Desorption/ionization of biomolecules from aqueous solutions at atmospheric pressure using an infrared laser at 3 μm

A new atmospheric pressure (AP) infrared (IR) matrix-assisted laser desorption/ionization (MALDI) ion source was developed and interfaced with a Thermo Finnigan LCQ ion trap mass spectrometer. The source utilized a miniature all-solid-state optical parametric oscillator (OPO)-based IR laser system tunable in the lambda = 1.5-4 microm spectral range and a nitrogen ultraviolet (UV) laser (lambda = 337 nm) for use in comparative studies. The system demonstrated comparable performance at 3 microm and 337 nm wavelengths if UV matrices were used. However, AP IR-MALDI using a 3 microm wavelength showed good performance with a much broader choice of matrices including glycerol and liquid water. AP IR-MALDI mass spectra of peptides in the mass range up to 2000 Da were obtained directly from aqueous solutions at atmospheric conditions for the first time. A potential use of the new AP IR-MALDI ion source includes direct MS analysis of biological cells and tissues in a normal atmospheric environment as well as on-line coupling of mass spectrometers with liquid separation techniques.     

Intercomparison of simultaneously obtained infrared (4.8 microm) and visible (515-715 nm) ozone spectra using ACE-FTS and MAESTRO

Laboratory ozone absorption spectra were measured simultaneously in the visible (515-715 nm) and infrared (2070-2140 cm(-1)) spectral regions using SCISAT-1's MAESTRO (Measurement of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and ACE-FTS (Atmospheric Chemistry Experiment-Fourier Transform Spectrometer) spectrometers. An intercomparison of these measurements was used to assess the relative accuracy of HITRAN absolute line strengths, for which there was a 4% change between the 2000 and 2004 versions. Results reported here show that Chappuis band cross section strengths are more consistent with the HITRAN 2004 4.8 microm band line strengths than with the 2000 compilation.     

Vibrational and electronic absorption spectroscopy of dibenzo[b,def]chrysene and its ions

The vibrational and electronic absorption spectra of dibenzo[b,def]chrysene (DBC) and its ions in argon matrixes have been recorded. Assignment of the observed infrared (IR) bands has been made by comparison with the density functional theory (DFT) computations of harmonic vibrational frequencies (with 6-31G(d,p) or 6-311+G(d,p) basis sets). Extensive time-dependent (TD) DFT calculations of vertical excitation energies have aided in the assignment of the experimental electronic absorption transitions. In general, the theoretical predictions are in good agreement with the observed ultraviolet and visible bands. By correlating IR and UV-visible band intensities (after UV photolysis), it has been shown that both DBC cations and anions are formed. The IR band intensity distributions of the DBC ions differ markedly from neutral DBC. A synthetic spectrum composed of neutral, cationic, and anionic DBC contributions compares reasonably well with the interstellar features of the "unidentified infrared" (UIR) bands from the reflection nebula NGC 7023. Finally, it is shown that the electronic absorption bands of the DBC ions lie in close proximity to several of the diffuse interstellar visible absorption bands (DIBs).     

IR,Raman, and UV/Vis Spectra of Corannulene for Use in Possible Interstellar Identification

The spectroscopic characterization of corannulene (C₂₀H₁₀) is carried out by several techniques. The high purity of the material synthesized for this study was confirmed by gas chromatography‐mass spectrometry (GC‐MS). During a high‐performance liquid chromatography (HPLC) process, the absorption spectrum of corannulene in the ultraviolet (UV) and visible (vis) ranges is obtained. The infrared (IR) absorption spectrum is measured in CsI pellets, and the Raman scattering spectrum is recorded for pure crystal grains. In addition to room temperature measurements, absorption spectroscopy in an argon matrix at 12 K is also performed in the IR and UV/Vis ranges. The experimental spectra are compared with theoretical Raman and IR spectra and with calculated electronic transitions. All calculations are based on the density functional theory (DFT), either normal or time‐dependent (TDDFT). Our results are discussed in view of their possible application in the search for corannulene in the interstellar medium.     

