Identification of a TGBA liquid crystal phase via its defects

We have shown that cholesteryl nonanoate, a thermotropic compound which is well known to exhibit pretransitional effects at the smectic A (SmA) cholesteric (N*) transition (W.L. McMillan, Phys. Rev. A 4, 1238 (1971); 6, 936 (1972)), has in fact a TGBA phase in between. Our arguments rely on the observation of new TGBA defects, either in Robinson spherulites cooled from the N* phase or in free-standing films. The same new defects can be obtained in a well-documented TGBA phase of a tolane compound. We analyze qualitatively the TGBA defects in both geometries, in particular their relation to the disclination radius of the N* Robinson spherulites. Received 12 February 2001     

Commensurate and incommensurate hydrogen bonds. An exercise in crystal engineering.

Ureas characteristically form one-dimensional hydrogen-bonded alpha-networks with a repeat distance of about 4.60 A. Oxamides form similar alpha-networks with a longer 5.05 A repeat distance. The urea of glycine and the oxamide of glycine were each cocrystallized with a series of four bipyridines, including two urea derivatives and two oxamide derivatives. This series of eight cocrystals was studied by X-ray diffraction in order to see what would happen when molecules that would normally form alpha-networks with incommensurate distances were forced into the same crystal. The two all-urea crystals and the two all-oxamide crystals contained the expected alpha-networks with repeat distances in accordance with normal urea or oxamide values. Four of the crystals were mixed, containing both oxamide and urea molecules. Three consisted of two-dimensional beta-networks with alternating parallel urea and oxamide subnetworks. The repeat distances averaged 4.87 A, a value close to the value expected for oxamides, but shorter than any previously observed examples. In the fourth mixed crystal, the urea alpha-network formed with a normal urea repeat distance, but the oxamide network did not form, the oxamide adopting an unusual molecular conformation that maximizes intramolecular hydrogen bonds instead.     

Fission Mode Description of Mass Distributions for Fissioning Systems Ranging from Mass 230 to 262

Data on fragment mass yields in spontaneous and thermal neutron induced fission of wide range of nuclides from light actinides through heavy actinides were analyzed and completely described as mass distribution parameters, based on the concept of multimodal fission. The evidence that supports the existence of multi-components in the mass distribution of fission fragments, bimodal asymmetric mode in light actinide fission, bimodal symmetric mode in heavy actinide fission, and the existence of the boundaries of fission asymmetry has been obtained.     

Processing the capillary viscometry data of fluids with yield stress

The capillary viscometer is used to measure the shear stress-shear rate relationship of a wide range of purely viscous fluids. It is however not considered as an appropriate instrument for obtaining the yield stress and the post-yield behaviour of fluids that have a yield stress. This is partly because conventional methods of processing the capillary viscometry data of purely viscous fluids cannot be applied to similar data of fluids with yield stress. The unavoidable experimental noise in the capillary data, particularly at low shear rates, also makes it difficult to obtain a reliable estimate of the yield stress from capillary data. In this investigation the problem of converting the capillary viscometry data of yield stress fluids into a shear stress-shear rate curve and a yield stress is formulated as a Volterra integral equation of the first kind. This is an ill-posed problem i.e. noise in the data will be amplified by inappropriate methods of data processing. A method, based on Tikhonov regularisation that takes into account the ill-posed nature of the problem, is then developed to solve this problem for fluids with yield stress. The performance of this method is assessed by applying it to a set of “synthetic” capillary viscometry data with added random noise and to a set of experimental data for a concentrated suspension of TiO₂ taken from the literature. In both cases Tikhonov regularisation was able to extract the complete shear properties of these fluids from capillary viscometry data alone. Received: 22 November 1999/Accepted: 17 December 1999     

