Interfacing an analogue infrared spectrometer to a microcomputer

An Apple microcomputer has been interfaced to a Perkin-Elmer model 577 infrared spectrometer. The spectral data are digitized with the aid of an in-house designed 12-bit analogue-to-digital interface unit. Control and status signals are obtained from the spectrometer and an optical encoder unit is used to provide an accurate wavenumber marker for the conversion and data recording. The digital data are formatted by the microcomputer and then can be manipulated by programs already developed for handling spectral data recorded from digital spectrometers.     

Fourier transform raman spectroscopy using a bench-top fourier transform infrared spectrometer

The use of a bench top FTIR spectrometer for near infrared Fourier transform Raman spectroscopy is demonstrated. The use of near infrared excitation results in fluorescence free Raman spectra allowing previously difficult samples to be measured.     

Enhancement of chromatographic detail using infrared spectra from chromatography/infrared spectrometer systems

Working with chromatography/infrared spectroscopy data, the technique of local baseline correction in the calculation of the chromatographic intensities from each spectrum is used to provide improved chromatographic detection. The technique reduces chromatographic baseline drift, and produces broad-band (universal) chromatograms with noise levels approaching those obtained from narrow-band specific chromatograms. Chromatograms produced from the ratio of two selected band chromatograms can quickly profile a trend in a homologous series of compounds, test a chromatographic peak for compositional uniformity, or show shifts in composition across a polymer chromatographic series.     

Gas-phase structure of a pi-allyl-palladium complex: efficient infrared spectroscopy in a 7 T Fourier transform mass spectrometer

The performance of infrared (IR) spectroscopy of gas-phase ions in a commercially available 7 T Fourier transform ion cyclotron resonance mass spectrometer has been characterized. A pi-allyl-palladium reactive intermediate, [(pi-allyl)Pd(P(C6H5)3)2]+, involved in the catalytic allylation of amine is studied. A solution of this transition metal complex is electrosprayed, and the IR multiple photon dissociation (IRMPD) spectrum of the mass-selected ions is recorded in two spectral ranges. The fingerprint spectrum (650-1550 cm(-1)) is recorded using the Orsay free-electron laser, and the dependence of the IRMPD efficiency on laser power and irradiation time is characterized. The DFT-calculated IR absorption spectrum of the [(pi-allyl)Pd(P(C6H5)3)2]+ complex shows good agreement with the experimental spectrum. The pi-interaction between the palladium and the allyl moiety is reflected by the assignment of the IRMPD bands, and the observed allylic CH2 wagging modes appear to form a sensitive probe for the pi-interaction strength in metal-pi-allyl complexes. This spectral assignment is further supported by the analysis of the different IRMPD photofragmentation patterns observed at different photon energies, which are found to result from wavelength-specific photofragmentations. Nine peaks are well-resolved in the experimental spectrum, for which the bandwidth (fwhm) is on the order of 15 cm(-1). Resonances with a calculated IR intensity of 5 km/mol or larger are shown to be amenable for IRMPD, indicating an excellent sensitivity of our new experimental setup. Finally, the IR spectrum has also been recorded in the CH stretching region (2950-3150 cm(-1)) using a tabletop IR optical parametric oscillator/amplifier (OPO/OPA) laser source.     

Experimental optimization of p-polarized MAIR spectrometry performed on a fourier transform infrared spectrometer.

Optimized experimental conditions of infrared p-polarized multiple-angle incidence resolution spectrometry (p-MAIRS) for the analysis of ultrathin films on glass have been explored. When the original MAIRS technique is employed for thin-film analysis on a substrate of germanium or silicon, which exhibits a high refractive index, an established experimental condition without optimization can be adapted for the measurements. On the other hand, the p-MAIRS technique that has been developed for analysis on a low-refractive-index material requires, however, optimization of the experimental parameters for a 'quantitative' molecular orientation analysis. The optimization cannot be performed by considering only for optics in the spectrometer, but for optics concerning the substrate should also be considered. In the present study, an optimized condition for infrared p-MAIRS analysis on glass has been revealed, which can be used for quantitative molecular orientation analysis in ultrathin films on glass.     