Remote determination of oxygen and water at millimetre wave frequencies using a fibre optic communications network

This paper describes the development of a remote millimetre wave (MMW) spectrometer capable of operation in the 57-66, 114-128 and 171-189 GHz bands. A 9.5-10.5 GHz signal from a yttrium iron garnet (YIG) source is carried via an infrared (IR) laser down a 1 km fibre-optic cable using a high-speed communications modulator. The 6th harmonic of the transmitted microwave signal is generated directly with an active sextrupler, which permits working in the 57-66 GHz band. For operation at 114-128 and 171-189 GHz, the 57-66 GHz output from the sextrupler is doubled or tripled by a further harmonic generator. Absorption line strength measurements and hence sample concentration determinations are undertaken using a Fabry-Perot cavity absorption cell. The spectroscopic data are recovered from the remote spectrometer by transmitting the rectified signal back over a further fibre-optic cable. Also described are the methods of cavity stabilisation and control across this fibre optic network. Oxygen determinations in the 57-66 and 114-128 GHz bands are performed to evaluate the performance of the spectrometer. A determination of water vapour in air at atmospheric pressure, at 183 GHz, is also presented, over a range of ∼5×10⁻⁵ to ∼0.025 volume fraction in air.     

Synthesis, structural and photocatalytic studies of Mn-doped CdS nanoparticles

Mn-doped CdS nanoparticles (Cd_1?x Mn _x S; where x = 0.00–0.10) were synthesized by a chemical precipitation method. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscope, transmission electron microscope (TEM), and UV–Vis spectrometer. The XRD and TEM measurements show that the size of crystallites is in the range of 10–40 nm. Optical measurements indicated a red shift in the absorption band edge upon Mn doping. The direct allowed band gaps of undoped and Mn-doped CdS nanoparticles measured by UV–Vis spectrometer were 2.3 and 2.4 eV at 400 °C, respectively. Photocatalytic activities of CdS and Mn-doped CdS were evaluated by irradiating the solution to ultraviolet light and taking methyl orange (MO) as organic dye. It was found that 5 mol% Mn-doped CdS bleaches MO much faster than undoped CdS upon its exposure to the ultraviolet light. The experiment demonstrated that the photo-degradation efficiency of 5 mol% Mn-doped CdS was significantly higher than that of undoped CdS.     

Measuring acetylene concentrations using a frequency chirped continuous wave diode laser operating in the near infrared

Two frequency chirped continuous wave diode lasers operating in the near infrared (IR) at wavelengths of lambda approximately 1.535 microm and lambda approximately 1.520 microm have been used to measure acetylene concentrations using the P(17) and R(9) rotational lines of the (nu1 + nu3) vibrational combination band. The diode lasers were frequency chirped by applying an electrical current pulse to the laser driver at a repetition rate of greater than 1 kHz. As the laser is operated at high repetition rates, more than 1000 spectra per second can, in principle, be acquired and summed, allowing fast accumulation of data, rapid averaging and consequent improvement of the signal to noise ratio and detection limit. Experiments were performed using a single-pass cell with a path length of 16.4 cm, and also an astigmatic multi-pass absorption cell aligned to give a path length of 56 m. Detection limits corresponding to minimum detectable absorption coefficients, alpha(min), of 5.6 x 10(-5) and 7.8 x 10(-8) cm(-1), respectively, were obtained over a 4 s detection bandwidth. These detection limits would correspond to mixing ratios of 21 parts per million by volume (ppmv) and 59 parts per billion by volume (ppbv) of acetylene at 1 atm in air, with the deleterious effects of pressure broadening accounted for. The single-pass cell was used to perform breakthrough volume (BTV) experiments for the low volume adsorbent traps used to pre-concentrate organic compounds in air, taking advantage of the capability of the system to measure concentrations in real time.     

