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PubMed2005

Excitation of the shear horizontal mode in a monolayer by inelastic helium atom scattering.

Inelastic scattering of a low-energy atomic helium beam (HAS) by a physisorbed monolayer is treated in the one-phonon approximation using a time-dependent wave packet formulation. The calculations show that modes with shear horizontal polarization can be excited near high symmetry azimuths of the monolayer, in agreement with recent experiments. The parameters of the calculations are chosen to match the conditions of HAS experiments for triangular incommensurate monolayer solids of xenon, krypton, and argon adsorbed on the (111) face of platinum, and the results show many of the systematic experimental trends for relative excitation probability of the shear horizontal and longitudinal acoustic phonon branches. The inelastic scattering at beam energies near 8 meV is exceedingly sensitive to small misalignment between the scattering plane and the high symmetry directions of the monolayer solid. The diffraction and inelastic processes arise from a strong coupling of the incident atom to the target and the calculated results show large departures from expectations based on analogies to inelastic thermal neutron scattering.

Journal Article↗
PubMed2005

Quantum vibrational state-dependent potentials for classical many-body simulations.

In this paper, we present a method for constructing simple state-dependent many-body potentials for quantum vibrations in a classical bath. The approach is based on an adiabatic separation between high-frequency quantum vibrational modes of the solute and the lower frequency classical motion of the solvent, and on a first-order perturbation theory description of the dependence of the quantum energies on bath configuration. In the simplest realization of the method, the delocalized quantum probability density of the vibrational mode is approximated by a sum of two delta functions, with positions and weights chosen to represent the lowest three moments of the exact distribution. Thus, in the many-body description of the system, each atom describing the quantum vibration is represented by a pair of particles. These quantum particles are held in rigid relative position and interact with the bath via potentials the magnitudes of which are modified by the delta-function weights. The resulting approach allows the classical molecular dynamics of molecules in arbitrary quantum vibrational states to be simulated with a little more effort than a purely classical description. The applicability of the method is illustrated in many-body simulations of the dephasing of vibrational superposition states of I(2) in a cryogenic krypton matrix, yielding results in good agreement with experiment.

Journal Article↗
PubMed2005

Electronic spectroscopy of toluene-rare-gas clusters: the external heavy atom effect and vibrational predissociation.

Toluene-X van der Waals clusters (where X = Ne, Ne2, Ar, Ar2, Kr, Xe) have been investigated by fluorescence excitation spectroscopy in the region of the S1-S0 transition. With the exception of Xe, for each rare-gas studied, we have assigned cluster transitions in the region of all the strong monomer vibrational bands up to 1000 cm(-1) above the origin band. We have further investigated the S1 relaxation dynamics for each vibrational level of each complex, via their fluorescence decay profiles. Clustering with neon has little appreciable effect on the vibrationless S1 lifetime. By contrast, the clusters with argon and krypton exhibit markedly shorter fluorescence lifetimes compared with the monomer. The effect is so severe in the case of toluene-Xe clusters that no fluorescence signals were observed. We interpret these results in terms of an external heavy atom effect in which the rate of intersystem crossing in toluene is influenced by the cluster partner. For clusters built upon excited S1 vibrational levels, the situation is potentially complicated by intramolecular vibrational redistribution and vibrational predissociation (VP). The majority of the fluorescence decay profiles were satisfactorily modeled using single exponential decays. The emission following pumping of the 37(1) level in the toluene-Kr cluster, however, is an exception. We have modeled the decay of this level with a simple kinetic scheme including VP and determined a predissociation rate of (1.04 +/- 0.54) x 10(7) s(-1).

Journal Article↗
PubMed2005

Time-resolved coherent anti-Stokes Raman-scattering measurements of I2 in solid Kr: vibrational dephasing on the ground electronic state at 2.6-32 K.

Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out for iodine (I2) in solid krypton matrices. The dependence of vibrational dephasing time on temperature and vibrational quantum number v is studied. The v dependence is approximately quadratic, while the temperature dependence of both vibrational dephasing and spectral shift, although weak, fits the exponential form characteristic of dephasing by pseudolocal phonons. The analysis of the data indicates that the frequency of the pseudolocal phonons is approximately 30 cm(-1). The longest dephasing times are observed for v = 2 being approximately 300 ps and limited by inhomogeneous broadening. An increase in the dephasing rate of v = 2 as the temperature is lowered to T = 2.6 K is taken as a clear indication of lattice-strain-induced inhomogeneity of the ensemble coherence.

Journal Article↗
PubMed2006

Fragmentation dynamics of argon clusters (Ar(n), n = 2 to 11) following electron-impact ionization: modeling and comparison with experiment.

The fragmentation dynamics of argon clusters ionized by electron impact is investigated for initial cluster sizes up to n = 11 atoms. The dynamics of the argon atoms is modeled using a mixed quantum-classical method in which the nuclei are treated classically and the transitions between electronic states quantum mechanically. The potential-energy surfaces are derived from a diatomics-in-molecules model with the addition of the induced dipole-induced dipole and spin-orbit interactions. The results show extensive and fast fragmentation. The dimer is the most abundant ionic fragment, with a proportion increasing from 66% for n = 2 to a maximum of 95% for n = 6 and then decreasing down to 67% for n = 11. The next abundant fragment is the monomer for n < 7 and the trimer otherwise. The parent ion dissociation lifetimes are all in the range of 1 ps. Long-lived trajectories appear for initial cluster sizes of seven and higher, and favor the formation of the larger fragments (trimers and tetramers). Our results show quantitative agreement with available experimental results concerning the extensive character of the fragmentation: Ar+ and Ar2(+) are the only ionic fragments for sizes up to five atoms; their overall proportion is in quantitative agreement for all the studied sizes; Ar2(+) is the main fragment for all sizes; stable Ar3(+) fragments only appear for n > or = 5, and their proportion increases smoothly with cluster size from there. However, the individual ionic monomer and dimer fragment proportions differ. The experimental ones exhibit oscillations with initial cluster size, with a slight tendency to decrease on average for the monomer. In contrast our results show a monotonic, systematic evolution, similar to what was found in our earlier studies on neon and krypton clusters. Several hypotheses are discussed in order to find the origin of this discrepancy. Finally, the metastable II(1/2)u and II(1/2)g states of Ar2(+) are found to decay with a lifetime of 3.5 and 0.1 ps, respectively, due to spin-orbit coupling. The difference with the commonly accepted microsecond range value for rare-gas dimer ions could originate from the role of autoionizing states in the formation of the parent ions.

Journal Article↗
PubMed2006

Stability of rare gas structure H clathrate hydrates.

Molecular dynamics simulations are used to study the stability of structure H (sH) clathrate hydrates with the rare gases Ne, Ar, Kr, and Xe. Simulations on a 3 x 3 x 3 sH unit cell replica are performed at ambient pressure at 40 and 100 K temperatures. The small and medium (s+m) cages of the sH unit cell are assigned rare gas guest occupancies of 1 and for large (l) cages guest occupancies of 1-6 are considered. Radial distribution functions for guest pairs with occupancies in the l-l, l-(s+m), and (s+m)-(s+m) cages are presented. The unit cell volumes and configurational energies are studied as a function of large cage occupancy for the rare gases. Free energy calculations are carried out to determine the stability of clathrates for large cage occupancies at 100 K and 1 bar and 20 kbar pressures. These studies show that the most stable argon clathrate has five guests in the large cages. For krypton and xenon the most stable configurations have three and two guests in the large cages, respectively.

Journal Article↗
PubMed2006

Effect of three-body interactions on the vapor-liquid phase equilibria of binary fluid mixtures.

Gibbs-Duhem Monte Carlo simulations are reported for the vapor-liquid phase coexistence of binary argon+krypton mixtures at different temperatures. The calculations employ accurate two-body potentials in addition to contributions from three-body dispersion interactions resulting from third-order triple-dipole interactions. A comparison is made with experiment that illustrates the role of three-body interactions on the phase envelope. In all cases the simulations represent genuine predictions with input parameters obtained independently from sources other than phase equilibria data. Two-body interactions alone are insufficient to adequately describe vapor-liquid coexistence. In contrast, the addition of three-body interactions results in very good agreement with experiment. In addition to the exact calculation of three-body interactions, calculations are reported with an approximate formula for three-body interactions, which also yields good results.

