Ligand-field analysis of an Er(III) complex with a heptadentate tripodal N4O3 ligand

Polarized absorption and emission spectra of trigonal single crystals of an Er(III) complex coordinated to a heptadentate tripodal ligand are reported at temperatures between 8 and 298 K. The assigned energy levels below the onset of ligand absorption (< 25 000 cm(-1)) are fitted to a parametrized electronic Hamiltonian. The C-3 site symmetry of the Er(HI) ion requires eight parameters for a full description of the ligand field within a one-electron operator description. This compound shows unusually large splittings of the multiplets, and the fitted parameters imply that this heptadentate ligand imparts the largest ligand field reported for an Er(III) complex. The ligand field was also interpreted within the angular overlap model (AOM). We derive the AOM matrix to include both sigma and anisotropic pi bonding and show that a useful description of the C-3 ligand field can be made using only five parameters. The success of the AOM description is encouraging for applications on isomorphous complexes within the lanthanide series and in describing the ligand field of low-symmetry complexes with less parameters than in the usual spherical harmonic expansion.

Elucidation of reaction scheme describing malondialdehyde-acetaldehyde-protein adduct formation

Malondialdehyde and acetaldehyde react together with proteins and form hybrid protein conjugates designated as MAA adducts, which have been detected in livers of ethanol-fed animals. Our previous studies have shown that MAA adducts are comprised of two distinct products. One adduct is composed of two molecules of malondialdehyde and one molecule of acetaldehyde and was identified as the 4-methpl-1,4-dihydropyridine-3,5-dicarbaldehyde derivative of an amino group (MHHDC adduct). The other adduct is a 1:1 adduct of malondialdehyde and acetaldehyde and was identified as the 2-formyl-3-(alkylamino)butanal derivative of an amino group (FAAB adduct). In this study, information on the mechanism of MAA adduct formation was obtained, focusing on whether the FAAB adduct serves as a precursor for the MDHDC adduct. Upon the basis of chemical analysis and NMR spectroscopy, two initial reaction steps appear to be a prerequisite for MDHDC formation. One step involves the reaction of one molecule of malondialdehyde and one of acetaldehyde with an amino group of a protein to form the FAAB product, while the other step involves the generation of a malondialdehyde-enamine. It appears that generation of the MDHDC adduct requires the FAAB moiety to be transferred to the nitrogen of the MDA-enamine. For efficient reaction of FAAB with the enamine to take place, additional experiments indicated that these two intermediates likely must be in positions on the protein of close proximity to each other. Further studies showed that the incubation of liver proteins from ethanol-fed rats with MDA resulted in a marked generation of MDHDC adducts, indicating the presence of a pool of FAAB adducts in the liver of ethanol-fed animals. Overall, these findings show that MDHDC-protein adduct formation occurs via the reaction of the FAAB moiety with a malondialdehyde-enamine, and further suggest that a similar mechanism may be operative in vivo in the liver during prolonged ethanol consumption.

Lipophilic methotrexate conjugates with glucose-lipoamino acid moieties: Synthesis and in vitro antitumor activity

To obtain methotrexate (MTX) derivatives with a balanced hydrolipophilic character, we synthesized a series of conjugates in which the drug was linked to lipoamino acid (LAA)-glucose residues (LAAG-MTX). These conjugates displayed increased solubility in polar media compared with the corresponding LAA-MTX conjugates previously described. In vitro biological testing of LAAG-MTX indicated that the introduction of the sugar moiety decreased the biological activity of these MTX conjugates. The tetradecyl derivative 6b, however, was effective in inhibiting the dihydrofolate reductase activity in vitro and showed an inhibitory effect on human lymphoblastoid cell growth. (C) 2001 Wiley-Liss, Inc.

Theory of a mode-locked atom laser with toroidal geometry

We consider a possible technique for mode locking an atom laser, based on the generation of a dark soliton in a ring-shaped Bose-Einstein condensate, with repulsive atomic interactions. The soliton is a kink, with angular momentum per particle equal to (h) over bar /2. It emerges naturally when the condensate is stirred at the soliton velocity and cleansed with a periodic out coupler. The result is a replicating coherent field inside the atom laser, stabilized by topology. We give a numerical demonstration of the generation and stabilization of the soliton.

