An evaluation of infrared microwindows for ozone retrievals using the Eureka Bruker 125HR Fourier transform spectrometer

A Bruker 125HR Fourier transform spectrometer was installed at the Polar Environment Atmospheric Research Laboratory (PEARL) at Eureka, Nunavut, Canada in the summer of 2006 to study atmospheric composition. Using the optimal estimation method, typically over a limited spectral region called a microwindow, information about the vertical distribution of trace gas species that have absorption bands in the mid-infrared spectral range can be retrieved. Total and partial columns can also be determined to show the temporal evolution of the target gas. For ozone in particular, retrievals have been performed using several of its many mid-infrared absorption features, resulting in a lack of consistency in the literature in the microwindows chosen for retrievals. This work focuses on the optimization of the ozone retrieval, assessing a set of 22 microwindows between 780 and 3052 cm⁻¹ to determine which is best suited to conditions at Eureka. The 1000-1004.5 cm⁻¹ spectral interval is shown to be the most sensitive to both the stratosphere and troposphere. This microwindow gives the highest number of degrees of freedom for signal (∼7 for total column), and the smallest total error (4.3%) compared with 21 other spectral regions. Retrievals performed with this microwindow agree well with results obtained from other instruments on-site. Total column ozone measured by the Bruker 125HR in this microwindow agreed to 2% with two other Fourier transform spectrometers, to 0.7% with a Brewer spectrophotometer, to 8% with a SAOZ UV-VIS spectrometer, and to 7% with ozone sondes.     

Syntheses and characterization of nickel(II) dithiocarbamate complexes containing NiS4 and NiS2PN moieties: Nickel sulphide nanoparticles from a single source precursor

In this study, ammonium N-benzyldithiocarbamate was synthesized and used to prepare homoleptic Ni(II) bis(N-benzyldithiocarbamate) (1) and heteroleptic Ni(II) complexes involving isocyanate (2) and cyanide (3) ions. The complexes were characterized by elemental analysis, Fourier transform infra-red (FTIR), and NMR (¹H and ¹³C) spectroscopic techniques. Complex 2 was further characterized by single crystal X-ray diffraction analysis. The FTIR showed bidentate co-ordination for all the complexes as the v(CN) stretching frequency were in the 980–1050 cm^?1 region without any splitting. Thermal decomposition profile of the complexes showed decomposition resulting in the formation of nickel sulphides. The homoleptic complex 1 was utilized as single source precursor (SSP) to prepare Nickel sulphide nanoparticles. The synthesis of the nanoparticles was conducted using different capping molecules (with various alkyl chain lengths), and at different reaction temperature and time. Pure phase Heazlewoodite (Ni₃S₂) nanoparticles were obtained from the X-ray diffraction study. The TEM analysis showed that the type of capping agent, reaction temperature, and time of reaction have significant effect on the morphology and size of the nanoparticles. The optical properties of the nanoparticles were studied using absorption and fluorescence spectroscopies, and they displayed evidence of quantum confinement effect.     

Assessment of hand-held Raman instrumentation for in situ screening for potentially counterfeit artesunate antimalarial tablets by FT-Raman spectroscopy and direct ionization mass spectrometry

Pharmaceutical counterfeiting has become a significant public health problem worldwide and new, rapid, user-friendly, reliable and inexpensive methods for drug quality screening are needed. This work illustrates the chemical characterization of genuine and fake artesunate antimalarial tablets by portable Raman spectroscopy and validation by FT-Raman spectroscopy and ambient mass spectrometry. The applicability of a compact and robust portable Raman spectrometer (TruScan™) for the in situ chemical identification of counterfeit tablets is reported.     

