Seasonal and diurnal variations in ultraviolet-B and ultraviolet-A irradiances at and below the sea surface at Helgoland (North Sea) over a 6-year period

Ultraviolet(UV) radiation at four wavelengths (305, 320, 340 and 380 nm) and photosynthetically active radiation (PAR) were measured from May 1994 to October 1999 using Biospherical UV radiometers. A surface reference sensor located on the roof of the Marine Station at Helgoland recorded values every 5 min, and an equivalent profiling underwater sensor was used for measurements in the sea at approximately monthly intervals. The ratio of 305-nm radiation to PAR varied seasonally, with a 14-fold increase from winter to summer. A much weaker seasonal trend (ca. 1.5-fold) was apparent in the ratio of 320-nm radiation to PAR, but there was no seasonal trend in the ratios of 340- or 380-nm radiation to PAR. The year-to-year variations in 305-nm radiation were also much greater relative to PAR than for the other UV wavelengths, but there was no evidence of a change in the 305 nm:PAR ratio over the study period. The ratios of both 305- and 320-nm radiation to PAR increased from dawn to midday, but those of 340- and 380-nm radiation were almost constant through the day, except shortly before sunrise and after sunset when the proportions of 340- and 380-nm radiation increased. Underwater measurements of PAR and UV suggest that the 1% depth for 305-nm radiation was little more than 1 m, but this estimate is valid only for summer and autumn because, in other seasons, few reliable readings for 305-nm radiation could be obtained underwater, and no attenuation coefficient could be calculated. The 1% depths recorded for the other UV wavelengths in the middle 6 months of the year were 2.0 m for 320 nm, 2.6 m for 340 nm and 4.6 m for 380 nm, compared with 12 m for PAR, but the attenuation of all wavebands increased sharply in October and remained higher until March. An analysis of the influence of sun angle, total column ozone concentration, the proportion of skylight, and cloud cover on the ratio of UV wavelengths to PAR in surface irradiance demonstrated that solar angle has a greater influence than ozone concentration on the irradiance at 305 nm, and that the typical occurrence of ozone

Comparison between fluid simulations and experiments in inductively coupled argon/chlorine plasmas

Comparisons of 2D fluid simulations with experimental measurements of Ar/Cl-2 plasmas in a low-pressure inductively coupled reactor are reported. Simulations show that the wall recombination coefficient of Cl atom (gamma) is a crucial parameter of the model and that neutral densities are very sensitive to its variations. The best agreement between model and experiment is obtained for gamma = 0.02, which is much lower than the value predicted for stainless steel walls (gamma = 0.6). This is consistent with reactor wall contaminations classically observed in such discharges. The electron density, negative ion fraction and Cl atom density have been investigated under various conditions of chlorine and argon concentrations, gas pressure and applied rf input power. The plasma electronegativity decreases with rf power and increases with chlorine concentration. At high pressure, the power absorption and distribution of charged particles become more localized below the quartz window. Although the experimental trends are well reproduced by the simulations, the calculated charged particle densities are systematically overestimated by a factor of 3-5. The reasons for this discrepancy are discussed in the paper.

Formation of Novel Di-Nuclear Lanthanide Luminescent Sm(III), Eu(III) and Tb(III) Triple Stranded Helicates from a C2 Symmetrically 2,6-Dicarboxylic Amide based 1,3-Xylene Ligand in CH3CN

The synthesis of the C2-symmetrical ligand 1 consisting of two naphthalene units connected to two pyridine-2,6-dicarboxamide moieties linked by a xylene spacer and the formation of LnIII-based (Ln1/4 Sm, Eu, Tb, and Lu) dimetallic helicates [Ln2 · 13] in MeCN by means of a metal-directed synthesis is described. By analyzing the metal-induced changes in the absorption and the fluorescence of 1, the formation of the helicates, and the presence of a second species [Ln2 · 12] was confirmed by nonlinear- regression analysis. While significant changes were observed in the photophysical properties of 1, the most dramatic changes were observed in the metal-centred lanthanide emissions, upon excitation of the naphthalene antennae. From the changes in the lanthanide emission, we were able to demonstrate that these helicates were formed in high yields (ca. 90% after the addition of 0.6 equiv. of LnIII), with high binding constants, which matched well with that determined from the changes in the absorption spectra. The formation of the LuIII helicate, [ Lu2 · 13 ] , was also investigated for comparison purposes, as we were unable to obtain accurate binding constants from the changes in the fluorescence emission upon formation of [Sm2 · 13], [Eu2 · 13], and [Tb2 · 13].

