Natural abundance 13C13C coupling constants observed via double quantum coherence. The two-dimensional ‘inadequate’ experiment for 13C NMR spectral analysis of erythronolide - B

A one- and a two-dimensional INADEQUATE NMR experiment afforded one-bond ¹³C¹³C coupling constants at natural abundance and total unambiguous signal assignment for erythronolide-B (1). ¹³C¹³C coupling constants at natural abundance and total unambiguous signal assignment for erythronolide-B (1).     

Synthesis and structures of Pb3O2(CH3COO)2·0.5H2O and Pb2O(HCOO)2: two corrosion products revisited

Reactions of carboxylic acids with lead play an important role in the atmospheric corrosion of lead and lead-tin alloys. This is of particular concern for the preservation of lead-based cultural objects, including historic lead-tin alloy organ pipes. Two initial corrosion products, Pb(3)O(2)(CH(3)COO)(2)·0.5H(2)O (1) and Pb(2)O(HCOO)(2) (2), had been identified through powder diffraction fingerprints in the Powder Diffraction File, but their structures had never been determined. We have crystallized both compounds using hydrothermal solution conditions, and structures were determined using laboratory and synchrotron single-crystal X-ray diffraction data. Compound 1 crystallizes in P1, and 2 in Cccm. These compounds may be viewed as inorganic-organic networks containing single and double chains of edge-sharing Pb(4)O tetrahedra and have structural similarities to inorganic basic lead compounds. Bond valence sum analysis has been applied to the hemidirected lead coordination environments in each compound. Atmospheric exposure experiments contribute to understanding of the potential for conversion of these short-term corrosion products to hydrocerussite, Pb(3)(CO(3))(2)(OH)(2), previously identified as a long-term corrosion product on lead-rich objects. Each compound was also characterized by elemental analysis, thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), and Raman spectroscopy.     

High temperature crystal structures and superionic properties of SrCl2, SrBr2, BaCl2 and BaBr2

The structural properties of the binary alkaline-earth halides SrCl₂, SrBr₂, BaCl₂ and BaBr₂ have been investigated from ambient temperature up to close to their melting points, using the neutron powder diffraction technique. Fluorite-structured SrCl₂ undergoes a gradual transition to a superionic phase at 900–1100 K, characterised by an increasing concentration of anion Frenkel defects. At a temperature of 920(3) K, the tetragonal phase of SrBr₂ undergoes a first-order transition to a cubic fluorite phase. This high temperature phase shows the presence of extensive disorder within the anion sublattice, which differs from that found in superionic SrCl₂. BaCl₂ and BaBr₂ both adopt the cotunnite crystal structure under ambient conditions. BaCl₂ undergoes a first-order structural transition at 917(5) K to a disordered fluorite-structured phase. The relationship between the (disordered) crystal structures and the ionic conductivity behaviour is discussed and the influence of the size of the mobile anion on the superionic behaviour is explored.     

Thrust programs for minimum propellant consumption during the vertical take-off and landing of a rocket

In this paper, the thrust programs for minimum propellant consumption during vertical take-off and landing maneuvers of a rocket in a vacuum are derived for an arbitrary central gravitational field. It is shown that, regardless of the mathematical form of the attracting force, the extremal arc for take-off is composed of a maximum thrust subarc followed by a coasting subarc, and the extremal arc for landing is composed of a coasting subarc followed by a maximum thrust subarc.     

Development of proposed federal standard 1070: 62.5/125-μm graded-index, multimode optical fiber waveguides for on-premises applications

This paper describes a process that has been successful in generating a specification to guide the user community in the procurement of single-size, multimode optical fiber for on-premises applications. This process began with an attempt to adopt an industry standard as a federal standard that would eliminate a multiplicity of choices available from the marketplace. The initial EIA-458-A Standard contained four “preferred” sizes. Discussions both in a government standards committee and in an applications-oriented industry (EIA) working group indicated the desirability of recommending a single fiber size. The process by which the industry committee selected the 62.5-μm core diameter/125-μm cladding diameter multimode fiber is presented.

The next element of the process was that of selecting the appropriate standard performance measures and attributes that would assure minimum performance of graded parameters such as attenuation and bandwidth, as well as a uniform specification of the product. The vehicle selected for this specification was the EIA 492-Series Generic, Sectional, and Blank Detail Specifications. Inputs were solicited from all of the identified U.S. manufacturers of this fiber size. Those inputs were coordinated and integrated into a detail specification, which is now being circulated by the EIA on a standards proposal ballot. After ballot approval, it will be published as an ANSIIEIA standard specification. Similar work has been initiated to develop a detail specification for fiber optic cables based on a related set (472-Series) of EIA specifications.

The process of developing a detail specification that assures conformance of the product to dimensional and strength tolerances as well as performance measures requires considerable coordination and iteration. No proprietary information or processes are contained in the specification so that the industry participants are free to compete on price and performance as long as compliance with the specification can be demonstrated.     

A new approach for the formation of fused cyclooctane or cyclohexane rings

The intramolecular regioselective addition of unsymmetrical allylsilanes to conjugated dienones is shown to permit facile entry into 5-6, 6-6, 5-8, and 6-8 bicyclic ring systems.     

On the photoisomerisation of 13-desmethyl-retinal

All mono-$\text{cis}$-isomers of 13-desmethyl-retinal have been prepared fro the alll-$\text{trans}$-compound by photoisomerisation. The various isomers were separated by HPLC and identified by their 400 MHz-¹NMR-spectra.     

The calculation of monocyclic molecular structures using MINDO/3

A comparison is made of the experimentally determined structures for some 4, 5, and 6 membered monocyclic rings and the MINDO/3 calculated structures. Among several systematic deficiencies the calculated ring structures are found to be too flat. This is attributed to the fact that MINDO/3 underestimates 1,4-eclipsing interactions.