Journal Article↗
PubMed1992

Methods for the large-scale synthesis of psoralen furan-side monoadducts and diadducts.

We report methods for the preparation of multimicromole quantities of extremely pure uniquely photo-adducted psoralen-DNA furan-side monoadducts and diadducts (cross-links). The methods use high-intensity krypton and argon ion lasers in the photoreactions and HPLC methods to purify the required oligonucleotides containing the photoadducts. With these methods we have synthesized 2-3 mumol of 8-mer psoralen furan-side monoadduct and diadduct. These methods allow one to generate large amounts of psoralenated DNA oligonucleotides and facilitate their study by NMR and x-ray crystallography.

Base Sequence↗
PubMed1997

Expression of transforming growth factor-beta mRNA in experimental choroidal neovascularization.

PURPOSE: Transforming growth factor beta (TGF-beta) is a multifunctional cytokine that modulates biological events as diverse as wound healing and angiogenesis and which may be important in the pathogenesis of choroidal neovascularization. We investigated the mRNA expression of TGF-beta isoforms in a model of experimental choroidal neovascularization induced by krypton-laser photocoagulation. METHODS: Rat TGF-beta 1, mouse TGF-beta 2 or TGF-beta 3 cDNAs was inserted into the pBluescript vector to prepare antisense and sense riboprobes. Intense laser burns were applied to the posterior poles of the eyes of pigmented rats according to a protocol described for producing choroidal neovascularization in these animals. At intervals up to 4 weeks after photocoagulation, the eyes were obtained and cut into thin sections. The sections were subjected to in situ hybridization with digoxigenin (DIG)-labeled single-strand riboprobes synthesized from each TGF-beta cDNA. RESULTS: In normal adult rat retinas and choroids, TGF-beta 1 mRNA was found only in cells of the ganglion cell layer, TGF-beta 2 mRNA was found in cells of the ganglion cell layer and choriocapillaris endothelium, whereas TGF-beta 3 mRNA was not detected at all. During the process of neovascularization, TGF-beta 1 and TGF-beta 2 mRNAs (the latter being expressed more prominently) were detected in retinal pigment epithelial cells, fibroblast-like cells and the endothelium of the neovascular region. TGF-beta 2 was the predominant isoform of TGF-beta, and its expression was especially strong in the endothelium of the choroidal neovascularization at 2 weeks. However, TGF-beta mRNAs was decreased in cells 4 weeks after photocoagulation. CONCLUSIONS: Our findings suggest that TGF-beta may act in the retina as a neurotrophic agent, since TGF-beta 1 is normally transcribed in ganglion cells and TGF-beta 2 is also transcribed in ganglion cells and choriocapillaris endothelium. TGF-beta 1 and TGF-beta 2 mRNA expression were increased in photocoagulated lesions from 3 days to 2 weeks after laser treatment. Therefore, it is likely that TGF-beta acts as a mediator of the neovascularization process.

Animals↗
PubMed1999

Expression of vascular endothelial growth factor and its receptor (KDR/flk-1) mRNA in experimental choroidal neovascularization.

PURPOSE: Vascular endothelial growth factor (VEGF) is an angiogenic peptide that has been suggested to be important in the pathogenesis of choroidal neovascularization. We investigated the transcription of VEGF and its receptor KDR/flk-1 genes during the development of experimentally induced choroidal neovascularization. METHODS: Rat VEGF or KDR cDNA was inserted in PGEM or pBluescript to prepare antisense or sense riboprobes. Multiple krypton laser burns were applied to the posterior pole of pigmented rat eyes according to a previously described protocol which produces choroidal neovascularization. At intervals of up to 4 weeks after photocoagulation, the eyes were removed and cut into thin sections. The sections were subjected to in situ hybridization with digoxigenin (DIG)-labeled single-strand rat VEGF and KDR cDNA riboprobes. RESULTS: In normal adult rat retinas, VEGF and KDR mRNA expression was mainly observed in the ganglion cell and the inner nuclear layers. During the development of neovascularization, VEGF and KDR mRNAs were detected in retinal pigment epithelial-like cells, fibroblast-like cells and endothelial cells in neovascular lesions. The level of expression was strongest at 1 week after photocoagulation in lasered lesions, and decreased by 4 weeks after photocoagulation. CONCLUSIONS: Our findings demonstrate that expression of VEGF and its receptor KDR may play a role in the formation of experimentally induced choroidal neovascularization. In this study, VEGF and its receptor were co-localized, suggesting that an autocrine and/or paracrine mechanism may be operative.

