HTFFR kinetics studies: A chemiluminescence titration method for the determination of absolutes Sn concentrations

Absolute gas phase Sn concentrations in the range 1 × 10¹³ ? [Sn] ? 1 × 10¹⁴ ml^?1 have been determined utilizing a technique based on the rapid (at T ? 900 K) titration reaction Sn + NO₂ → SnO + NO (k(900–1100 K) ≈ 1 × 10^?10 ml molecule^?1 s^?1) and the chemiluminescent indicator reaction Sn + N₂O → SnO + N₂ + hv(SnO a³ Σ-X¹Σ).     

Low-temperature properties of CePd2In

We report measurements of the specific heatC _p(T), electrical resistivity ϱ(T) and magnetic susceptibility ξ(T) of hexagonal CePd₂In, at low temperatures. Anomalies inC _p(T), χ(T) and ϱ(T) atT=1.23 K, indicate a phase transition, most likely to an antiferromagnetically-ordered phase. The electronic entropy reachesR ln2 per mole Ce at 9.2K, suggesting that the phase transition involves a doublet state. The ordered phase coexists with moderately correlated itinerant electrons.     

Conformational interconversions in supersonic jets: Matrix IR spectroscopy and model calculations

Terminal conformer populations in supersonic molecular beams have been measured by use of matrix IR spectroscopy. the experimental technique is based on trapping of the beam molecules in to a cryogenic matrix. The ratio of conformational isomers is determined by comparing intensity ratios of infrared absorption bands with those found in analogous experiments with thermal effusive molecular beams. supersonic beams of pure 1,2-difluoroethane a considerable depopulation fo the less stable trans conformer is found, the lowest terminal conformational temperature reached being T_c^t8 = 207 (3) K. In seeded argon beams the cooling of the conformational distribution was found to be weaker. In supersonic beams of 1,2-dichloroethane and of methyl nitrite no significant conformational cooling was found. The experimental results are discussed in terms of a kinetic model of conformational interconversion in the flow field of a continuum free jet. The calculation indicate that conformational cooling by supersonic expansion may be expected only for molecules with a low energy barrier to internal rotation.     

Photofragmentation of Dibenzyl Ketone in the Presence of Tetramethylpiperidine Derivatives. Studies on light stabilizer mechanisms [1]

The interaction of selected tetramethylpiperidine derivatives with radicals arising from the Norrish-type I cleavage of dibenzyl ketone under oxygen was studied. Product analyses and kinetic studies showed that the investigated sterically hindered piperidine derivatives have a pronounced effect on both the nature and distribution of the products of photolysis of dibenzyl ketone in the presence of oxygen. Observations indicated that the phenylperacetoxyl radical is formed as an intermediate during irradiation and that it interacts with the additives used. Possible mechanisms of the reactions studied are discussed. The observation that oxidation of an isolated double bond by the radicals formed in dibenzyl ketone photolysis under oxygen is strongly inhibited in the presence of the studied sterically hindered amines is discussed in the light of the results presented. The findings are considered in relation to the problem of polymer stabilization.     

Infrared spectra of 1,2-difluoroethane aggregates obtained by matrix trapping of effusive and supersonic molecular beams

The formation of molecular aggregates was investigated by matrix ir spectroscopy. Molecular beams of 1,2-difluoroethane (DFE), either from an effusive or from a supersonic source, were deposited with an excess of argon onto a cryocooled target. (DFE)_x aggregates were formed either in the seeded supersonic beam or upon deposition of a matrix with a low $\text{M}\text{A}$ ratio. In the former case the ir matrix spectra were found to depend on the carrier gas used and to be different from the spectra obtained by deposition of effusive beams. The experimental results suggest the use of supersonic molecular beams for the selective isolation of specific aggregates in cryogenic matrices.     

Mid infrared resonant cavity detectors and lasers with epitaxial lead-chalcogenides

Wavelength tunable emitters and detectors in the mid-IR wavelength region allow applications including thermal imaging and gas spectroscopy. One way to realize such tunable devices is by using a resonant cavity. By mechanically changing the cavity length with MEMS mirror techniques, the wavelengths may be tuned over a considerable range.     

Flexible Rolled Thick‐Film Miniaturized Flow‐Cell for Minimally Invasive Amperometric Sensing

We describe here a miniaturized flexible thick‐film electrochemical biosensor flow detector, suitable for insertion into the lacrimal canaliculus towards minimally invasive amperometric monitoring of biomarkers in the tear fluid. Our focus here is on the microfabrication and in‐vitro testing of the new laterally rolled screen‐printed sensor. The new device responds rapidly and sensitively to dynamic changes in the levels of norepinephrine and glucose (the later in connection to glucose‐oxidase containing ink). Coverage of the enzyme electrode with an electropolymerized polytyramine minimizes contributions from the common electroactive interferences ascorbic and uric acids. Such attractive performance indicates great promise for minimally invasive monitoring of health biomarkers in the tear fluid, or in alternative usage such as capillary microelectrophoresis, ultralow volume sampling, or in‐flow (tubular) systems for batch processing of blood or culture media.     

