Direct and indirect DIET and DIMET from semiconductor and metal surfaces: what can we learn from 'toy models'?

Desorption induced by electronic transitions (DIET) and its variant DIMET (M = 'Multiple'), are among the simplest possible "reactions" of ad-species involving ultra-short lived electronically excited states at surfaces. The non-adiabatic bond-cleavage can be enforced, for example, with laser irradiation or with electrons or holes emitted from the tip of a scanning tunnelling microscope (STM). The transient creation of excited intermediates can proceed directly (localised to the adsorbate-substrate complex), or indirectly (i.e., through the substrate). To understand the basic processes, simple one-mode two-state "toy models" such as the Menzel-Gomer-Redhead (MGR) or the Antoniewicz scenarios have proven very useful in the past. We adopt and extend MGR- and Antoniewicz-type models together with numerically exact open-system density matrix theory to address a few actual problems/experiments in DI(M)ET: (1) Direct, laser-induced desorption of H(D) from Si(100) surfaces which has been realised in the continuous-wave DIET regime only recently [T. Vondrak and X.-Y. Zhu, Phys. Rev. Lett., 1999, 82, 1967], is studied and compared to so-far hypothetical femtosecond laser desorption. The possibility of controlling the reaction by shaping the laser pulses is addressed. (2) For the same system, temperature effects are studied for electron- or hole-stimulated desorption with an STM [T. C. Shen, C. Wang, G. C. Abeln, T. R. Tucker, J. W. Lyding, Ph. Avouris and R. E. Walkup, Science, 1995, 268, 1590; C. Thirstrup, M. Sakurai, T. Nakayama and K. Stokbro, Surf. Sci., 1999, 424, L329]. A modified version of Gadzuk's "sudden transition and averaging" approach is adopted which accounts for temperature dependent excited state lifetimes. (3) For photodesorption of NO from Pt(111), based on quantum dynamical simulations possible experimental tests involving static electric fields are suggested to address the relevance of the recently challenged [F. M. Zimmermann, Surf. Sci., 1997. 390, 174], "negative ion resonance" model of the Antoniewicz type.     

Cucurbitacin and Triterpenoid Glycosides from Hemsleya giganthy

From rhizomes of Hemsleya giganthy collected in Shichuan of China,16 compounds were isolated.Among them,three compounds (8,9,15)are new natural products called Hemslecins G;Hemsgiganosides A and B;respectively.Their structures were elucidated as 7-hydroxy-23,24-dihydro-cucurbitacin F-25-O-acetate(8);3-O-(6‘‘‘‘‘‘‘‘-butyl ester-)-β-D-glu-curono-pyranosyl)-oleanolic acid-28-O-α-L-arabinopyranoside(9);3-O-β-D-glucuropyranosyl oleanolic acid-28-O-β-D-gluco pyranosyl-(1→6)-β-D-glucopyranoside(15)by spectroscopic and chemical means.     

Eudesmanes and Eudesmanoic Glucosides from Laggera pterodonta

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New flavone and isoflavone glycoside from Belamcanda chinensis

The new flavone, 5,4'-dihydroxy-6,7-methylenedioxy-3'-methoxyflavone, and one new isoflavone glycoside, 3',5'-dimethoxy irisolone-4'-O-β-D-glucoside were isolated from the rhizomes of Belamcanda chinensis. Their structures were established based on the spectroscopic methods.     

