Convergent Syntheses of 3,6-Dihydroxydec-4-enolides

The total syntheses of the 3,6-dihydroxydecanolide from Cordyceps militaris and the novel C-3 epimer are reported using a diastereoselective Nozaki-Hiyama-Kishi reaction in the key cyclization to generate the 6R stereocenter.     

Catalytic Enantioselective Desymmetrisation as a Tool for the Synthesis of Hodgkinsine and Hodgkinsine B

Two palladium‐catalysed amination protocols are deployed in the desymmetrisation of the complex dimeric alkaloid meso‐chimonanthine. The power of these transformations is showcased in an efficient formal and total synthesis of the natural products hodgkinsine and hodgkinsine B, respectively.     

A mathematical basis for strain-gradient plasticity theory—Part I: Scalar plastic multiplier

Strain-gradient plasticity theories are reviewed in which some measure of the plastic strain rate is treated as an independent kinematic variable. Dislocation arguments are invoked in order to provide a physical basis for the hardening at interfaces. A phenomenological, flow theory version of gradient plasticity is constructed in which stress measures, work-conjugate to plastic strain and its gradient, satisfy a yield condition. Plastic work is also done at internal interfaces and a yield surface is postulated for the work-conjugate stress quantities at the interface. Thereby, the theory has the potential to account for grain size effects in polycrystals. Both the bulk and interfacial stresses are taken to be dissipative in nature and due attention is paid to ensure that positive plastic work is done. It is shown that the mathematical structure of the elasto-plastic strain-gradient theory has similarities to conventional rigid-plasticity theory. Uniqueness and extremum principles are constructed for the solution of boundary value problems.     

A mathematical basis for strain-gradient plasticity theory. Part II: Tensorial plastic multiplier

A phenomenological, flow theory version of gradient plasticity for isotropic and anisotropic solids is constructed along the lines of Gudmundson [Gudmundson, P., 2004. A unified treatment of strain-gradient plasticity. J. Mech. Phys. Solids 52, 1379-1406]. Both energetic and dissipative stresses are considered in order to develop a kinematic hardening theory, which in the absence of gradient terms reduces to conventional J₂ flow theory with kinematic hardening. The dissipative stress measures, work-conjugate to plastic strain and its gradient, satisfy a yield condition with associated plastic flow. The theory includes interfacial terms: elastic energy is stored and plastic work is dissipated at internal interfaces, and a yield surface is postulated for the work-conjugate stress quantities at the interface. Uniqueness and extremum principles are constructed for the solution of boundary value problems, for both the rate-dependent and the rate-independent cases. In the absence of strain gradient and interface effects, the minimum principles reduce to the classical extremum principles for a kinematically hardening elasto-plastic solid. A rigid-hardening version of the theory is also stated and the resulting theory gives rise to an extension to the classical limit load theorems. This has particular appeal as previous trial fields for limit load analysis can be used to generate immediately size-dependent bounds on limit loads.     

Prediction and realisation of high mobility and degenerate p-type conductivity in CaCuP thin films

Phosphides are interesting candidates for hole transport materials and p-type transparent conducting applications, capable of achieving greater valence band dispersion than their oxide counterparts due to the higher lying energy and increased size of the P 3p orbital. After computational identification of the indirect-gap semiconductor CaCuP as a promising candidate, we now report reactive sputter deposition of phase-pure p-type CaCuP thin films. Their intrinsic hole concentration and hole mobility exceed 1 × 10²⁰ cm⁻³ and 35 cm² V⁻¹ s⁻¹ at room temperature, respectively. Transport calculations indicate potential for even higher mobilities. Copper vacancies are identified as the main source of conductivity, displaying markedly different behaviour compared to typical p-type transparent conductors, leading to improved electronic properties. The optical transparency of CaCuP films is lower than expected from first principles calculations of phonon-mediated indirect transitions. This discrepancy could be partly attributed to crystalline imperfections within the films, increasing the strength of indirect transitions. We determine the transparent conductor figure of merit of CaCuP films as a function of composition, revealing links between stoichiometry, crystalline quality, and opto-electronic properties. These findings provide a promising initial assessment of the viability of CaCuP as a p-type transparent contact.

We synthesize air-stable, p-type CaCuP thin films with high hole concentration and high hole mobility as potential p-type transparent conductors. We study their optoelectronic properties in detail by advanced experimental and computational methods.     

Synthesis of thioridazine-VLA-4 antagonist hybrids using N-propargyl northioridazine enantiomers

Abstract

Herein, we report the synthesis of thioridazine-VLA-4 hybrid epimers. These hybrid molecules were obtained by means of a click reaction involving N-propargyl northioridazine enantiomers and an azide containing VLA-4 antagonist. A synthesis of northioridazine enantiomers from racemic thioridazine was developed and the absolute stereochemistry was confirmed by X-ray crystallography. Access to N-substituted thioridazine analogs may reveal that this phenothiazine core has therapeutic potential in other disease avenues.     

Local layer structure of the steep field line defect in surface-stabilized ferroelectric liquid crystal cells

The local layer structure of one type of DC electric field induced line defect observed in CS-1014 surface stabilized ferroelectric liquid crystal electro-optic cells has been determined using X-ray scattering and optical microscopy. The characterized defect is a high contrast defect line distinct from other field lines in that a defect mirror image is not produced when the DC field direction is reversed.     

Surfactin-like structures of five cyclic depsipeptides from the marine isolate ofBacillus pumilus

Five cyclic depsipeptides with molecular masses of 1007, 1021, 1021, 1035, and 1035 were obtained fromBacillus pumilus KMM 150 associated with Australian marine spongeIrcinia sp. Their structures were assigned by mass spectrometric techniques (high-resolution fast atom bombardment and electron impact mass spectrometry), chemical modification, and extensive spectroscopic analysis, including several types of two-dimensional NMR.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 979–983, May, 1995.The authors are grateful to Dr. V. V. Mikhailov, the Head of the Laboratory of marine microbiology of PIBC of the Far-Eastern Branch of the RAS, and to Dr. E. P. Ivanova for isolation, systematic determination, and cultivation of the strain KMM 150. The authors are also thankful to T. I. Zykova for carrying out the fermentative hydrolysis of peptide4c.     

Critical path analysis and resource constrained project scheduling — Theory and practice

Critical path techniques have been in documented use since the mid 1950's and are now widely used in most aspects of project planning and control. Interest in this area in recent years has been mainly concerned with making the best use of scarce resources throughout the duration of a project and a considerable amount of work has been undertaken in this area by both theorists and practitioners in project management. There is still however an apparent gap between the published theoretical work and the requirements of project schedulers and managers in the field and this paper briefly describes the different approaches taken, how they differ and suggests where future effort may be directed.     

Application of a resolution enhancement technique to the FTIR characterisation of propylene/ethylene copolymers

FTIR methods for determining the composition and ethylene sequencing in propylene/ethylene copolymers are presented and quantified by comparison to¹³C NMR data.