Effect of quantum interference on a three-level atom driven by two laser fields

We study the effect of quantum interference on the population distribution and absorptive properties of a V-type three-level atom driven by two lasers of unequal intensities and different angular frequencies. Three coupling configurations of the lasers to the atom are analysed: (a) both lasers coupled to the same atomic transition, (b) each laser coupled to different atomic transition and (c) each laser coupled to both atomic transitions. Dressed stales for the three coupling configurations are identified, and the population distribution and absorptive properties of the weaker field are interpreted in terms of transition dipole moments and transition frequencies among these dressed states. In particular, we find that in the first two cases there is no population inversion between the bare atomic states, but the population can be trapped in a superposition of the dressed states induced by quantum interference and the stronger held. We show that the trapping of the population, which results from the cancellation of transition dipole moments, does not prevent the weaker field to be coupled to the cancelled (dark) transitions. As a result, the weaker field can be strongly amplified on transparent transitions. In the case of each laser coupled to both atomic transitions the population can be trapped in a linear superposition of the excited bare atomic states leaving the ground state unpopulated in the steady state. Moreover, we find that the absorption rate of the weaker field depends on the detuning of the strong field from the atomic resonances and the splitting between the atomic excited states. When the strong held is resonant to one of the atomic transitions a quasi-trapping effect appears in one of the dressed states. In the quasi-trapping situation all the transition dipole moments are different from zero, which allows the weaker field to be amplified on the inverted transitions. When the strong field is tuned halfway between the atomic excited states, the population is completely trapped in one of the dressed states and no amplification is found for the weaker field.

Optically driven micromachine elements

We report on a proof of principle demonstration of an optically driven micromachine element. Optical angular momentum is transferred from a circularly polarized laser beam to a birefringent particle confined in an optical tweezers trap. The optical torque causes the particle to spin at up to 350 Hz, and this torque is harnessed to drive an optically trapped microfabricated structure. We describe a photolithographic method for producing the microstructures and show how a light driven motor could be used in a micromachine system. (C) 2001 American Institute of Physics.

Endemism and cryptogenesis in 'segmented' mites: A review of Australian Alicorhagiidae, Terpnacaridae, Oehserchestidae and Grandjeanicidae (Acari : sarcoptiformes)

Endeostigmata are early derivative acariform mites, fossils of which are known from the Devonian. Extant species bear numerous plesiomorphies, the most striking being remnant opisthosomal segmentation. Also, many are all-female parthenogens with broad geographical distributions. Many of the species reported in the present study may represent clones of ancient Gondwana species. Before the present study only a handful of endeostigmatans had been reported from Australia. A key to the families of Endeostigmata is provided in the present paper, along with a review of the Australian fauna of the families Alicorhagiidae (new record), Grandjeanicidae (new record), Oehserchestidae (new record), and Terpnacaridae. Terpnacarus gibbosus (Womersley) is redescribed. A report of the first records of the cosmopolitan parthenogens Alicorhagia usitata Theron et al., Alycosmesis palmata (Oudemans), Stigmalychus veretrum Theron et al., Terpnacarus carolinaensis Theron, and Oehserchestes arboriger (Theron) in Australia is provided, along with a description of the new species Grandjeanicus theroni (Grandjeanicidae). Terpnacarus variolus Shiba and T. glebulentus Theron are junior synonyms of T. gibbosus.

The development and application of a novel safety-catch linker for BOC-based assembly of libraries of cyclic peptides

Cyclic peptides are appealing targets in the drug-discovery process. Unfortunately, there currently exist no robust solid-phase strategies that allow the synthesis of large arrays of discrete cyclic peptides. Existing strategies are complicated, when synthesizing large libraries, by the extensive workup that is required to extract the cyclic product from the deprotection/cleavage mixture. To overcome this, we have developed a new safety-catch linker. The safety-catch concept described here involves the use of a protected catechol derivative in which one of the hydroxyls is masked with a benzyl group during peptide synthesis, thus making the linker deactivated to aminolysis. This masked derivative of the linker allows BOC solid-phase peptide assembly of the linear precursor. Prior to cyclization, the linker is activated and the linear peptide deprotected using conditions commonly employed (TFMSA), resulting in deprotected peptide attached to the activated form of the linker. Scavengers and deprotection adducts are removed by simple washing and filtration. Upon neutralization of the N-terminal amine, cyclization with concomitant cleavage from the resin yields the cyclic peptide in DMF solution. Workup is simple solvent removal. To exemplify this strategy, several cyclic peptides were synthesized targeted toward the somatostatin and integrin receptors. From this initial study and to show the strength of this method, we were able to synthesize a cyclic-peptide library containing over 400 members. This linker technology provides a new solid-phase avenue to access large arrays of cyclic peptides.