Two-stage dilute-acid pretreatment of softwoods

Whole treechips obtained from softwood forest thinnings were pretreated via single-and two-stage dilute-sulfuric acid pretreatment. Whole-tree chips were impregnated with dilute sulfuric acid and steam treated in a 4-L steam explosion reactor. In single-stage pretreatment, wood chips were treated using a wide range of severity. In two-stage pretreatment, the first stage was carried out at low severity tomaximize hemicellulose recovery. Solubilized sugars were recovered from the first-stage prehydrolysate by washing with water. In the second stage, water-insoluble solids from first-stage prehydrolysate were impregnated with dilute sulfuric acid, then steam treated at more severe conditions to hydrolyze a portion of the remaining cellulose to glucose and to improve the enzyme digestibility. The total sugar yields obtained after enzymatic hydrolysis of two-stage dilute acid-pretreated samples were compared with sugar yields from single-stage pretreatment. The overall sugar yield from two-stage dilute-acid pretreatment was approx 10% higher, and the net enzyme requirement was reduced by about 50%. Simultaneous saccharification and fermentation using an adapted Saccharomyces cerevisiae yeast strain further improved cellulose conversion yield and lowered the enzyme requirement.     

Slip-shakedown analysis of a system of circular beams in frictional contact

In automotive components, the cumulative microslip phenomenon is often observed for engine assemblies. This phenomenon results in an accumulation of the relative slips in a preferred tangential direction on the contact interface of two solids under cyclic loadings. A significant relative displacement may occur and leads to the assembly failure. In particular, a global rotation of the bearing shell may result from this mechanism of cumulated slips in conrod big end systems. To discuss this rotation problem, a model of two circular beams in frictional contact and submitted to a periodical rotating load is considered here. The aim is to give some simplified estimates of the critical rotation load based on a slip-shakedown analysis. The discussion holds for Tresca friction and can be extended to Coulomb friction under the assumption of small coupling. The static and kinematic slip-shakedown approaches are discussed. The obtained analytical results are shown to be in agreement with the finite element computations.     

Interaction of Triatomic Germanium with Lithium Atoms: Electronic Structure and Stability of Ge3Lin Clusters

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Side Chain Influence on Electrochemical and Photovoltaic Properties of Yne‐Containing Poly(phenylene vinylene)s

Summary: The electrochemical behaviour of four types of (phenylene ethynylene)‐alt‐(phenylene vinylene) hybrid polymers, 1 , 2 , 3 , and 4 have been investigated with respect to the influence of the grafted alkoxy side chains. In the case of the fully substituted polymers 2 , 3 , and 4 , the strong insulating nature of longer linear octadecyl or bulky branched 2‐ethylhexyl side chains lowers the HOMO levels of the polymers thereby increasing the discrepancy, ΔE_g, between the electrochemical, Eequation/tex2gif-stack-1.gif, and the optical, Eequation/tex2gif-stack-2.gif, bandgap energies. Thus it is not possible to establish a direct correlation between the open circuit voltage, V_OC, of bulk heterojunction solar cell devices of the configuration glass substrate/ITO/PEDOT:PSS/polymer 3 :PCBM(1:3, w/w)/LiF/Al and the HOMO energy levels of polymer 3 solely, as postulated in the literature. The photovoltaic (PV) parameters greatly depend on the grafted side chains.

Linear I–V curves of solar cell devices from polymers 3a – d , measured in the dark and under 100 mW · cm⁻² solar simulator illumination.     

Synthesis of aromatic polythioamide-oxothioxoquinazolines from bis(1,3,4-thiadiazoline-5-thione) and aromatic bis-o-amino esters

Aromatic polythioamide-oxothioxoquinazolines were synthesized by the polycondensation of 2,2′-(m-phenylene)bis-1,3,4-thiadiazoline-5-thione with aromatic bis-o-amino esters. The polymerizations were carried out at 160°C in acidic media such as m-cresol, sulfolane, and polyphosphoric acid to produce polymers with reduced viscosities up to 0.5 dL/g. These polymers were soluble in polar aprotic solvents like N-methyl-2-pyrrolidone and some acidic media including m-cresol. The polythioamide-oxothioxoquinazolines showed relatively good thermal stability with 10% weight loss at 344–394°C in air.