyclic five‐membered transition state mechanism producing E‐2‐pentene and carbon monoxide. The present results support that uncatalyzed α‐β‐unsaturated aldehydes decarbonylate through a three‐membered cyclic transition state type of mechanism. Copyright © 2014 John Wiley & Sons, Ltd.