Postural control of the trunk in response to lateral support surface translations during trunk movement and loading

The postural response to translation of the support surface may be influenced by the performance of an ongoing voluntary task. This study was designed to test this proposal by applying lateral perturbations while subjects handled a load in the frontal plane. Measurements were made of medio-lateral displacement of the centre of pressure, angular displacement of the trunk and thigh in the frontal plane and intra-abdominal pressure. Subjects were translated randomly to the left and right in a variety of conditions that involved standing either quietly or with a 5 kg load in their left hand, which they were required either to hold statically or to lift or lower. The results indicate that when the perturbation occurred towards the loaded left side the subjects were able to return their centre of pressure, trunk and thigh rapidly and accurately to the initial position. However, when the perturbation occurred towards the right (away from the load) this correction was delayed and associated with multiple changes in direction of movement, suggesting decreased efficiency of the postural response. This reduced efficiency can be explained by a conflict between the motor commands for the ongoing voluntary task and the postural response, and/or by the mechanical effect of the asymmetrical addition of load to the trunk.

The Alcohol Helplessness Scale and its prediction of depression among problem drinkers

Event-specific scales commonly have greater power than generalized scales in prediction of specific disorders and in testing mediator models for predicting such disorders. Therefore, in a preliminary study, a 6-item Alcohol Helplessness Scale was constructed and found to be reliable for a sample of 98 problem drinkers. Hierarchical multiple regression and its derivative path analysis were used to test whether helplessness and self-efficacy moderate or mediate the link between alcohol dependence and depression, A test of a moderation model was not supported, whereas a test of a mediation model was supported. Helplessness and self-efficacy both significantly and independently mediated between alcohol dependence and depression. Nevertheless, a significant direct effect of alcohol dependence on depression also remained, (C) 2001 John Wiley & Sons, Inc.

Efficient time-independent wave packet scattering calculations within a Lanczos subspace: H+O-2 (J=0) state-to-state reaction probabilities

An efficient Lanczos subspace method has been devised for calculating state-to-state reaction probabilities. The method recasts the time-independent wave packet Lippmann-Schwinger equation [Kouri , Chem. Phys. Lett. 203, 166 (1993)] inside a tridiagonal (Lanczos) representation in which action of the causal Green's operator is affected easily with a QR algorithm. The method is designed to yield all state-to-state reaction probabilities from a given reactant-channel wave packet using a single Lanczos subspace; the spectral properties of the tridiagonal Hamiltonian allow calculations to be undertaken at arbitrary energies within the spectral range of the initial wave packet. The method is applied to a H+O-2 system (J=0), and the results indicate the approach is accurate and stable. (C) 2002 American Institute of Physics.

Chebyshev real wave packet propagation: H+O-2 (J=0) state-to-state reactive scattering calculations

In this paper we explore the relative performance of two recently developed wave packet methodologies for reactive scattering, namely the real wave packet Chebyshev domain propagation of Gray and Balint-Kurti [J. Chem. Phys. 108, 950 (1998)] and the Lanczos subspace wave packet approach of Smith [J. Chem. Phys. 116, 2354 (2002); Chem. Phys. Lett. 336, 149 (2001)]. In the former method, a modified Schrodinger equation is employed to propagate the real part of the wave packet via the well-known Chebyshev iteration. While the time-dependent wave packet from the modified Schrodinger equation is different from that obtained using the standard Schrodinger equation, time-to-energy Fourier transformation yields wave functions which differ only trivially by normalization. In the Lanczos subspace approach the linear system of equations defining the action of the Green operator may be solved via either time-dependent or time-independent methods, both of which are extremely efficient due to the simple tridiagonal structure of the Hamiltonian in the Lanczos representation. The two different wave packet methods are applied to three dimensional reactive scattering of H+O-2 (total J=0). State-to-state reaction probabilities, product state distributions, as well as initial-state-resolved cumulative reaction probabilities are examined. (C) 2002 American Institute of Physics.

