New labdane-type diterpenoids from Leonurus heterophyllus SW

Five new natural labdane-type diterpenoids (5-9), designated leoheteronins A-E, together with four known diterpenoids (1-4), two phytosterols as a mixture of beta-sitosterol and stigmasterol, and the flavone genkwanin (10) were isolated from the aerial parts of Leonurus heterophyllus SW. (Lamiaceae) collected in northern Vietnam. Compound 1 was isolated for the first time from a Leonurus species, and 10 is considered to be a chemotaxonomic marker of the Leonurus genus. Their structures were determined using spectroscopic analyses.     

Optimal admission and pricing control problem with deterministic service times and sideline profit

We consider a discrete-time admission control problem in a company operating in service industries with two classes of customers. For the first class of customers, the company then (1) has an option to accept or reject him/her (admission control), or (2) decides on an offering price (pricing control). The second-class (sideline) customers are only served if no first-class customers are in the system, and this yields the sideline profit. In this paper, we discuss both admission control and pricing control problems within an identical framework, and we examine the properties of the optimal policies to maximize the total expected present discounted net profits. We show that when the sideline profit is large, the optimal policies may not be monotone in the number of first-class customers in the system.     

Surface-enhanced vibrational investigation of adsorbed analgesics

Adsorption properties of acetylsalicylic acid (AA), ibuprofen and acetaminophen deposited from volatile solvents with varying protic/aprotic properties on vacuum-evaporated silver films were characterized using surface-enhanced infrared absorption (SEIRA) and surface-enhanced Raman spectroscopy (SERS). SERS preferentially enhances monolayer Raman shifts, while SEIRA can enhance the infrared absorbance of the monolayer and multilayers. To our best knowledge, this is the first reported study of these molecules using a combination of SERS/SEIRA. SERS revealed that AA and ibuprofen adsorbed ionically in monolayers, independent of the deposition solvents used in the process. SEIRA experiments showed that AA multilayers condensed molecularly using a deposition solvent with polar bonds. However, when an alkane deposition solvent with non-polar bonds such as n-heptane was used, AA adsorbed as acetylsalicylate ions in the first few multilayers, while ibuprofen always adsorbed as the free acid in the multilayer. These ionization trends depend upon the affinity of AA and ibuprofen for the underlying silver film. TPD experiments on silver powders further demonstrated that ibuprofen affinity for silver was less than AA. Furthermore, SEIRA indicated that acetaminophen adsorbed as multilayers of metastable polymorphs using protic or polar aprotic deposition solvents. Protic deposition solvents gave higher quality SERS spectra of an acetaminophen monolayer in comparison to polar aprotic deposition solvents. Such studies could find significant applications in biochemical and nanotechnology processes such as drug delivery, catalysis, and tissue engineering and will contribute to the understanding of the impact and fate of analgesics released into the environment.     

Two new phenolic amides from the seeds of Pharbitis nil

Two new phenolic amides, pharnilatins A (1) and B (2), were isolated from the seeds of Pharbitis nil. These new compounds possess a p-coumaroyl unit with a structurally unique side chain, (2S,3S)-2,3-dihydroxyputrescine. The chemical structures and absolute stereochemistries of the new compounds were determined on the basis of spectroscopic analyses including 1D- and 2D-NMR experiments and chemical reactions. Compounds 1 and 2 exhibited cytotoxicity against A549, SK-OV-3, SK-MEL-2, and HCT-15 human tumor cells. However, none of the compounds inhibited nitric oxide (NO) production in lipopolysaccharide (LPS)-activated microglia cells.     

