Low-frequency Raman spectra of nitric acid hydrates

Raman spectra of solid nitric acid hydrates (NAM, alpha- and beta-NAD, alpha- and beta-NAT, and NAP) are obtained in the low-frequency region 20-175 cm(-1) where phonon bands show characteristic patterns. This fingerprint information, intimately related to the structure and symmetry of the unit cell, is well suited for observation of phase changes in solid nitric acid hydrates and allows the distinction of mixtures of different hydrate phases. The low-frequency spectra are correlated with the spectra of the respective symmetric NO stretching vibration (1000-1080 cm(-1)), with literature data, and with X-ray diffraction patterns.     

Pattern formation during the CO-oxidation involving subsurface oxygen

This paper focuses on subsurface oxygen and its influence on pattern formation during CO-oxidation on platinum surfaces. For the observation of spatiotemporal pattern formation during catalytic reactions the photoelectron emission microscope (PEEM) has proven to be an excellent real-time imaging instrument, capable of tracking local work function changes. The existence of subsurface oxygen on platinumlike surfaces has been extensively discussed and for palladium its presence has been clearly established during rate oscillations. Subsurface oxygen is defined at this point as an atomic O species located directly underneath the uppermost metal crystal layer; its dipole moment therefore considerably lowers the work function of the surface. Here we review some of the investigations involving subsurface oxygen, focusing on the role subsurface oxygen might play in pattern formation during CO-oxidation on platinum. We will also present some new results, where this species clearly interacts with chemisorbed oxygen under restrictions by boundary conditions on the Pt(110) single crystal. These previously (through microlithography) constructed domain boundaries on the surface are made out of Rh or Pd, and they are acting as an additional source of CO molecules for the Pt surface. (c) 2002 American Institute of Physics.     

Synthesis of the ABC ring system of Azaspiracid. 2. A systematic study into the effect of C(16) and C(17) substitution on bis-spirocyclization

[reaction: see text] A systematic study into the effect of C(16) and C(17) substitution on the stereochemical outcome of bis-spirocyclization to form the ABC ring system of azaspiracid is disclosed. Successful construction of the natural 10R,13R bis-spirocyclic stereochemistry has been accomplished on the C(16) benzyloxy-containing precursor.     

A combined matrix isolation and ab initio study of bromine oxides

Bromine oxides have been generated by passing a mixture of Br(2)/O(2)/Ar through a microwave discharge. The products were stabilized at 6.5 K in an excess amount of argon. Infrared spectroscopy was used to analyze the species formed; experiments with enriched (18)O(2) and ab initio calculations were carried out to assist in the assignment of the spectra. Besides the known species BrO, OBrO, and BrBrO, spectroscopic evidence for BrOBrO, BrBrO(2), and a new isomer of Br(2)O(3) is reported for the first time. Extensive comparisons are drawn between the present studies and previous experimental and theoretical works. The chemistry involved in the production of the observed compounds is discussed. The assignments are corroborated by the good correlation between observed and calculated band positions and intensities.     

Alpha-Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase

In this work, earlier studies reporting α-H₂CO₃ are revised. The cryo-technique pioneered by Hage, Hallbrucker, and Mayer (HHM) is adapted to supposedly prepare carbonic acid from KHCO₃. In methanolic solution, methylation of the salt is found, which upon acidification transforms to the monomethyl ester of carbonic acid (CAME, HO-CO-OCH₃). Infrared spectroscopy data both of the solid at 210 K and of the evaporated molecules trapped and isolated in argon matrix at 10 K are presented. The interpretation of the observed bands on the basis of carbonic acid [as suggested originally by HHM in their publications from 1993–1997 and taken over by Winkel et al., J. Am. Chem. Soc. 2007 and Bernard et al., Angew. Chem. Int. Ed. 2011] is inferior compared with the interpretation on the basis of CAME. The assignment relies on isotope substitution experiments, including deuteration of the OH- and CH₃- groups as well as ¹²C and ¹³C isotope exchange and on variation of the solvents in both preparation steps. The interpretation of the single molecule spectroscopy experiments is aided by a comprehensive calculation of high-level ab initio frequencies for gas-phase molecules and clusters in the harmonic approximation. This analysis provides evidence for the existence of not only single CAME molecules but also CAME dimers and water complexes in the argon matrix. Furthermore, different conformational CAME isomers are identified, where conformational isomerism is triggered in experiments through UV irradiation. In contrast to earlier studies, this analysis allows explanation of almost every single band of the complex spectra in the range between 4000 and 600 cm⁻¹.     

Conducting polythiophenes with a broad spectrum of reactive groups

The development of reliable and reproducible chemistries for the immobilization of biomolecules to a conducting polymer is a key challenge in the design and preparation of a CP‐based biosensor. In this article, the syntheses and electropolymerization of a series of new 3‐alkylthiophene derivatives functionalized with the most used reactive groups in immobilization chemistry, including maleimide, azide, and anhydride, are described. Despite the nucleophilic or electrophilic nature of the reactive groups, the synthesized thiophene monomers exhibit rather good polymerizability, and the reactive groups withstand the polymerization conditions and are correctly incorporated into the resulting electroactive polymers. The reactivity of the pendant reactive groups of the resulting polymers to attach biomolecules has been examined with different redox‐active, photoactive compounds as well as recognition elements as model compounds. It has been confirmed that with well‐established procedures developed for the immobilization of enzymes, the model compounds can be easily and selectively bound onto these new conducting polymers without the loss of their optical and electrochemical activity. Therefore, these conductive materials with a broad spectrum of reactive groups will provide a useful platform for developing CP‐based biosensors for a wide range of applications. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4547–4558, 2005