Red Mechanoluminescence and Photoluminescence from Novel Europium Complexes

IntroductionMechanoluminescence(ML)islightemissioncausedbymechanicalforcesuchasgrinding,cuttingandsoon.AlthoughsomeofinorganicandorganicmolecularsolidsshowML,theMLmechanismhasnotbeenclearlyelucidatedyetl-4.The'compound,whichshowsallofML,photoluminescence(PL)andelectroluminescence(EL)properties,hasneverbeenreported.Recently,organiceuropium-compIexeshaveattractedsignificantinterestforthedevelopmentofELdevices5-'.ItisconsideredthateuropiumcomplexesareoneofthebestredELmaterialsduetotheirgo…     

Medium-sized and strained heterocycles from non-catalysed and gold-catalysed conversions of β-carbolines

2-Allyl-1-vinyl-β-carbolines and dihydropyrrolo-β-carbolines react with activated internal alkynes through novel rearrangement reactions leading to complex polycyclic structures. Favored reaction pathways depend on reaction conditions and on the presence of gold catalysts. In particular, upon reaction with 2 equiv. of the alkyne, new hexacyclic structures 10 are formed with total stereocontrol.     

New Eudesmane and Eremophilane Derivatives from Laggera Alata

From the aerial part of Laggera alata,a novel erenophilanoid(1)as well as two new eudesmanoids(2-3)were isolated.Their structures were elucidated by 2D-NMR technique and Xray diffraction studies.The cytotoxic activities of these sesquiterpenes were also investigated.     

Isolation and Characterization of Antimicrobial Polypeptide from Loach

A novel antimicrobial polypeptide was isoated and characterized from loach,misgurnus anguillicaudatus.The polypeptide,named MAPP,is a single-chain polypeptide with Mw adout 9,800 Dalton and pI about 4.78:the N-tag of MAPP was CFGWN.MAPP showed good inhibition against various bacteria including Bacillus subtilis.Escherichia coli and Staphylococcus aureus.MAPP could be used as a lead compound in antibiotics drug discovery.     

Lethaclado acid A and B from Lethariella cladonioides

Two new compounds,lethaclado acid A(1) and B(2),were isolated from the acetone extract of Lethariella cladonioides.Their structures were elucidated on the basis of 1D and 2D NMR as well as ESI-MS spectral data.     

Isolation and Characterization of C-phycocyanin from Spirulina Platensis

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Synthesis and asymmetric oxidation of thioglycosides derived from neomenthanethiol and α-d-galactose

6-Deoxy-6-[(1S,2S,5R)-2-isopropyl-5-methylcyclohexylsulfanyl]-1,2:3,4-di-O-isopropylidene-α-d-galactopyranose was synthesized in 94% yield from 1,2 : 3,4-di-O-isopropylidene-α-d-galactopyranose and neomenthanethiol, and its oxidation gave the corresponding diastereoisomeric sulfoxides in up to 84% yield and de values of up to 52%. The isopropylidene protective groups were removed from the sulfide and sulfoxides by treatment with trifluoroacetic acid in chloroform.     

Synthesis of Cyclohexyl and Isopropyl Ketones from Benzimidazole Methiodide Salt and Grignard Reagents

The reaction of 2-alkyl-l, 3-dimethylbenzimidazolinm salts with Grignard reagents gave addition products which were hy-drelyzed to give ketones. A new method for the preparation of cyclohexyl ketones and isopropyl ketones is provided.     

Direct patterning of nanostructured ceramics from solution—differences from conventional printing and lithographic methods

We have proposed an innovative concept and technology, “soft processing” or “soft solution processing,” which aims at low energetic (environmentally benign) fabrication of shaped, sized, located, and oriented ceramic materials by chemical reactions in or from solutions. By activating or stimulating those reactions locally and/or moving the reaction point dynamically, we can obtain patterned ceramic films directly in solution without any postheating, masking, or etching. Using those “direct patterning” concepts and technologies, we have developed methods for direct patterning of CdS, PbS, and CaWO₄ on paper substrates by ink-jet reaction at RT and TiO₂ patterning on a glass substrate by ink-jet deposition at <573 K. Furthermore, we have succeeded in fabricating a BaTiO₃ pattern by a laser beam-assisted process and a carbon pattern by a needle electrode, directly in solutions at ambient temperatures and pressures.     

