Preparative isolation of (+)-beta-eudesmol fromAmyris balsamifera

Summary Optically pure (+)-beta-eudesmol is a possible starting material for the synthesis of several termite defense compounds. A two step procedure for the isolation of gram quantities of (+)-beta-eudesmol from commercially availableAmyris balsamifera oil (syn. West Indian sandalwood oil), containing 8% beta-eudesmol, was developed. Step one consisted of an efficient vacuum distillation of the total oil. Step two was a medium pressure LC separation with an AgNO₃ impregnated silica gel stationary phase. Several other separation procedures failed due to the presence of many closely related sesquiterpene alcohols (75% of the oil).     

Buckling delamination in compressed multilayers on curved substrates with accompanying ridge cracks

Residually compressed films and coatings are susceptible to buckle delamination. The buckles often have linear or telephone cord morphology. When the films are brittle, such buckles are susceptible to the formation of ridge cracks that extend along their length, terminating close to the propagating front. The ridge-cracked buckles are invariably straight-sided (not telephone cord) and differ in width. Buckle delaminations of this type occur on flat and curved substrates: having greatest technological relevance in the latter. They occur not only in single layer films but also in multilayers, such as thermal barrier systems. Establishing the mechanics of ridge-cracked buckle delaminations for multilayers on curved substrates serves two purposes. (a) It allows the prediction of buckle delamination and spalling for technologically important systems. (b) It provides a test protocol for measuring properties such as the delamination toughness of the interface and the stresses in the layers. Both objectives are addressed in the article: the latter by devising an inverse algorithm. Implementation of the algorithm is demonstrated for diamond-like carbon films on planar glass substrates and a thermal barrier multilayer on a curved superalloy substrate.     

Optical spectroscopy of Dysprosium Aluminum Garnet (DAG)

The absorption spectrum of antiferromagnetic dysprosium aluminium garnet (DAG) (T _N =2.50 °K) has been investigated at low temperatures. The groundstate splitting due to all interactions in the antiferromagnetic state is (5.27±0.10) cm^?1 extrapolated to 0 °K. The temperature dependence of the lineshift of the absorption lines is measured. Zeeman effect studies give theg-tensor of the groundstate asg _z =18.4±0.5,g _x =g _y =0.5±0.2. The studies also allow the determination of the critical fields asH _c ^[100] =(5.0±0.1) koe,H _c ^[111] =(3.9±0.2) koe andH _c ^[110] =(4.9±0.6) koe. In addition an investigation of a number of satellite lines is performed. Some of them can be interpreted as spin wave sidebands (Stokes and anti-Stokes); others obviously come from dysprosium ions which have impurity ions on regular lattice sites as neighbours.     

Optical investigation of metamagnetic DyAlO3

We have investigated the optical absorption spectra of metamagnetic DyAlO₃ (T _N =3.4 °K) above and below the Néel temperature. We find that the magnetic interactions are predominantly between the ions along the crystallographicc-axis; the interaction energy between two ions isW _C =? (2.9±0.6) cm^?1. Additional line-shifts below 3.4 °K yield the Néel temperature. Zeeman effect studies give the magnetic moment of the groundstate as μ=(9.2 ± 0.9)μ _B . The direction of the magnetic moments is in thea-b plane, with angles of ± 33.5° and ± 146.5° from theb-axis. The Zeeman effect studies reveal two metamagnetic transitions (forH _ext∥μ) at 7.0 and 7.3 kOe respectively. Additional susceptibility and Mössbauer measurements confirm the Néel temperature and the magnetic moment.     

Akustische wellen in Gebieten,die von zwei lokal gestorten parallelen ebenen begrenzt sind

We consider acoustic waves in domains with boundaries, coinciding with two parallel planes outside a sufficiently large sphere. Several results on spectral properties of the Laplace operator in such domains are derived and used to prove uniqueness and existence of a solution of the Dirichlet boundary value problem for the reduced wave equation under additional restrictions. In particular, a class of domains is described for which no eigenvalues are present.     

