Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH): products and mechanism of Cl atom initiated oxidation in the presence of NOx

Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C(4)F(9)CH(2)CH(2)OH, 4:2 FTOH) in the presence of NO(x) in 700 Torr of N(2)/O(2) diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy, radicals derived from 4:2 FTOH. Cl atoms react with C(4)F(9)CH(2)CH(2)OH to give C(4)F(9)CH(2)C(*)HOH radicals which add O(2) to give chemically activated alpha-hydroxyperoxy radicals, [C(4)F(9)CH(2)C(OO(*))HOH]*. In 700 Torr of N(2)/O(2) at 296 K, approximately 50% of the [C(4)F(9)CH(2)C(OO(*))HOH]* radicals decompose "promptly" to give HO(2) radicals and C(4)F(9)CH(2)CHO, the remaining [C(4)F(9)CH(2)C(OO(*))HOH]* radicals undergo collisional deactivation to give thermalized peroxy radicals, C(4)F(9)CH(2)C(OO(*))HOH. Decomposition to HO(2) and C(4)F(9)CH(2)CHO is the dominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalized peroxy radicals react to give C(4)F(9)CH(2)C(O(*))HOH radicals which then decompose at a rate >2.5 x 10(6) s(-1) to give HC(O)OH and the alkyl radical C(4)F(9)CH(2)(*). The primary products of 4:2 FTOH oxidation in the presence of excess NO(x) are C(4)F(9)CH(2)CHO, C(4)F(9)CHO, and HCOOH. Secondary products include C(4)F(9)CH(2)C(O)O(2)NO(2), C(4)F(9)C(O)O(2)NO(2), and COF(2). In contrast to experiments conducted in the absence of NO(x), there was no evidence (<2% yield) for the formation of the perfluorinated acid C(4)F(9)C(O)OH. The results are discussed with regard to the atmospheric chemistry of fluorotelomer alcohols.     

Measurement of nitric oxide by 4,5-diaminofluorescein without interferences

The fluorescent reagent 4,5-diaminofluorescein (DAF-2) has been widely used for specific and quantitative measurements of nitric oxide (NO) in biological tissues. Recently it was reported that dehydroascorbic acid (DHA) and ascorbic acid (AA) interfere with the measurement of NO using DAF-2. A new method of assaying NO using DAF-2 eliminates these interferences; when frozen on dry ice, the NO in the original solution still diffuses and can react with an adjacent frozen block of DAF-2, but the confounding compounds such as DHA do not. Thus, placing the microliter-volume frozen blocks of solutions containing NO and the solutions of DAF-2 adjacent to each other for 30 min results in the concentration dependent formation of fluorescent product (DAF-2T) from the reaction of NO with DAF-2. The product has been characterized and the method validated using both fluorescence spectroscopy and capillary electrophoresis with laser induced fluorescence detection. With this approach, the presence of DHA and AA does not interfere with NO measurements, and product formation is inhibited in the presence of NO scavengers added to either of the solutions before freezing. The contactless DAF-2 method successfully assays NO in nitric oxide synthase-positive vertebrate and invertebrate tissues. This method allows nondestructive NO detection in biological samples that can subsequently be used for morphological and/or biochemical studies.     

A polymer-based microfluidic device for immunosensing biochips

This paper describes the design, fabrication, and test of a PDMS/PMMA-laminated microfluidic device for an immunosensing biochip. A poly(dimethyl siloxane)(PDMS) top substrate molded by polymer casting and a poly(methyl methacrylate)(PMMA) bottom substrate fabricated by hot embossing are bonded with pressure and hermetically sealed. Two inlet ports and an air vent are opened through the PDMS top substrate, while gold electrodes for electrochemical biosensing are patterned onto the PMMA bottom substrate. The analyte sample is loaded from the sample inlet port to the detection chamber by capillary force, without any external intervening forces. For this and to control the time duration of sample fluid in each compartment of the device, including the inlet port, diffusion barrier, reaction chamber, flow-delay neck, and detection chamber, the fluid conduit has been designed with various geometries of channel width, depth, and shape. Especially, the fluid path has been designed so that the sample flow naturally stops after filling the detection chamber to allow sufficient time for biochemical reaction and subsequent washing steps. As model immunosensing tests for the microfluidic device, functionalizations of ferritin and biotin to the sensing surfaces on gold electrodes and their biospecific interactions with antiferritin antiserum and streptavidin have been investigated. An electrochemical detection method for immunosensing by biocatalyzed precipitation has been developed and applied for signal registration. With the biochip, the whole immunosensing processes could be completed within 30 min.     