Diode laser emission linewidth determination: application to H2O line profile studies in the 5 and 1.4 microm regions

In order to study absorption line profiles using the stabilized diode laser spectrometer of Laboratoire de Physique Moléculaire et Applications (LPMA), a reliable determination of the emission line shape of different diodes laser is needed. In the near infrared region (1.39 and 1.66 microm) we used Distributed Feed Back diode lasers which operate around room temperature and in the middle infrared (5 and 8 microm) we used lead salt diode lasers cooled in a helium closed cycle cryostat or in a liquid nitrogen dewar. Some results obtained in H2O line profile studies in the 1.39 and 5 microm regions are presented as examples demonstrating how absorption line profile measurements can lead to erroneous values of the spectroscopic parameters when the contribution of the diode laser emission line width is neglected.     

Changes in chemical composition and collagen structure of dentine tissue after erbium laser irradiation

Erbium laser radiation has a great affinity for the water molecule, which is present in quantity in biological hard tissues. The objective of this work is to identify chemical changes by infrared spectroscopy of irradiated dentine by an Er:YAG-2.94 microm laser. The irradiation was performed with fluences between 0.365 and 1.94 J/cm2. For the infrared analysis a Fourier transform infrared spectrometer was used. After the irradiation were observed: loss of water, alteration of the structure and composition of the collagen, and increase of the OH- radical. These alterations can be identified by a decrease in intensity of the water band between 2800-3800 cm(-1), OH- band at 3575 cm(-1) and bands ascribed to organic matrix between 2800-3400 cm(-1) and 1100-1400 cm(-1).     

Time-resolved Fourier transform infrared spectrometry using a microfabricated continuous flow mixer: application to protein conformation study using the example of ubiquitin

We report on the use of time-resolved Fourier transform infrared spectroscopy (FT-IR) to study chemically induced conformational changes of proteins using the example of ubiquitin. For this purpose a micromachined mixer is coupled to a conventional IR transmission cell with a pathlength of 25 microm and operated in both the continuous and the stopped-flow mode. This experimental set-up allows the elucidation of reaction pathways in the time frame of about 500 milliseconds to seconds with little reagent consumption and low pressure. For continuous flow measurements employed in the time frame from 0.5 to 1.4 s the reaction time is determined by the flow rate used as the connection between the point of confluence in the micromixer and the flow cell was kept constant in all experiments. For stopped-flow experiments (>1.4 s) the time is determined by data acquisition of the rapid scanning infrared spectrometer. Ubiquitin, a small well-known protein with 76 amino acid residues, changes its conformation from native to A-state with the addition of methanol under low pH conditions. We investigated the conformational change in the time frame from 0.5 to 10 s by mixing ubiquitin (20% methanol-d(4)) with an 80% methanol-d(4) solution at pD 2 by evaluating the time dependent changes in the amide I band of the protein.     

Spectroscopy of Dibenzorubicene: Experimental Data for a Search in Interstellar Spectra

We report on the characterization of dibenzo[cde,opq]rubicene (C₃₀H₁₄). The molecule was studied in solution at room temperature with absorption spectroscopy in the visible (vis) and ultraviolet (UV) wavelength ranges, and with emission spectroscopy. The infrared (IR), visible, ultraviolet, and vacuum ultraviolet (VUV) absorption spectra of a thin film were measured also at room temperature. In addition, the UV/vis absorption spectrum was measured at cryogenic temperatures using the matrix isolation spectroscopy technique. The interpretation of spectra was supported by theoretical calculations based on semiempirical and ab initio models, as well as on density functional theory. Finally, the results of the laboratory study were compared with interstellar spectra.     

Low density solid ozone

We report a very low density ( approximately 0.5 g/cm(3)) structure of solid ozone. It is produced by irradiation of solid oxygen with 100 keV protons at 20 K followed by heating to sublime unconverted oxygen. Upon heating to 47 K the porous ozone compacts to a density of approximately 1.6 g/cm(3) and crystallizes. We use a detailed analysis of the main infrared absorption band of the porous ozone to interpret previous research, where solid oxygen was irradiated by UV light and keV electrons.     