Prediction of absolute rate coefficients and product branching ratios for the C(P-3) plus allene reaction system

Complex chemical reactions in the gas phase can be decomposed into a network of elementary (e.g., unimolecular and bimolecular) steps which may involve multiple reactant channels, multiple intermediates, and multiple products. The modeling of such reactions involves describing the molecular species and their transformation by reaction at a detailed level. Here we focus on a detailed modeling of the C(P-3)+allene (C3H4) reaction, for which molecular beam experiments and theoretical calculations have previously been performed. In our previous calculations, product branching ratios for a nonrotating isomerizing unimolecular system were predicted. We extend the previous calculations to predict absolute unimolecular rate coefficients and branching ratios using microcanonical variational transition state theory (mu-VTST) with full energy and angular momentum resolution. Our calculation of the initial capture rate is facilitated by systematic ab initio potential energy surface calculations that describe the interaction potential between carbon and allene as a function of the angle of attack. Furthermore, the chemical kinetic scheme is enhanced to explicitly treat the entrance channels in terms of a predicted overall input flux and also to allow for the possibility of redissociation via the entrance channels. Thus, the computation of total bimolecular reaction rates and partial capture rates is now possible. (C) 2002 American Institute of Physics.

Coexistence of stability and mobility in postural control: evidence from postural compensation for respiration

This study evaluated the extent to which movement of the lower limbs and pelvis may compensate for the disturbance to posture that results from respiratory movement of the thorax and abdomen. Motion of the neck, pelvis, leg and centre of pressure (COP) were recorded with high resolution in conjunction with electromyographic activity (EMG) of flexor and extensor muscles of the trunk and hip. Respiration was measured from ribcage motion. Subjects breathed quietly, and with increased volume due to hypercapnoca (as a result of breathing with increased dead-space) and a voluntary increase in respiration. Additional recordings were made during apnoea. The relationship between respiration and other parameters was measured from the correlation between data in the frequency domain (i.e. coherence) and from time-locked averages triggered from respiration. In quiet standing, small angular displacements (similar to0.5degrees) of the trunk and leg were identified in raw data. Correspondingly, there were peaks in the power spectra of the angular movements and EMG. While body movement and EMG were coherent with respiration (>0.5), the coherence between respiration and COP displacement was low (

Structural ordering of coal char during heat treatment and its impact on reactivity

The effect of heat treatment on the structure of an Australian semi-anthracite char was studied in detail in the 850-1150degreesC temperature range using XRD, HRTEM, and electrical resistivity techniques. It was found that the carbon crystallite size in the char does not change significantly during heat treatment in the temperature range studied, for both the raw coal and its ash-free derivative obtained by acid treatment. However, the fraction of the organized carbon in the raw coal chars, determined by XRD, increased with increase of heat treatment time and temperature, while that for the ash-free coal chars remained almost unchanged. This suggests the occurrence of catalytic ordering during heat treatment, supported by the observation that the electrical resistivity of the raw coal chars decreased with heat treatment, while that of the ash-free coal chars did not vary significantly. Further confirmatory evidence was provided by high resolution transmission electron micrographs depicting well-organized carbon layers surrounding iron particles. It is also found that the fraction of organized carbon does not reach unity, but attains an apparent equilibrium value that increases with increase in temperature, providing an apparent heat of ordering of 71.7 kJ mol(-1) in the temperature range studied. Good temperature-independent correlation was found between the electrical resistivity and the organized carbon fraction, indicating that electrical resistivity is indeed structure sensitive. Good correlation was also found between the electrical resistivity and the reactivity of coal char. All these results strongly suggest that the thermal deactivation is the result of a crystallite-perfecting process, which is effectively catalyzed by the inorganic matter in the coal char. Based on kinetic interpretation of the data it is concluded that the process is diffusion controlled, most likely involving transport of iron in the inter-crystallite nanospaces in the temperature range studied. The activation energy of this transport process is found to be very low, at about 11.8 kJ mol(-1), which is corroborated by model-free correlation of the temporal variation of organized carbon fraction as well as electrical resistivity data using the superposition method, and is suggestive of surface transport of iron. (C) 2002 Elsevier Science Ltd. All rights reserved.