Role of molecular conformations in rubrene thin film growth

A systematic analysis of the growth of rubrene (C42H28), an organic molecule that currently attracts considerable attention with regard to its application in molecular electronics, is carried out by using x-ray absorption spectroscopy and thermal desorption spectroscopy. The results allow us to unravel a fundamental mechanism that effectively limits organic epitaxy for a large class of organic molecules. If the structure of the free molecule differs substantially from that of the corresponding molecular structure in the bulk, the crystallization is severely hampered.     

Size-dependent electron-impact detachment of internally cold Cn- and Aln- clusters

The cross sections for electron detachment of internally cold Cn- and Aln- clusters were measured using an electrostatic ion beam trap fitted with an internal electron target. The measured electron-impact detachment cross sections for the Cn- (n = 1-9) clusters exhibit even-odd oscillations reflecting the binding energy trend, namely, higher cross sections for weaker binding. Surprisingly, however, these cross sections increase on the average with cluster size, n, in spite of the increase in electron binding. In contrast, the Aln- (n = 2-5) clusters follow the known scaling laws for electron detachment. We suggest that the size-dependent polarizability of these clusters is responsible for the observed behavior.     

Unambiguous identification of three beta-decaying isomers in 70Cu

Using resonant laser ionization, beta-decay studies, and for the first time mass measurements, three beta-decaying states have been unambiguously identified in 70Cu. A mass excess of -62 976.1(1.6) keV and a half-life of 44.5(2) s for the (6-) ground state have been determined. The level energies of the (3-) isomer at 101.1(3) keV with T(1/2)=33(2) s and the 1+ isomer at 242.4(3) keV with T(1/2)=6.6(2) s are confirmed by high-precision mass measurements. The low-lying levels of 70Cu populated in the decay of 70Ni and in transfer reactions compare well with large-scale shell-model calculations, and the wave functions appear to be dominated by one proton-one neutron configurations outside the closed Z=28 shell and N=40 subshell. This does not apply to the 1+ state at 1980 keV which exhibits a particular feeding and deexcitation pattern not reproduced by the shell-model calculations.     

Conformational analysis of methylphenidate: comparison of molecular orbital and molecular mechanics methods

Summary Methylphenidate (MP) binds to the cocaine binding site on the dopamine transporter and inhibits reuptake of dopamine, but does not appear to have the same abuse potential as cocaine. This study, part of a comprehensive effort to identify a drug treatment for cocaine abuse, investigates the effect of choice of calculation technique and of solvent model on the conformational potential energy surface (PES) of MP and a rigid methylphenidate (RMP) analogue which exhibits the same dopamine transporter binding affinity as MP. Conformational analysis was carried out by the AM1 and AM1/SM5.4 semiempirical molecular orbital methods, a molecular mechanics method (Tripos force field with the dielectric set equal to that of vacuum or water) and the HF/6-31G* molecular orbital method in vacuum phase. Although all three methods differ somewhat in the local details of the PES, the general trends are the same for neutral and protonated MP. In vacuum phase, protonation has a distinctive effect in decreasing the regions of space available to the local conformational minima. Solvent has little effect on the PES of the neutral molecule and tends to stabilize the protonated species. The random search (RS) conformational analysis technique using the Tripos force field was found to be capable of locating the minima found by the molecular orbital methods using systematic grid search. This suggests that the RS/Tripos force field/vacuum phase protocol is a reasonable choice for locating the local minima of MP. However, the Tripos force field gave significantly larger phenyl ring rotational barriers than the molecular orbital methods for MP and RMP. For both the neutral and protonated cases, all three methods found the phenyl ring rotational barriers for the RMP conformers/invertamers (denoted as cte, tte, and cta) to be: cte, tte> MP > cta. Solvation has negligible effect on the phenyl ring rotational barrier of RMP. The B3LYP/6-31G* density functional method was used to calculate the phenyl ring rotational barrier for neutral MP and gave results very similar to those of the HF/6-31G* method.     

Formation of branched calixarene aggregates-a time-resolved static light scattering study

Mixtures of a calix[4]arene and a naphthyridine derivative dissolved in 1,2-dichlorobenzene form thermoreversible aggregates. The aggregation process was followed by means of time-resolved multiangle light scattering at two different mixing ratios, 1:3 and 1:4, yielding a detailed record of the relative mass, the radius of gyration, and the particle scattering function of the growing aggregates. On the basis of these data, a conclusive model of the structure is presented for the developing aggregates: monomers aggregate to wormlike filaments which form branching points. Formation of branching points proceeds in a frequency and distribution which is similar to the polycondensation of ABC monomers toward non-randomly branched macromolecules (Burchard, W. Macromolecules 1977, 10, 919-927). Thus, aggregation results in hyperbranched-like particles with striking analogies to the polymerization of glucose to amylopectin.     