Anti-stokes Raman study of vibrational cooling dynamics in the primary photochemistry of rhodopsin

Picosecond Stokes and anti-Stokes Raman spectra are used to probe the structural dynamics and reactive energy flow in the primary cis-to-trans isomerization reaction of rhodopsin. The appearance of characteristic ethylenic, hydrogen out-of-plane (HOOP), and low-wavenumber photoproduct bands in the Raman spectra is instrument-response-limited, consistent with a subpicosecond product appearance time. Intense high and low-frequency anti-Stokes peaks demonstrate that the all-trans photoproduct is produced vibrationally hot on the ground-state surface. Specifically, the low-frequency modes at 282, 350, and 477 cm(-1) are highly vibrationally excited (T > 2000 K) immediately following isomerization, revealing that these low-frequency motions directly participate in the reactive curve-crossing process. The anti-Stokes modes are characterized by a approximately 2.5 ps temporal decay that coincides with the conversion of photorhodopsin to bathorhodopsin. This correspondence shows that the photo-to-batho transition is a ground-state cooling process and that energy storage in the primary visual photoproduct is complete on the picosecond time scale. Finally, unique Stokes vibrations at 290, 992, 1254, 1290, and 1569 cm(-1) arising from the excited state of rhodopsin are observed only at 0 ps delay.     

Crystal structure of a partly self-complementary peptide nucleic acid (PNA) oligomer showing a duplex-triplex network

The X-ray structure of a partly self-complementary peptide nucleic acid (PNA) decamer (H-GTAGATCACT-l-Lys-NH(2)) to 2.60 A resolution is reported. The structure is mainly controlled by the canonical Watson-Crick base pairs formed by the self-complementary stretch of four bases in the middle of the decamer (G(4)A(5)T(6)C(7)). One right- and one left-handed Watson-Crick duplex are formed. The two PNA units C(9)T(10) change helical handedness, so that each PNA strand contains both a right- and a left-handed section. The changed handedness in C(9)T(10) allows formation of Hoogsteen hydrogen bonding between C(9)T(10) and G(4)A(5) of a PNA strand in an adjacent Watson-Crick double helix of the same handedness. Thereby, a PNA-PNA-PNA triplex is formed. The PNA unit A(3) forms a noncanonical base pair with A(8) in a symmetry-related strand of opposite handedness; the base pair is of the A-A reverse Hoogsteen type. The structural diversity of this PNA demonstrates how the PNA backbone is able to adapt to structures governed by the stacking and hydrogen-bonding interactions between the nucleobases. The crystal structure further shows how PNA oligomers containing limited sequence complementarity may form complex hydrogen-bonding networks.     

Conjugated enynes as a new type of substrates for olefin metathesis

[reaction: see text] It has been demonstrated for the first time that conjugated enynes can be employed as a facile substrate in olefin metathesis with the use of a bispyridine-substituted ruthenium benzylidene catalyst. Cross-metathesis of the enynes with alkenes turns out to proceed with preferential formation of (Z)-isomers over (E)-isomers up to >25:1 in moderate to good yields. The intramolecular version of conjugated enynes affords novel butadienyl cycloalkenes, which are a highly useful synthetic building blocks, in acceptable yields.     