Routine determination of the absorption and dispersion spectra of solids with a Fourier-transform infrared spectrometer

A method is given for the routine determination of the absorption and refractive index spectra of solids from their Fourier-transform infrared (F.t.i.r.) specular reflection spectra. The innovation responsible for making these determinations routine and rapid is the application of the fast Fourier-transform software of the F.t.i.r. spectrometer in the calculation of the optical constants. For strongly absorbing materials, accurate values of the resonance absorption frequencies and corresponding absorptivities cannot be obtained from either the reflectance or transmittance spectra. The absorption and refractive index spectra of fused silica are determined here by this method. Starting with a reflection spectrum, the entire procedure requires only 20 min at a resolution of 2 cm^?1. These calculations are impossible with the existing software of most small F.t.i.r. spectrometers; minor software modifications reduce the time required to a few minutes.     

Negative chemical ionization and accurate mass measurement applications for a linked gas chromatography/Fourier transform infrared spectrometer/Fourier transform mass spectrometer

Summary The analytical utility of a linked GC/FTIR/ FTMS system operating in accurate mass and negative CI modes is demonstrated. In addition to the complementary information derived from IR and MS search results, accurate mass measurement data (average error of 4.2 ppm) is employed in the analysis of a seven component mixture. A post search filter uses accurate mass data to eliminate spectral search results with incorrect elemental compositions. An alternate positive ion EI and negative ion CI GC/IR/MS analysis is also performed on a mixture of substituted phenyl aldehydes and ketones. The reagent gas, ammonia, is introduced by pulsed valve thus minimizing crossover spectral contamination while maximizing spectral resolution. Proton abstraction by the amide produces an intense (M-1)^– for all compounds in the mixture. Molecular weight information from the negative CI data is used in a post search filter to improve the reliability of both IR and MS search results.

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Anwendung der negativen chemischen Ionisation und genauer Massenmessungen für ein gekoppeltes GC/FTIR/FTMS-System

Zusammenfassung Die analytische Anwendbarkeit eines gekoppelten GC/FTIR/FTMS-Systems mit akkurater Massenmessung und NCI-Betrieb wird dargestellt. Zusätzlich zu den komplementären Informationen aus IR- und MS- Bibliothekssuchen werden Daten aus akkuraten Massenmessungen (mittlerer Fehler 4.2 ppm) bei der Analyse einer Mischung aus sieben Komponenten mit herangezogen. Im Anschluß an die Bibliothekssuche eliminiert ein Filter mit Hilfe der akkuraten Massen Ergebnisse mit fehlerhafter Elementarzusammensetzung. Von einer Mischung aus substituierten Phenylaldehyden und -ketonen wird eine Analyse mit alternierender Registrierung von positiven EI- und negativen CI-Spektren durch ein GC/IR/-MS-System ausgeführt. Das Reaktandgas Ammoniak wird über ein gepulstes Ventil zugegeben, um bei maximaler spektraler Auflösung minimale Störung durch Verunreinigung zu erhalten. Durch Abstraktion eines Protons von der Amidfunktion werden von allen Komponenten der Mischung intensive (M-1)-Ionen gebildet. Molekulargewichtsinformationen aus dem NCI-Experiment werden als Filter verwendet, mit dem die Zuverlässigkeit des Suchens in IR- und MS-Datenbanken erhöht werden kann.

     

Castanospermine-trehazolin hybrids: a new family of glycomimetics with tuneable glycosidase inhibitory properties

Bicyclic azasugar glycomimetics related to castanospermine and trehazolin have been prepared from sugar carbodiimides via aminooxazoline intermediates; preliminary enzyme inhibition tests showed a marked dependence of the selectivity and potency towards alpha and beta-glucosidases upon the nature of the exocyclic substituent.     

Model systems for flavoenzyme activity: a tuneable intramolecularly hydrogen bonded flavin-diamidopyridine complex

We report the electrochemically tuneable intramolecular hydrogen bonding interactions between a covalently linked flavin-diamidopyridine unit.     