Surface modification of Sylgard-184 poly(dimethyl siloxane) networks by ultraviolet and ultraviolet/ozone treatment

We report on the surface modification of Sylgard-184 poly(dimethyl siloxane) (PDMS) networks by ultraviolet (UV) radiation and ultraviolet/ozone (UVO) treatment. The effects of the UV light wavelength and ambient conditions on the surface properties of Sylgard-184 are probed using a battery of experimental probes, including static contact angle measurements, Fourier transform infrared spectroscopy, near-edge X-ray absorption fine structure, and X-ray reflectivity. Our results reveal that when exposed to UV, the PDMS macromolecules in the surface region of Sylgard-184 undergo chain scission, involving both the main chain backbone and the side groups. The radicals formed during this process recombine and form a network whose wetting properties are similar to those of a UV-modified model PDMS. In contrast to the UV radiation, the UVO treatment causes very significant changes in the surface and near-surface structure of Sylgard-184. Specifically, the molecular oxygen and ozone created during the UVO process interact with the UV-modified specimen. As a result of these interactions, the surface of the sample contains a large number of hydrophilic (mainly -OH) groups. In addition, the material density within the first approximately 5 nm reaches about 50% of that of pure silica. A major conclusion that can be drawn from the results and analysis described in this work is that the presence of the silica fillers in Sylgard-184 does not alter the surface properties of the UVO- and UV-modified Sylgard-184.     

Synthesis, characterization and fluorescence studies of 3,5-diaryl substituted 2-pyrazolines

A series of 2-pyrazolines have been synthesized from α, β unsaturated ketones and hydrazine hydrate with acetic/formic acid in ethanol/DMSO. The structures of 2-pyrazolines have been established by spectroscopic techniques i.e. UV, IR, (1)H NMR, (13)C NMR and micro element analysis. Fluorescence spectra were recorded in the solution at fixed concentration and same excitation wavelength at 290 nm. The absorption band positions of all the compounds broadly lie between 280 and 336 nm and fluorescence band positions in the range between 300 and 370 nm, the near ultraviolet region.     

Temperature dependent structured absorption spectra of molecular chlorine

A dual wavelength range spectrometer system has been designed and constructed which can simultaneously perform single pass UV absorption spectroscopy and cavity enhanced absorption spectroscopy in the green region of the visible spectrum. Using the system the absorption spectrum of molecular chlorine has been measured, in the wavelength range 509-570 nm, using cavity enhanced absorption spectroscopy. Absolute absorption cross sections were obtained by simultaneous measurement of the UV spectrum to obtain the Cl(2) concentration. These are the first temperature dependent measurements of the Cl(2) absorption cross sections in this region which are vibronically resolved. Laboratory measurements were conducted at four temperatures (298, 273, 233, and 197 K). Spectral modelling of the Cl(2) B(3)Π(0(u)(+))-X(1)Σ(g)(+) electronic transition has been performed, the results of which are in good agreement with our measured spectra.     

Amino acids (l-arginine and l-alanine) passivated CdS nanoparticles: Synthesis of spherical hierarchical structure and nonlinear optical properties

CdS nanoparticles (NPs) passivated with amino acids (l-alanine and l-arginine) having spherical hierarchical morphology were synthesized by room temperature wet chemical method. Synthesized NPs were characterized by ultraviolet–visible (UV–vis) spectroscopy to study the variation of band gaps with concentration of surface modifying agents. Increase in band gap has been observed with the increase in concentration of surface modifying agents and was found more prominent for CdS NPs passivated with l-alanine. Powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis were carried out for the study of crystal structure and morphology of CdS NPs. The average particle size of CdS NPs calculated from Debye-Scherer formula was found to less than 5 nm and agrees well with those determined from UV–vis spectra and TEM data. Fourier transform infrared (FT-IR) spectroscopy was performed to know the functional groups of the grown NPs. Peaks in FT-IR spectra indicate the formation of CdS NPs and capping with l-alanine and l-arginine. Photoluminescence spectra of these NPs were also studied. Finally, colloidal solution of CdS-PVAc was subjected to Z-scan experiment under low power cw laser illumination to characterize them for third order nonlinear optical properties. CdS-PVAc colloidal solution shows enhanced nonlinear absorption due to RSA and weak FCA on account of two photon absorption processes triggered by thermal effect.     