Animals↗
PubMed2003

Measurement and analysis of visual acuity in multicenter randomized clinical trials in the United States: findings from a survey.

PURPOSE: To describe visual acuity (VA) testing and scoring methods used in multicenter randomized clinical trials in ophthalmology in the United States (USA) sponsored by the National Eye Institute (NEI). METHODS: A survey was conducted among multicenter studies in the US that included one or more randomized clinical trials and were sponsored by the NEI, National Institutes of Health. To be included in the survey, a study had to have VA reported in one or more publications or patient eligibility based on VA, a majority of study subjects 13 years of age or older, and a patient population primarily or exclusively from the US. A standard survey form was completed for each study based on information presented in the study manual of procedures and publications. Findings were summarized and displayed with frequency distributions. RESULTS: The survey included 24 studies, each with enrollment initiated in the period 1972 to 1999. VA was one of the study eligibility criteria for 19 (79%) studies, and VA or change in VA was the primary outcome in 12 (50%) studies. ETDRS charts have been employed in 16 of 19 studies initiated after the charts were published in 1982. All studies but one specified in the documents reviewed that VA testing was performed at multiple VA test distances. For studies that used ETDRS charts, methods of converting VA scores obtained at different test distances to a common scale fell into two categories: 11 studies used a method similar in nature to that first reported in the Macular Photocoagulation Study, and 7 studies used a method similar in nature to that first reported in the Krypton-Argon Regression of Neovascularization Study. conclusion The development of the ETDRS charts and a custom light box has led to more uniformity in VA test charts and chart illumination. However, details of VA measurement protocols vary widely from study to study. To assure comparable data across studies and ocular conditions, it would be useful to have a standard VA testing and scoring protocol with provisions for testing different levels of visual acuity that recommends a single method for converting scores from different test distances to a common scale and standard conversion of "off the chart" VA levels for calculation of means and changes in VA.

Data Collection↗
PubMed2006

Photodynamic therapy of experimental choroidal neovascularization in the mouse.

PURPOSE: To evaluate the qualitative and quantitative effects of verteporfin photodynamic therapy (PDT) on laser-induced choroidal neovascularization (CNV) in the mouse. METHODS: PDT was applied to the normal mouse fundus using light doses of 32, 64, and 83 s, and histological analysis of the treated areas was performed. CNV was induced using krypton laser photocoagulation of the fundus, and the CNV lesions were subsequently treated with PDT using light doses of 32, 64, and 83 s. Enucleated eyes were analyzed with light and transmission electron microscopies, and measurements of CNV size were done on histologic sections and on isolectin B4-stained choroidal flat mounts. RESULTS: PDT induced a light dose-dependent damage to the surrounding neural retina in normal eyes. At a light dose of 32 s, minimal damage was detected in the neural retina, whereas higher light doses caused distortion and disruption of the outer and inner nuclear layers and of the retinal pigment epithelium. When PDT was applied over laser-induced CNV lesions, the relative height of the lesions was significantly reduced (p < 0.05) using all light doses. Transmission electron microscopy 1 day after PDT treatment revealed occlusion of many of the CNV vessels. One week after PDT treatment, the CNV lesions contained patent vessels irrespective of light dose applied. Accordingly, PDT treatment inhibited (p < 0.05) but did not halt CNV lesion growth. CONCLUSIONS: PDT treatment of laser-induced CNV may create an acute occlusion of neovessels and an inhibition of CNV lesion growth without apparent injury to the surrounding neural retina. However, PDT-treated areas will remain vascularized with continued growth of the CNV lesion, which in turn may explain the often limited effect of PDT in patients with neovascular age-related macular degeneration. Elevating the PDT light dose will not increase the treatment effect substantially but may lead to increased collateral injury.