Sol–gel composite coatings from methyltriethoxysilane and polymethylhydrosiloxane

New composite coatings were prepared by mixing pre-hydrolyzed methyltriethoxysilane (MTES) sol by an acidic catalyst dibutyltin dilaurate (DBTDL) and polymethylhydrosiloxane (PMHS) in gasoline at room temperature. The gel process was thoroughly investigated regarding the use of different basic catalyst [3-aminopropyltriethoxysilane (APTES) or triethylamine (TEA)], as well as the ratios of pre-hydrolyzed MTES sol and PMHS with various content of active H. It was revealed that the composite coating from 2:1 ratio (w/w) of pre-hydrolyzed MTES sol with equimolar amounts of water and PMHS_1.55 under the catalysis of APTES demonstrated high pencil hardness, and excellent resistance against contamination and corrosion. This composite coating (MTPM21-A) was further characterized by FTIR, ²⁹Si NMR, DSC and TGA.     

New flavan and unusual chalcone glycosides from Drypetes parvifolia

Two new compounds 7-hydroxy-5-O-（β-D-glucopyranoside） flavan （1） and （Z）-4＇,6＇-dihydroxy-2＇-O-（β-D-glucopyranoside） chalcone （2）, along with eight known compounds, were isolated from the stem bark of Drypetes parvifolia （Euphorbiaceae）. Their structures were established on the basis of spectroscopic analysis and chemical evidence.     

Isolation and Characterization of an Antimicrobial Polypeptide from Loach

Hydrobionts formed their special defense systems during evolution. One such system is that of non-specific immunity which comprises a wide variety of peptides with potent antimicrobial activities1. The mechanism of action of most antimicrobial peptides was reported as that a few peptide molecules formed a channel on cell membrane, and the cell was then died of the outflowing of cellular contents. The above mechanism was different from that of antibiotics2, 3. It is a promising area to disc…     

A facile access to mono-C-alkynylated-o-carboranes from o-carboranes and arylsulfonylacetylenes

A facile access to mono-C-alkynyl-o-carboranes from o-carboranes and arylsulfonylacetylenes was developed. This facile process tolerates a wide variety of functional groups, occurs at mild conditions in onepot procedure with short reaction time. The obtained mono-C-alkynyl-o-carboranes can be easily derivatized to synthesize 1,2-difunctionalized o-carboranes. This work provides a useful tool for the functionalization of o-carboranes.     

Hybrid Sol-Gel Coatings Produced from TEOS and γ-MPS

Hybrids sols from tetraetoxysilane (TEOS) and 3-(methacryloxypropyl) trimethoxysilane (-MPS) were prepared in acid medium for different TEOS/-MPS ratios and were modified by the addition of a colloidal silica suspension. The stability of the different sols was evaluated by viscosity measurements; the sols showed a Newtonian behaviour and the ageing effect was negligible even after two months from their preparation. Coatings were obtained by dipping at different withdrawal rates and heat-treated between 150 and 250°C. Transparent coatings with thickness higher than 4 m were reached for most of the studied compositions. The surface microhardness of coatings for each composition and thermal treatment was evaluated by the pencil hardness test. The thermal stability was followed by simultaneous thermogravimetric and differential thermal analysis (TGA-DTA) determining the limit temperatures at which the coatings can be treated without losingits hybrid character. A structural analysis was made by deconvolution of Fourier transformed infrared spectra (FTIR) of self-supported films observing the influence of the organic groups on the silica network.     

Synthesis of Large-ring Cycloalkanediones from Bis-Grignard Reagent and Dinitriles

1, 6-Cyclododecanedione and 1, 8-cyclotetradecanedione were prepared from bis-Grignard reagent and dinitriles. This is a convenient synthetic method for large-ring cycloalkanediones.     

Isolation and Crystal Structure of Xanthones from Swertia Chirayita

1 INTRODUCTION Swertia chirayita (Buch.-Ham.) grows abundantly in the temperate regions of Himalayas. It is used in Tibetan folk medicine as the traditional remedy for chronic fever, anaemia, asthma, liver disorders, hepatitis and stomachic. Recently, th…