Corynebactin and enterobactin: related siderophores of opposite chirality

Most species of bacteria employ siderophores to acquire iron. The chirality of the ferric siderophore complex plays an important role in cell recognition, uptake, and utilization. Corynebactin, isolated from Gram-positive bacteria, is structurally similar to enterobactin, a well known siderophore isolated from Gram-negative bacteria, but contains L-theronine instead of L-serine in the trilactone backbone. Corynebactin also contains a glycine spacer unit in each of the chelating arms. A hybrid analogue (serine-corynebactin) has been synthesized. The chirality and relative conformational stability of the three ferric complexes of enterobactin, corynebactin, and the hybrid has been investigated. In contrast to enterobactin, corynebactin assumes a Lambda configuration. However, the ferric serine-corynebactin hybrid forms a racemic mixture, only slightly favoring the Lambda conformation.     

Ketalizations of aryl ω-(2-imidazolyl)alkyl ketones by glycerol and 3-mercapto-1,2-propanediol. synthesis and characterization of cis- and trans-{2-aryl-2-[ω-(2-imidazolyl)alkyl](1,3-dioxolan-4-yl and 1,3-oxathiolan-5-yl)}methanols

Aryl 2-[(2-imidazolyl)ethyl or 3-(2-imidazolyl)propyl]ketones were ketalized by glycerol or 3-mercapto-1,2-propanediol in boiling benzene in the presence of 4-toluenesulfonic acid to provide the title compounds. The aryl substituents are 4-chloro-, 4-bromo-, 4-fluoro-, or 2,4-dichlorophenyl. While aryl (2-imidazolyl)methyl ketones condensed with glycerol to form cis- and trans-{2-aryl-2-[(2-imidazolyl)methyl]-4-(hydroxymethyl)}-1,3-dioxolanes, related condensations with 3-mercapto-1,2-propanediol, under similar, or even more stringent reaction conditions, produced no 1,3-oxathiolane analogs, with the starting ketones being recovered. Separation and structure determination of these racemic cis and trans isomeric products are described. The structure of these stereoisomers was established by means of ¹H and ¹³C nmr correlation and nOe experiments. Selective methylation of the N-unsubstituted 2-imidazolyl alcohols with one equivalent sodium hydride and methyl iodide provided the corresponding N-methyl alcohols in excellent yields. With excess benzoyl chloride, N-unsubstituted 2-imidazolyl alcohols were initially converted to O, N-dibenzoates from which the N-benzoyl group was easily cleaved by ammonium hydroxide in ethanol to provide benzoate esters.     

Modeling chemoadaptive behavior: X-ray structure of the trimethylamine oxide-urea (1∶4) complex

The structure of a trimethylamine oxide (TMAO)-urea 14 complex was investigated by x-ray crystallographic methods. C₃H₉NO, 4CH₄N₂O, M_r=315.33, monoclinic P2₁/n, a=11.004(2), b=9.8259, c=15.419(2),=106.88(4), V=1595.4(2) å₃, Z=4, D_x=1.313(1) g cm^–3, monochromatized Cu (=1.5418 å),=8.94 cm^–1, F(OOO)=680, temperature = 110K, final R=0.067, for 1786 unique observed reflections. Based on these studies and comparison with related compounds a model of the interaction of urea and TMAO with proteins, especially enzymes, is proposed. This is important in the physiology of many organisms, especially elasmobranchs. The counteracting effect of TMAO on urea perturbation of protein structure and function is interpreted in terms of water structure as a balance between the structure breaking effect of urea and the structure-stabilizing effect of TMAO.     

A new radiochemical procedure for uranium assay in environmental samples

A new and economical method for assay of environmental samples for uranium isotopes is proposed. Separation and radiochemical purification of uranium isotopes (²³⁴U,²³⁵U and²³⁸U) from other elements is achieved on a single anion exchange column by washing with various concentrations of hydrochloric acid. Iron, the principal interfering element is removed from the colum by washing with 4.5M hydrochloric acid with a combination of reducing agents under the conditions described. Weightless samples of uranium are prepared by either evaporation in a polished stainless steel dish or electroplated on a stainless steel planchet. This method is applicable for air particulates, soils, sediments, coal, water, vegetation, and biologicals. Text of the paper presented in the symposium on Practical Applications of Nuclear and Radiochemistry, at Las Vegas, Nevada, August 25–29, 1980. Submitted for publication in Advances in Chemistry Series.