Surface-enhanced Raman spectroscopy of DNA

We report a method for obtaining highly reproducible surface-enhanced Raman spectroscopy (SERS) of single and double-stranded thiolated DNA oligomers. Following a protocol that relaxes the DNA into an extended conformation, SERS spectra of DNA oligonucleotides are found to be extremely similar, strongly dominated by the Stokes modes of adenine. A spectral correlation function analysis useful for assessing reproducibility and for quantifying the highly complex changes corresponding to modifications in molecular conformation of the adsorbate molecules is introduced. This approach is used to monitor the interaction of DNA with cisplatin, a chemotherapy agent in widespread use.     

Steric course of some cyclopropanation reactions of L-threo-hex-4-enopyranosides

Completely protected 4-deoxy-α-L-threo-hex-4-enopyranosides 1c,d undergo the dichlorocarbene addition affording exclusively diastereomeric adducts 5c,d with the cyclopropane ring anti to the C-3 alkyloxy substituent, while the reaction with 3-unprotected derivatives 1a,b affords a mixture of syn and anti derivatives. Under the Simmons-Smith cyclopropanation adducts 2a-d with a syn stereochemistry are obtained. Starting from 5b, the cyclopropanated sugar 3b is obtained by reduction with LiAlH₄, thus the two diastereomers 2b and 3b can be stereoselectively obtained through the two different pathways. For a useful comparison, 4-deoxy-β-L-threo-hex-4-enopyranoside 1e was also subjected to the above two cyclopropanation methods affording the expected cycloadduct 2e and a diastereomeric mixture of dichlorocycloadducts 4e and 5e (4e/5e=2.8:1).     

Efficient Differentiation of the Hydroxyl Groups of 3,4-O-Isopropylidene-D-Galactopyranosides by Lipase Catalyzed Esterification and De - Esterification

Abstract

The Pseudomonas sp. (LPS) promoted acyl transfer from vinyl acetate to selected 3,4-O-isopropylidene-D-galactopyranosides takes place in a completely selective manner giving in high yield the corresponding 6-O-acetates. The acetylation rate is strongly dependent on the type and the orientation of the aglycon, varying from a maximum of reactivity for the 1-deoxy derivative, 1,5-anhydro-3,4-O-isopropylidene-D-galactitol (1d), to a minimum for β configurated alkyl glycosides and showing a complete loss of reactivity for 3′,4′:2,3:5,6-tri-O-isopropylidenelactose dimethyl acetal (1e). The latter compound is, however, selectively 6′-O-esterified in good yield by lipase from Candida Antarctica and vinyl acetate. Also the course of the enzymatic hydrolysis of 2,6-di-O-acetyl-3,4-O-isopropylidene-D-galactopyranosides 2 is dependent on the type of the aglycon, both for the reaction rate and the selectivity. The 2-O-acetates 4 are selectively obtained in good yields with porcine pancreatic lipase (PPL) promoted hydrolysis in the case of β and α-methyl, and 1-deoxy derivatives (2a, 2b and 2d), while for β-benzyl (2c) and lactose (2e) analogues satisfactory results are obtained with lipase from Mucor miehei (IM20).

     

Early transition-metal perfluoroalkyl complexes

Elusive early transition-metal perfluoroalkyl complexes have been isolated and structurally characterized for the first time. Trifluoromethyltrimethylsilane, CF3SiMe3, serves as an excellent trifluoromethyl group-transfer reagent and reacts with the known Ti(IV) fluoride complex Cp2TiF2 to yield the novel Ti(IV) trifluoromethyl fluoride compound, Cp2Ti(CF3)(F) (1). Reaction of complex 1 with trimethylsilyltriflate (Me3SiOTf) affords the Ti(IV) trifluoromethyl triflate complex Cp2Ti(CF3)(OTf) (2). Both titanium perfluoroalkyl compounds have been characterized spectroscopically and by single-crystal X-ray analysis. The Ti-CF3 linkage in these complexes is remarkably robust and shows no evidence of an alpha-fluoride interaction (Ti...F-CF2) between the electrophilic Ti(IV) metal center and any of the C-F bonds in the trifluoromethyl group in the solid state or in solution.