Electronic structure near metal-metal interfaces

A review will be given of recent calculations on metal films which give information about metal-metal interfaces. The systems discussed will include palladium on niobium, cesium on tungsten, and nickel on copper. In general it is found that the electronic structure closely resembles the bulk within one or two atomic layers of the interface. Using these methods it is possible to calculate directly the interface energy.     

Accurate determination of traces of sodium and potassium in rocks by ion exchange followed by atomic absorption spectroscopy

Sodium and potassium (5–1000 p.p.m.) in rocks such as peridotites and dunites can be determined accurately by ion-exchange separation followed by atomic absorption spectrophotometry. The samples are decomposed in sulphuric, hydrochloric and hydrofluoric acid mixtures, and after removal of hydrofluoric acid the cations are absorbed on a 90-ml column of AG50W-X8 cation-exchange resin. Vanadium and other anion-forming elements are eluted with 0.01 M nitric acid containing hydrogen peroxide. Then the alkali metals are eluted with 0.50 M nitric acid, while Mg, Mn, Ca, Ti, Al, Fe and other multivalent elements are retained by the column. The eluate fractions containing the respective alkali metals are measured directly by atomic absorption spectrophotometry against standards in 0.50 M nitric acid. Relevant elution curves, results for synthetic mixtures and for three international rock standards are presented and discussed.     

CIRCULAR DICHROISM SPECTRA OF SYSTEM I PARTICLES FROM NORMAL CHLOROPLASTS AND CAROTENOID-DEFICIENT MUTANTS OF MAIZE

Abstract— Circular dichroism (CD) spectra were studied in System I particles prepared by digitonin fragmentation of chloroplasts of normal maize and carotenoid-deficient mutants. CD bands of pigment molecules were found to be higher in particles than in solutions. This phenomenon was most pronounced for the particles containing the carotenoid composition of normal chloroplast lamellae. The CD signal of chlorophylls bound to particles of carotenoid-deficient chloroplasts was closer to that found in solutions. This indicates that aggregation and/or binding of chlorophylls in carotenoid-deficient mutants may be less extensive than in normal chloroplasts.     

Requirements for the formation of a chiral template

The chemisorptive enantioselectivity of propylene oxide is examined on Pd(111) surfaces templated by chiral 2-methylbutanoate and 2-aminobutanoate species. It has been found previously that chiral propylene oxide is chemisorbed enantiospecifically onto Pd(111) surfaces modified by either (R)- or (S)-2-butoxide. The enantiomeric excess (ee) varied with template coverage, reaching a maximum of approximately 31%. Templating the surface using 2-methylbutanoate, where the chiral center is identical to that in the 2-butoxide species, but is now anchored to the surface by a carboxylate rather than an alkoxide linkage, shows no enantiospecificity. The enantioselectivity is restored when the methyl group is replaced by an amine group, where a maximum ee value of approximately 27% is found. DFT calculations and infrared measurements suggest that the structures of the butyl group on the surface are similar for both 2-butoxide and 2-methylbutanoate species, implying that gross conformational changes are not responsible for differences in chemisorptive enantioselectivity. There is no clear correlation between the location of the chiral center and enantioselectivity, suggesting that differences in the template adsorption site are also not responsible for the lack of enantioselectivity. It is proposed that the 2-butyl group in 2-methylbutanoate species is less rigidly bonded to the surface than that in 2-butoxides, allowing the chiral center to rotate azimuthally. It is postulated that the role of the amino group in 2-aminobutanoate species is to anchor the chiral group to the surface to inhibit azimuthal rotation.     

Giant Coster-Kronig transitions and intrinsic line shapes of the anomalous Pd M45VV Auger spectrum of Pd/Ag(100) dilute surface alloys

The Pd M4VV and M5VV Auger spectra of the 0.1 ML Pd/Ag(100) dilute surface alloy have been measured using Auger-photoelectron coincidence spectroscopy. The M4VV spectrum indicates that Pd 3d(3/2) core holes have a Coster-Kronig decay rate that is approximately 10 times that of Pd metal. Our calculations show that this giant enhancement arises from the local electronic structure of excited Pd atoms at the surface. Anomalous features in the Auger line shape are similar to those seen in dilute bulk PdAg alloys, and these features in the M5VV and M4VV lines are in good agreement with theoretical predictions.     

Regulating Molecular Recognition with C‐Shaped Strips Attained by Chirality‐Assisted Synthesis

Chirality‐assisted synthesis (CAS) is a general approach to control the shapes of large molecular strips. CAS is based on enantiomerically pure building blocks that are designed to strictly couple in a single geometric orientation. Fully shape‐persistent structures can thus be created, even in the form of linear chains. With CAS, selective recognition between large host and guest molecules can reliably be designed de novo. To demonstrate this concept, three C‐shaped strips that can embrace a pillar[5]arene macrocycle were synthesized. The pillar[5]arene bound to the strips was a better host for electron‐deficient guests than the free macrocycle. Experimental and computational evidence is provided for these unique cooperative interactions to illustrate how CAS could open the door towards the precise positioning of functional groups for regulated supramolecular recognition and catalysis.     

A divalent germanium complex of calix[5]arene

The reaction of the germylene Ge[N(SiMe(3))(2)](2) with calix[5]arene yields the first example of a group 14 calix[5]arene complex. The crystal structure of this material has been obtained and contains two calix[5]arene macrocycles held together by a Ge(2)O(2) rhombus.     

Trapping a labile adduct formed between an ortho-quinone methide and 2'-deoxycytidine

Selective oxidation by bis[(trifluoroacetoxy)iodo]benzene (BTI) provides an effective trap for quenching adducts formed reversibly between dC and an ortho-quinone methide (QM) under physiological conditions. A model adduct generated by 4-methyl-o-QM and 2'-deoxycytidine is rapidly converted by intramolecular cyclization and loss of aromaticity to a characteristic product for quantifying QM alkylation. However, BTI induces a surprising rearrangement driven by overoxidation of a derivative lacking an alkyl substituent at the 4-position of the QM.