Animals↗
PubMed1982

Heavy ion effects on yeast cells: induction of canavanine-resistant mutants.

The induction of forward mutations (resistance to canavanine) by heavy ion bombardment was investigated in wild type haploid yeast Saccharomyces cerevisiae. Accelerated ions of argon, titanium, nickel, krypton, xenon, lead and uranium with specific energies between 1.7 and 9.25 MeV/u were obtained from the UNILAC machine at the Gesellschaft für Schwerionenforschung, Darmstadt/Germany. LET-values ranged from 1200 to about 15 000 keV/microns. There was no unequivocal dependence of mutation induction cross section on either LET or Z*2/beta 2, but also a prominent influence of ion specific energy. This is explained by the action of long-ranging delta-electrons.

Canavanine↗
PubMed2006

Measurement of amphotericin B concentration by resonant Raman spectroscopy--a novel technique that may be useful for non-invasive monitoring.

We wished to determine whether Resonant Raman Spectroscopy (RRS) could be used to measure Amphotericin B (AmB) at therapeutic and subtherapeutic concentrations in a model system mimicking the anterior chamber of the eye. The goal was to develop a technique for non-invasive measurement of AmB levels in the aqueous humor (AH) of the eye. A krypton-ion laser source (406.7 nm) was used for excitation and Resonant Raman Spectra were captured with a confocal system in an anterior chamber (AC) model. These spectra were used to develop a correlation curve for prediction of AmB levels. Subsequently, one rabbit was evaluated with this system after 5 days of intravenous AmB administration (1 mg/kg/day) and AmB concentrations measured by RRS were compared to those measured by high-performance liquid chromatography (HPLC). AmB exhibited a unique spectral peak at 1557 cm(-1). Integrated area of this peak linearly correlated with AmB concentration in our model AC. When integrated peak area from multiple in vivo measurements in one animal at steady-state was plotted on this correlation curve, we were able to predict AmB levels. These closely approximated those measured by HPLC. These measurements were not significantly affected by photobleaching or depth profile at acquisition. RRS at 406.7 nm is a method that may be useful for non-invasive monitoring of intraocular AmB levels. This instrument can help physicians decide when repeat, invasive delivery of this drug is warranted based on measurement of actual drug levels in the AH. Also, there is the potential to measure the ocular concentrations of other pharmaceutical agents with similar instruments.

Amphotericin B↗
PubMed2000

Treatment of facial telangiectasias with a diode-pumped Nd:YAG laser at 532 nm.

OBJECTIVE: Facial telangiectasias are a common cause of cosmetic concern. Current treatment modalities present various untoward effects and limits. The pulsed dye laser has been considered the gold standard in efficacy and safety; unfortunately it causes postoperative intracutaneous hematomata, discouraging many patients from undergoing this treatment. Several other vascular lasers (argon, tunable dye, copper, krypton, etc.) are disadvantaged by the risk of hypopigmented and atrophic scars. MATERIALS AND METHODS: We assessed a recent powerful version of the potassium titanyl phosphate (KTP) 532 nm laser, which delivers sufficient energy in single pulse lasting 10-50 msec (DioLite 532; IRIDEX, Mountain View, CA, USA). Collateral damage is reduced while the heating of the vessel is slow enough to avoid explosive photothermolysis with its associated purpura. Sixty six patients with facial telangiectasias were treated. RESULTS: In 62/66 patients (93.9%) we achieved a 75-100% clearance of the lesions, while two treatments were needed to reach an acceptable clearance in the remaining 4/66 patients (6.1%). The eventual need for more sessions was well tolerated because the acceptable postoperative appearance allowed patients to continue normal business and social activities between treatments. No permanent complications or undesired effects were noted. CONCLUSION: We conclude that this diode-pumped frequency-doubled Nd:YAG laser is an effective device for the treatment of facial telangiectasias, with a low profile of undesired effects that can be well tolerated by patients.