Transient infrared spectra of CH3SOO and CH3SO observed with a step-scan Fourier-transform spectrometer

A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to monitor time-resolved infrared absorption of transient species produced upon irradiation at 248 nm of a flowing mixture of CH(3)SSCH(3) and O(2) at 260 K. Two transient bands observed with origins at 1397±1 and 1110±3 cm(-1) are tentatively assigned to the antisymmetric CH(3)-deformation and O-O stretching modes of syn-CH(3)SOO, respectively; the observed band contour indicates that the less stable anti-CH(3)SOO conformer likely contributes to these absorption bands. A band with an origin at 1071±1 cm(-1), observed at a slightly later period, is assigned to the S=O stretching mode of CH(3)SO, likely produced via secondary reactions of CH(3)SOO. These bands fit satisfactorily with vibrational wavenumbers and rotational contours simulated based on rotational parameters of syn-CH(3)SOO, anti-CH(3)SOO, and CH(3)SO predicted with density-functional theories B3LYP/aug-cc-pVTZ and B3P86/aug-cc-pVTZ. Two additional bands near 1170 and 1120 cm(-1) observed at a later period are tentatively assigned to CH(3)S(O)OSCH(3) and CH(3)S(O)S(O)CH(3), respectively; both species are likely produced from self-reaction of CH(3)SOO. The production of SO(2) via secondary reactions was also observed and possible reaction mechanism is discussed.     

A collinear tandem time-of-flight mass spectrometer for infrared photodissociation spectroscopy of mass-selected ions

An apparatus based on collinear tandem time-of-flight mass spectrometer has been designed for the measurement of infrared photodissociation spectroscopy of mass-selected ions in the gas phase.The ions from a pulsed laser vaporization supersonic ion source are skimmed and mass separated by a Wiley-McLaren time-of-flight mass spectrometer.The ion of interest is mass selected,decelerated and dissociated by a tunable IR laser.The fragment and parent ions are reaccelerated and mass analyzed by the second time-of-flight mass spectrometer.A simple new assembly integrated with mass gate,deceleration and reacceleration ion optics was designed,which allows us to measure the infrared spectra of mass selected ions with high sensitivity and easy timing synchronization.     

Corrections for polarizer and spectrometer imperfections in the measurement of infrared dichronic ratios

The measurement of dichroic ratios in highly absorbing systems requires careful consideration of the effects of instrumental polarization sensitivity and of polarizer imperfections if accurate results are to be obtained. If the absorbances exceed about 1.5, corrections due to imperfect polarizers can become important but are fairly easily performed. With the polarizers set in the standard 45° geometry, the correction due to instrumental polarization sensitivity is small.     

Characteristics of several NIR tuneable diode lasers for spectroscopic based gas sensing: a comparison

Tuneable laser diodes were characterized and compared for use as tuneable sources in gas absorption spectroscopy. Specifically, the characteristics of monolithic widely tuneable single frequency lasers, such as sampled grating distributed Bragg reflector laser and modulated grating Y-branch laser diodes, recently developed for optical communications, with operating wavelengths in the 1,520 nm相似文献   

Evaluation of a differential mobility spectrometer/miniature mass spectrometer system

A planar differential mobility spectrometer (DMS) was coupled to a Mini 10 handheld rectilinear ion trap (RIT) mass spectrometer (MS) (total weight 10 kg), and the performance of the instrument was evaluated using illicit drug analysis. Coupling of DMS (which requires a continuous flow of drift gas) with a miniature MS (which operates best using sample introduction via a discontinuous atmospheric pressure interface, DAPI), was achieved with auxiliary pumping using a 5 L/min miniature diaphragm sample pump placed between the two devices. On-line ion mobility filtering showed to be advantageous in reducing the background chemical noise in the analysis of the psychotropic drug diazepam in urine using nanoelectrospray ionization. The combination of a miniature mass spectrometer with simple and rapid gas-phase ion separation by DMS allowed the characteristic fragmentation pattern of diazepam to be distinguished in a simple urine extract at lower limits of detection (50 ng/mL) than that achieved without DMS (200 ng/mL). The additional separation power of DMS facilitated the identification of two drugs of similar molecular weight, morphine (average MW = 285.34) and diazepam (average MW = 284.70), using a miniature mass spectrometer capable of unit resolution. The similarity in the proton affinities of these two compounds resulted in some cross-interference in the MS data due to facile ionization of the neutral form of the compound even when the ionic form had been separated by DMS.     

Electrochemically tuneable hydrogen bonding interactions between a phenyl-urea terminated dendrimer and phenanthrenequinone

Electrochemically tuneable hydrogen bonding interactions are described between a phenyl-urea terminated dendrimer and phenanthrenequinone.     

Model systems for flavoenzyme activity: an electrochemically tuneable model of roseoflavin

The electrochemically tuneable hydrogen bonding interactions between roseoflavin analogue and apoenzyme mimic are described.