Eclipsed Isopropyl Conformations of Two Dimeric Hydrazines

The X-ray structures of 4,10-di-tert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2(3,6)]tetradecane (s4iPr) and its 4,9-di-tert-butyl-5,10-diisopropyl isomer (a4iPr) are reported. Both compounds are in conformations having their in-N-alkyl groups (directed toward the central CH-CH bond of the molecule) anti to each other, as expected from previous work. The principal feature of interest is that one in-isopropyl group in each compound is in an eclipsed conformation, NN,C(alpha)Me twist angle -0.5(5) degrees for s4iPr and -6.4(4) degrees for a4iPr. Low energy (somewhat less) eclipsed in-isopropyl conformations are predicted by both molecular mechanics (MM2) and semiempirical quantum mechanical (AM1) calculations. The asymmetry of the potentially C(2) symmetric a4iPr because the two in-isopropyl groups are in different rotamers is apparently not a result of crystal packing forces, because a conformation with different isopropyl rotamers is the more stable one by at least 1.0 kcal/mol in solution, determined by (13)C-NMR spectroscopy. This result is not predicted by either calculation method. The "monomer", 2-tert-butyl-3-isopropyl-2,3-diazabicyclo[2.2.2]octane (3), proves to be a poor model for the conformations of 4iPr.     

Siliconizing as a method for the production of acid-resistant modifications of faujasite

It was shown that acid-resistant modifications of faujasite can be produced by its thermal treatment in silicon tetrafluoride vapor if the ratio of the atoms in the zeolite framework is increased as a result of such treatment to Si/Al 12. At lower degrees of isomorphous substitution of the atoms. the faujasite crystal lattice is destroyed in a 5 M solution of hydrochloric acid as a result of the low acid resistance of the aluminum-oxygen tetrahedra of the zeolite and of the imperfections in its structure.L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Kiev. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 1, pp. 51–54, January–February, 1996. Original article submitted March 20, 1995.     

High sensitivity flow-based analysis system using a semiconductor laser and thin long flow-through cell for the determination of total phosphorus in water

A highly sensitive detection system using a semiconductor laser (SCL) and a thin long flow-through cell (TLFCT) to match flow-based analysis, such as flow injection analysis (FIA), has been developed. The SCL was a GaAlAs semiconductor laser emitting at 780 nm (5 mW), and the TLFTC, which has a 100 mm thin long light path, was made of a poly(tetrafluoroethylene) (PTFE) rod. The sensitivity was essentially improved about 10-fold in comparison to usual FIA-spectrophotometry using a 10 mm conventional flow cell. When this detection system was applied to the determination of total phosphorus (P) in water by molybdenum-blue spectrophotometry, the relative standard deviation, detection limit and linear range were 1.0% (n = 10 at 20 mug P 1(-1)), 0.6 (3 sigma) and 1.0-50 mug P 1(-1), respectively, and the results for the samples were fairly consistent with those by the official method. It may also be possible to apply the present detection system to other flow-based analytical methods such as the liquid chromatography family.     

Complete separability of time-dependent second-order ordinary differential equations

Extending previous work on the geometric characterization of separability in the autonomous case, necessary and sufficient conditions are established for the complete separability of a system of time-dependent second-order ordinary differential equations. In deriving this result, extensive use is made of the theory of derivations of scalar and vector-valued forms along the projection :J ¹ EE of the first jet bundle of a fibre bundleE . Two illustrative examples are discussed, which fully demonstrate all aspects of the constructive nature of the theory.     

Spectral transport model for turbulence

The spectrum of inhomogeneous turbulence is modeled by an approach that is not limited to regimes of large Reynolds numbers or small mean-flow strain rates. In its simplest form and applied to incompressible flow, the model depends on five phenomenological constants defining the strength of turbulence coupling to mean flow, turbulence transport in physical and wave-number space, and mixing of stress-tensor components. The implications for homogeneous isotropic turbulence are investigated in detail and found to correspond well to the conclusions from more fundamental theories. Under appropriate limiting conditions, a turbulent system described by the model will relax over time into a state of approximate spectral equilibrium permitting a reduction to a one-point model for the system that is substantially like the familiar K- model. This yields preliminary estimates of the present model's parameters and points to the way to improved modeling of flows beyond the applicability of the K- method.     

Exact solution of a vertex model ind dimensions

We consider a class of vertex models describing directed lines on a lattice in arbitraryd dimensions, and solve the model exactly for the Cartesian lattice and in the case that each loop of lines carries a fugacity - 1. Our analysis, which can be carried out for arbitrary lattices, is based on an equivalence of the vertex model with a dimer problem. The dimer problem is, in turn, solved using the method of Pfaffians. It is found that the system is frozen below a critical temperatureT _cwith the critical exponent = (3 –d)/2.     

Relaxation and phonons in viscous and glassy orthoterphenyl by neutron scattering

We present an extended set of incoherent neutron scattering measurements on the van der Waals liquido-terphenyl, obtained by time-of-flight and backscattering spectroscopy. In the supercooled liquid regime, data from three instruments are combined and analysed in terms of the selfcorrelationS(Q, t). In the time range 1...100 ps, the crossover from -to -relaxation is well described by the masterfunction of mode coupling theory, and fitted parameters are consistent with the previously established critical temperatureT _c [Z. Phys. B83, 175 (1991)]. In the glassy regime, vibrations are harmonic and can be described by a density of states. Deviations at lowQ are quantitatively explained by a multiple scattering simulation. Throughout the article, experimental difficulties are discussed in some detail.     

Additive pulse mode-locked Nd: YAG laser

Additive pulse mode locking applied to lamppumped Nd: YAG lasers results in an attractive source of picosecond pulses at 1.06 m or 1.32 m with average powers at the Watt level. We provide detailed information on construction and operation and give data on performance. A modified active stabilization scheme allows not only improved stability of operation but also insight into the dynamics of pulse formation.     

Thermal diffusivity measurements of natural and isotopically enriched diamond by picosecond infrared transient grating experiments

The photopyroelectric (PPE) technique is used to measure the specific heat of YBa₂Cu₃O_7–X thin films. Hysteresis in the PPE amplitude is observed in the temperature range 90 K to 250 K. Peaks in the inverse PPE amplitude at T=110 K in the cooling path and at T230 K in the heating path are observed. The magnitude of hysteresis depends upon the thermal history of the sample.