How Can Rotaxanes Be Modified by Varying Functional Groups at the Axle?—A Combined Theoretical and Experimental Analysis of Thermochemistry and Electronic Effects

We present theoretically as well as experimentally determined thermochemical data of the non-covalent interactions in different axle-substituted pseudorotaxanes. The overall interaction energy lies in the region of 35 kJ mol(-1), independent of the substitution pattern at the axle. Because rearrangement energies of 7 and 3 kJ mol(-1) are required for wheel and axle, respectively, the sum of the net interactions of individual non-covalent bonds must exceed 10 kJ mol(-1) to achieve a successful host-guest interaction. The geometrical analysis shows three hydrogen bonds, and the close inspection of the individual dipole moments as well as the individual hydrogen bonds reveals trends according to the different functional groups at the axle. The individual trends for the different hydrogen bonds almost lead to a cancellation of the substitution effects. From solvent-effect considerations it can be predicted that the pseudorotaxane is stable in CHCl(3) and CH(2)Cl(2), whereas it would dethread in water. Comparing experimentally and theoretically calculated Gibbs free enthalpies, we find reasonable agreement if an exchange reaction of one solvent molecule instead of the direct formation reaction is considered.     

Synthesis of Amphiphilic Fullerene Derivatives and Their Incorporation in Langmuir and Langmuir‐Blodgett Films

Various amphiphilic fullerene derivatives were prepared by functionalization of [5,6]fullerene‐C₆₀‐I_h (C₆₀) with malonate or bis‐malonate derivatives obtained by esterification of the malonic acid mono‐esters 5 – 7 . Cyclopropafullerene 10 was obtained by protection of the carboxylic acid function of 6 as a tert‐butyl ester, followed by Bingel addition to C₆₀ and a deprotection step (Scheme 2). The preparation of 10 was also attempted directly from the malonic acid mono‐ester 6 under Bingel conditions. Surprisingly, the corresponding 3′‐iodo‐3′H‐cyclopropa[1,9][5,6]fullerene‐C₆₀‐I_h‐3′‐carboxylate 11 was formed instead of 10 (Scheme 3). The general character of this new reaction was confirmed by the preparation of 15 and 16 from the malonic acid mono‐esters 13 and 14 , respectively (Scheme 4). All the other amphiphilic fullerene derivatives were prepared by taking advantage of the versatile regioselective reaction developed by Diederich and co‐workers which led to macrocyclic bis‐adducts of C₆₀ by a cyclization reaction at the C‐sphere with bis‐malonate derivatives in a double Bingel cyclopropanation. The bis‐adducts 37 – 39 with a carboxylic acid polar head group and four pendant long alkyl chains of different length were prepared from diol 22 and acids 5 – 7 , respectively (Scheme 9). In addition, the amphiphilic fullerene derivatives 45, 46, 49, 54 , and 55 bearing different polar head groups and compound 19 with no polar head group were synthesized (Schemes 11–13, 15, and 5, resp.). The ability of all these compounds to form Langmuir monolayers at the air‐water interface was investigated in a systematic study. The films at the water surface were characterized by their surface pressure vs. molecular area isotherms, compression and expansion cycles, and Brewster‐angle microscopy. The spreading behavior of compound 10 was not good, the two long alkyl chains in 10 being insufficient to prevent aggregation resulting from the strong fullerene‐fullerene interactions. While no films could be obtained from compound 19 with no polar head group, all the corresponding amphiphilic fullerene bis‐adducts showed good spreading characteristics and reversible behavior upon successive compression/expansion cycles. The encapsulation of the fullerene in a cyclic addend surrounded by four long alkyl chains is, therefore, an efficient strategy to prevent the irreversible aggregation resulting from strong fullerene‐fullerene interactions usually observed for amphiphilic C₆₀ derivatives at the air‐water interface. The balance of hydrophobicity to hydrophilicity was modulated by changing the length of the surrounding alkyl chains or the nature of the polar head group. The best results in terms of film formation and stability were obtained with the compounds having the largest polar head group, i.e. 45 and 46 , and dodecyl chains. Finally, the Langmuir films obtained from the amphiphilic fullerene bis‐adducts were transferred onto solid substrates, yielding high‐quality Langmuir‐Blodgett films.