Photofragment coincidence imaging of small I-(H2O)n clusters excited to the charge-transfer-to-solvent state

The photodissociation dynamics of small I-(H2O)n(n=2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel (approximately 90%) is a two-body process forming neutral I+(H2O)n photofragments, and the minor channel is a three-body process forming I+(H2O)n-1+H2O fragments. Both processes display translational energy [P(ET)] distributions peaking at ET=0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather than to the CTTS state display the same two channels with similar P(ET) distributions. The observation of similar P(ET) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited [I(H2O)n-]* cluster or, less probably, that the presence of the excess electron has little effect on the departing I atom.     

Preparation and Ultrafast Optical Characterization of Metal and Semiconductor Colloidal Nano-Particles

The ultrafast dynamics of photoinduced electrons in several metal and semiconductor colloidal nanoparticle systems are characterized using femtosecond laser spectroscopy. Various preparation methods are used and, in several cases, modified for making particles with long-term stability and narrow and controllable size distributions. The particle size and size distribution are determined using transmission electron microscopy and electronic absorption spectroscopy. For aqueous gold and silver colloids, spatial size confinement is found to cause substantially slower electronic relaxation due to reduction of non-equilibrium electron transport and weaker electron-phonon coupling. In gold colloids, photoejection of electrons into the liquid is observed, which is attributed to a two-photon enhanced ionization process. The effect of surfactant on the electron dynamics in CdS colloids is examined and found to be significant, substantiating the notion that electrons are dominantly trapped at the liquid-solid interface. In Ru³⁺-doped TiO₂ colloids, the electronic decay is found to be as fast as or even faster than in undoped TiO₂ and other semiconductor colloids such as CdS, suggesting that ion doping of large bandgap semiconductor colloids is not necessarily effective in lengthening the electron lifetime. In almost all cases studied, the majority of the photoinduced electrons are found to decay within a few tens of picoseconds due to non-radiative relaxation. The results are discussed in the context of the potential applications of metal and semiconductor nano-particles in areas including photocatalysis and photoelectrochemistry.     

Studies on the mechanism of the photo-induced DNA damage in the presence of acridizinium salts-involvement of singlet oxygen and an unusual source for hydroxyl radicals

Mechanistic investigations of the photoinduced DNA damage by acridizinium salts (4a-azonia-anthracene derivatives) are presented. Irradiation of 9-bromoacridizinium in the presence of defined double- and single-stranded DNA oligomers under aerobic conditions leads to both frank strand breaks and alkali-labile sites as determined by polyacrylamide gel electrophoresis (PAGE). The extent of the DNA damage increases significantly in D(2)O and occurs selectively at guanosine residues. These observations reveal the formation of singlet oxygen ((1)O(2)) as reactive species, which oxidizes the DNA bases, above all the guanine bases. Further evidence for (1)O(2) formation was obtained from laser-flash spectroscopic investigations, which show intersystem crossing (S(1) to T(1)) of the excited states of the parent acridizinium and of the 9-bromo- and 9-amino-substituted derivatives. The resulting triplet state is efficiently quenched by oxygen (k(q) > 10(9) s(-)(1)M(-)(1)) to yield (1)O(2). Under anaerobic conditions, no significant alkali-labile lesions are observed, but frank strand breaks are induced; however, to lesser extent than under aerobic conditions. The DNA damage is suppressed in the presence of a radical scavenger, namely t-BuOH, and hydroxyl radicals are shown to be the reactive intermediates by trapping experiments with terephthalic acid. Moreover, the intercalated acridizinium molecules are not involved in the DNA damage reactions. The intercalated acridizinium salt leads to a primary PET reaction with the DNA bases; however, a fast BET transfer is proposed that regains the dye and the DNA, so that the excited intercalated dye does not contribute significantly to the overall DNA damage.