Photocatalytic studies of silver doped ZnO nanoparticles synthesized by chemical precipitation method

Ag-doped ZnO nanoparticles (Zn_1?xAg_xO; where x = 0.00–0.05) were synthesized by chemical precipitation method. The synthesized products were characterized by X-ray diffraction, scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–Vis spectrometer. The SEM and TEM micrographs revealed the agglomerated spherical-like morphology and the measurements show that the size of crystallites is in the range of 10–40 nm. Optical measurements indicated a red shift in the absorption band edge after Ag doping. The band gap values of as prepared undoped and doped with silver samples were found to decrease with increase in temperature from 300 to 800 °C. Photocatalytic activities of ZnO and Ag doped ZnO were evaluated by irradiating the sample solution to ultraviolet light by taking methylene blue as organic dye. The experiment demonstrated that the photo-degradation efficiency of 1 mol% Ag-doped ZnO was significantly higher than that of undoped and 2–5 mol% Ag doped ZnO under ultraviolet light irradiation.     

On-line capillary electrophoresis FTIR detection for the separation and characterization of proteins

Capillary electrophoresis (CE) with on-line FTIR spectroscopic detection was used to separate a mixture of three model proteins and to provide information on the dominant secondary structures of the separated proteins. On-line FTIR transmission measurements were achieved using a micro-machined flow cell made out of CaF₂ and SU-8 polymer which was attached to the fused silica capillaries using commercial O-rings. The IR beam was focused on the detection window using an off-axis parabolic mirror attached to an external optical port of the spectrometer. As the absorption of water heavily overlaps the so-called amide I band of the proteins the separations were carried out in heavy water (D₂O). The model proteins studied were myoglobin, α-lactalbumin and β-lactoglobulin having different secondary structures. It could be shown that the performance of the separation was comparable to conventional UV–vis detection and that the IR-peak positions of the proteins studied were the same as obtained in reference measurements using the ATR technique.     

原位聚合法制备透明聚苯乙烯的表征及其荧光性质研究

以极性较小的三异丙氧基铽为原料,选择与铽离子发光相匹配的乙酰丙酮为有机配体掺杂于苯乙烯（St）／少量的甲基丙烯酸甲酯（MMA）的混合单体中,通过原位本体聚合直接得到一类改性聚苯乙烯材料。并用红外光谱和紫外光谱表征其结构。可见光透过曲线表明这类改性聚苯乙烯材料具有高铽含量、高透过率的特点,用荧光光谱表征它们的荧光性能,结果表明：该材料在高铽含量下仍能发射很强的Tb3＋离子的特征荧光,未出现明显的荧光猝灭现象。     

Non-coherent visible and infrared radiation increase survival to UV (254 nm) in Escherichia coli K12

Interactions between visible or infrared (IR) and ultraviolet (UV, 254 nm) radiation have been studied in E. coli. Pre-illumination with non-coherent monochromatic 446, 466, 570 and 685 nm radiation, as well as with polychromatic red and IR radiation at room temperature, leads to increased cell survival after a subsequent irradiation with UV light. In the thermic range of the spectrum (red and IR), IR but not red light pre-treatment is able to increase cell survival to a subsequent lethal heat (51 degrees C) challenge, suggesting that increased UV survival may be due to IR-induced heat-shock response. On the other hand, visible-light-induced resistance may be due to a different mechanism, possibly involved with unknown bacterial light receptors.