Voronoi-cell finite difference method for accurate electronic structure calculation of polyatomic molecules on unstructured grids

We introduce a new numerical grid-based method on unstructured grids in the three-dimensional real-space to investigate the electronic structure of polyatomic molecules. The Voronoi-cell finite difference (VFD) method realizes a discrete Laplacian operator based on Voronoi cells and their natural neighbors, featuring high adaptivity and simplicity. To resolve multicenter Coulomb singularity in all-electron calculations of polyatomic molecules, this method utilizes highly adaptive molecular grids which consist of spherical atomic grids. It provides accurate and efficient solutions for the Schrödinger equation and the Poisson equation with the all-electron Coulomb potentials regardless of the coordinate system and the molecular symmetry. For numerical examples, we assess accuracy of the VFD method for electronic structures of one-electron polyatomic systems, and apply the method to the density-functional theory for many-electron polyatomic molecules.     

Highly alkoxylated PPV copolymers for PLEDs: Syntheses, optical properties and enhancement of device lifetimes

A series of solution processible light-emitting copolymers composed of tetraalkoxy-phenylenevinylene (TALK-PPV) and dialkoxy-phenylenevinylene (DALK-PPV) has been synthesized using the Gilch polymerization route. Thermal, optical and electrochemical properties of the synthesized copolymers [poly(TALKPV-co-DALKPV)s] have been investigated and compared with those of each homopolymers, poly[2-(3,7-dimethyloctyloxy)-3,5,6-trimethoxy]-1,4-phenylenevinylene] (TALK-PPV) and poly[2-(3′,7′-dimethyloctyloxy)-5-methoxy-1,4-phenylenevinylene] (DALK-PPV). The synthesized copolymers showed a high molecular weight (Mn=∼2-3.0×10⁵) and narrow polydispersity indices (∼3). Electroluminescent devices using the copolymers as the emissive layer have been fabricated with a configuration of ITO/PEDOT:PSS/polymers/Ca/Al. Interestingly the copolymer devices resulted in a more than 4-fold increase in device lifetime than the homopolymers, which might be due to the highly reduced steric hindrance of the polymer backbone by introducing DALKPV units between the adjacent highly alkoxylated TALKPV repeating units in the polymer backbone.     

Single-Benzene Dual-Emitters Harness Excited-State Antiaromaticity for White Light Generation and Fluorescence Imaging

Molecular emitters simultaneously generating light at different wavelengths have wide applications. With a small molecule, however, it is challenging to realize two independent radiative pathways. We invented the first examples of dual-emissive single-benzene fluorophores (SBFs). Two emissive tautomers are generated by synthetic modulation of the hydrogen bond acidity, which opens up pathways for excited-state proton transfer. White light is produced by a delicate balance between the energy and intensity of the emission from each tautomer. We show that the excited-state antiaromaticity of the benzene core itself dictates the proton movements driving the tautomer equilibrium. Using this simple benzene platform, a fluorinated SBF was synthesized with a record high solubility in perfluorocarbon solvents. White light-emitting devices and multicolor imaging of perfluorocarbon nanodroplets in live cells demonstrate the practical utility of these molecules.     

Isogeometric cable elements based on B-spline curves

Meccanica - In this paper, the isogeometric cable elements based on B-spline curves are developed for the static analysis of cable structures under conservative static loads. For this, the...     

Evaluation of transient turbulent flow fields using digital cinematographic particle image velocimetry

This paper describes an experimental development for temporal and spatial reconstruction of continuously varying flow fields by means of digital cinematographic particle image velocimetry (PIV). The system uses a copper-vapor laser illumination synchronized with a high-speed camera, and continuously samples at 250 fps to measure transient and non-periodic turbulent flows with relatively low frequencies, i.e., the surf zone turbulence produced by depth-limited wave break in a long laboratory flume. The use of the developed PIV system comprehensively records the temporal development of both phase-averaged and instantaneous turbulent vortex flows descended from the breaking waves to the bottom. Also, the measured power spectra show harmonic frequencies, ranging from the orbital frequency of 0.5 Hz up to the order of 5 Hz, and the well-known −5/3 dependence upon the turbulence fluctuation frequencies thereafter. Received: 2 December 1999/Accepted: 6 September 2000