Adult↗
PubMed1988

Reflection of laser light from ophthalmic contact lenses.

Reflections of laser radiation from ophthalmological contact lenses are measured and hazard analysis calculations are presented. Measurements were made on the contact lenses using ophthalmic argon and krypton lasers. Reflection coefficients were around 0.2% for lenses with 'anti-laser' coatings and in the region of 4% for uncoated lenses. It can be shown that the nominal ocular hazard distance for a typical ophthalmic argon laser beam reflected from a contact lens with a flat front surface is approximately 30 cm for a coated lens and 1 m for an uncoated lens. The necessity of protective glasses for attending staff in particular circumstances is reviewed.

Contact Lenses↗
PubMedDate not supplied

Physiological and pharmacological aspects of local transfer of substances in the ovarian adnexa in women.

An intimate arrangement between the utero-ovarian vein and the ovarian artery has been found in many species. The anatomical structure suggests the existence of a counter-current system of exchange, and many animal experiments point to a physiological importance of this transfer system. In man, the utero-ovarian vein forms a plexus around the ovarian artery. In-vitro experiments have demonstrated a local transfer of progesterone; in-vivo experiments have proved that krypton and progesterone can be transferred from the utero-ovarian vein to the ovarian artery. The physiological and pharmacological importance of the counter-current system is still under evaluation, and further investigations are needed. It has been suggested that counter-current transfer facilitates local communication between the ovary, Fallopian tube, and uterus. This may be important in a context of luteolysis, follicular selection and maturation, fertilization, and the recognition and maintenance of pregnancy. The pharmacological and therapeutic potential may be limited, as the ovarian adnexa are relatively difficult to access. Instillation of hormones into the uterine lumen will probably induce a higher plasma concentration in the ovarian arterial blood than in peripheral arterial plasma. A culdoscopic or endoscopic approach might permit introduction of long-acting depots in the uterine fundus near the Fallopian tubes and/or ovaries.

Animals↗
PubMed1993

Demonstration of Z-d(5BrCGAT5BrCG) and B-d(CGCGATCGCG) form crystal structures in DNA-cobalt hexammine complexes by Kr 647.1 nm excitation of Raman spectra.

Cobalt hexammine [Co(NH3)6(3+)] is an efficient DNA complexing agent which significantly perturbs nucleic acid secondary structure. We have employed red excitation (647.1 nm) from a krypton laser to obtain Raman spectra of the highly colored complexes formed between cobalt hexammine and crystals of the DNA oligomers, d(5BrCGAT5BrCG) and d(CGCGATCGCG), both of which incorporate out-of-alternation pyrimidine/purine sequences. The Co(NH3)6(3+) complex of d(5BrCGAT5BrCG) exhibits a typical Z-form Raman signature, similar to that reported previously for the alternating d(CGCGCG) sequence. Comparison of the Raman bands of d(5BrCGAT5BrCG) with those of other oligonucleotide and polynucleotide structures suggests that C3'-endo/syn and C3'-endo/anti thymidines may exhibit distinctive nucleoside conformation markers, and tentative assignments are proposed. The Raman markers for C2'-endo/anti adenosine in this Z-DNA are consistent with those reported previously for B-DNA crystals containing C2'-endo/anti dA. Raman bands of the cobalt hexammine complex of d(CGCGATCGCG) are those of B-DNA, but with significant differences from the previously characterized B-DNA dodecamer, d(CGCAAATTTGCG). The observed differences suggest an unusual deoxyguanosine conformer, possibly related to a previously characterized structural intermediate in the B-->Z transition. The present results show that crystallization of d(CGCGATCGCG) in the presence of cobalt hexammine is not alone sufficient to induce the left-handed Z-DNA conformation. This investigation represents the first application of off-resonance Raman spectroscopy for characterization of highly chromophoric DNA and illustrates the feasibility of the Raman method for investigating other structurally perturbed states of DNA-cobalt hexammine complexes.

Base Sequence↗