Cartan-decomposition subgroups of

For and , we give explicit, practical conditions that determine whether or not a closed, connected subgroup of has the property that there exists a compact subset of with . To do this, we fix a Cartan decomposition of , and then carry out an approximate calculation of for each closed, connected subgroup of .

     

Development of [j] in young, midwestern, American children

Beginning at the age of about 14 months, eight children who lived in a rhotic dialect region of the United States were recorded approximately every 2 months interacting with their parents. All were recorded until at least the age of 26 months, and some until the age of 31 months. Acoustic analyses of speech samples indicated that these young children acquired [inverted r] production ability at different ages for [inverted r]'s in different syllable positions. The children, as a group, had started to produce postvocalic and syllabic [inverted r] in an adult-like manner by the end of the recording sessions, but were not yet showing evidence of having acquired prevocalic [inverted r]. Articulatory limitations of young children are posited as a cause for the difference in development of [inverted r] according to syllable position. Specifically, it is speculated that adult-like prevocalic [inverted r] production requires two lingual constrictions: one in the mouth, and the other in the pharynx, while postvocalic and syllabic [inverted r] requires only one oral constriction. Two lingual constrictions could be difficult for young children to produce.     

Development of a cryopreservation protocol for the microcyclic rust-fungus Puccinia spegazzinii

The rust fungus Puccinia spegazzinii (Basidiomycotina: Uredinales) has been identified as a potential classical biological control agent for the invasive weed Mikania micrantha (Asteraceae). Long-term, live storage of this pathogen is required for reference. As biotrophs, almost all rusts species cannot be preserved by traditional cryopreservation protocols, which rely on in vitro culture techniques. In addition, the embedded teliospores and delicate basidiospores of this microcyclic rust are not amenable to direct plunge freezing. Continuous culture of the rust on living plants is both laborious and expensive, so a variety of approaches for cryopreservation and storage were tested. These methods included traditional approaches to fungal cryopreservation such as variation of cooling rate regime and alginate encapsulation techniques. However, an in situ cryopreservation technique was the only method identified as having any potential for the long-term cryopreservation of the 10 isolates tested. Material from either petiole or stem tissue remained viable after cryopreservation, determined by the ability of the material to produce basidiospores. However, despite great progress being made in developing an optimal cryopreservation method, infection of the host plant by basidiospores produced from previously cryopreserved teliospores, embedded in leaf petioles, was not achieved.     

On the feasibility of performing non-linear autocorrelation with attosecond pulse trains

We present experimental results in which a second-order effect, namely two-photon ionization of atomic He induced by a superposition of harmonics, is observed. The harmonics are generated in a Xe gas-jet using a 790-nm 10-Hz femtosecond Ti:sapphire laser and are subsequently focused into a He gas-jet with a Kirkpatrick–Baez arrangement. The superposition is formed by using a thin In filter and it comprises the 7th to 13th harmonics. Solving the time-dependent Schrödinger equation for He in a polychromatic laser field, the He ⁺ ion yield is calculated as a function of the total XUV intensity. Using the calculated yield and taking into account the focusing and transmission properties of the arrangement, the number of He ⁺ ions produced per laser pulse is estimated and is found to be in reasonable agreement with its measured value. The total number of ions produced non-resonantly follows a nearly quadratic dependence on the harmonic intensity, thus establishing the feasibility of a second-order auto-correlation measurement of the superposition of harmonics, i.e., of a direct temporal characterization of attosecond pulse trains.     

High-intensity laser induced ion acceleration from heavy-water droplets

Fusion neutrons from a heavy water droplet target irradiated with laser pulses of 3 x 10(19) W/cm(2) and from a deuterated secondary target are observed by a time-of-flight (TOF) neutron spectrometer. The observed TOF spectrum can be explained by fusion of deuterium ions simultaneously originating from two different sources: ion acceleration in the laser focus by ponderomotively induced charge separation and target-normal sheath acceleration off the target rear surface. The experimental findings agree well with 3D particle-in-cell simulations.