Species distribution and coordination of uranyl chloro complexes in acetonitrile

The complex formation of the uranyl ion, UO22+, with chloride ions in acetonitrile has been investigated by factor analysis of UV-vis absorption and U L-3 edge EXAFS (extended X-ray absorption fine structure) spectra. As a function of increasing [Cl-]/[UO22+] ratio, the five monomeric species [UO2(H2O)(5)](2+), [UO2Cl(H2O)(2)(MeCN)(2)](+), [UO2Cl2(H2O)(MeCN)(2)], [UO2Cl3(MeCN)(2)](-), and [UO2Cl4](2-) have been observed. The distances determined in the first coordination sphere are: U-O-ax = 1.77 angstrom, U-O-H2O = 2.43 angstrom, U-N-MeCN = 2.53 angstrom, and U-Cl = 2.68 angstrom. A crystalline material has been obtained from the intermediate solution with the [Cl-]/[UO22+] ratio of similar to 2, where [UO2Cl2(H2O)(MeCN)(2)] is the dominating species. The crystal structure analysis of this material revealed a tetrameric complex, [(UO2)(4)(mu(2)-Cl)(4)(mu(3)-O)(2)(H2O)(2)(CH3CN)(4)]center dot(CH3CN). The crystal data are: monoclinic, space group P2(1)/n, a 10.6388(5) angstrom, b = 14.8441(5) angstrom, c = 10.8521(5) angstrom, beta = 109.164(5)degrees, and Z = 2. The U(VI) coordination of the solution species [UO2Cl2(H2O)(MeCN)(2)] changes during the crystallization by replacing one MeCN molecule with a bridging mu(3)-O atom in the tetramer.

ISO-SWS observations of CO2 and H2O in R cassiopeiae

We present ISO-SWS spectra of the O-rich Mira variable R Gas, showing CO2 in absorption and emission, and H2O in absorption. The CO2 absorption feature is the 01(1)0 - 00(0)0 ro-vibrationaI band at 14.97 mu m. The emission features are the 10(0)0-01(1)0 and 11(1)0 - 02(2)0 re-vibrational transitions at 13.87 and 13.48 mu m respectively. The water absorption spectrum shows the nu(1) and nu(3) re-vibrational bands in the 2.75 - 3 mu m region. Using LTE models, we derive physical parameters for the features. We find the CO2 emission temperature to be similar to 1100 K. We discuss the nature of the CO2 feature at 15 mu m and show that it can be modeled as an emission/absorption band by deviating front thermal equilibrium for the population of the 01(1)0 vibrational level. The H2O absorption spectrum is shown to arise from gas at different temperatures, but can be fit reasonably well with two components at T = 950 K and T = 250 K. The CO2 emission and hut H2O absorption temperatures an similar, suggesting chat these features probe the same region of the inner envelope. We discuss the inner envelope chemistry using molecular equilibrium calculations and recent modeling work by Duari et al. (1999), and find our observations consistent with the results.

Interaction of High Intensity Picosecond Laser Pulses with Large Pre-formed Plasmas

The interaction of short (1-2 ps) laser pulses with solid targets at irradiances of over 1016 Wcm~2 , in the presence of a substantial prepulse has been investigated. High absorption of laser energy is found even at high angles of incidence, with evidence for a resonance absorption peak being found for S, P, and circular polarizations. It is considered that this may be a result of refraction and beam filamentation, which causes loss of distinct polarization. Measurements of hard X-ray emission (~ 100 keV) confirm a resonance absorption type peak at 45-50°, again for all three cases. Typically, 5-15% of the incident light is back-reflected by stimulated Brillouin scatter, with spatially resolved spectra showing evidence of beam hot-spots at high intensity. The possibility that filamentation and refraction of the beam can explain the lack of polarization dependence in the absorption and hard X-ray emission data is discussed.

Porphyrin and tetrabenzoporphyrin dendrimers: Tunable membrane-impermeable fluorescent pH nanosensors

The pH dependencies of the UV-vis and fluorescent spectra of new water-soluble dendritic porphyrins and tetrabenzoporphyrins were studied. Because of extended pi-conjugation and nonplanar distortion, the absorption and the emission bands of tetraaryltetrabenzoporphyrins (Ar4TBP) are red-shifted and do not overlap with those of regular tetraarylporphyrins (Ar4P). When encapsulated inside dendrimers with hydrophilic outer layers, Ar(4)Ps and Ar(4)TBPs become water soluble and can serve as pH indicators, with pKs adjustable by the peripheral charges on the dendrimers. Two new dendritic porphyrins, Gen 4 polyglutamic porphyrin dendrimer H2P-Glu(4)OH (1) with 64 peripheral carboxylates and Gen 1 poly(ester amide) Newkome-type tetrabenzoporphyrin dendrimer H2TBP-Nw(1)OH (2) with 36 peripheral carboxylates, were synthesized and characterized. The pKs of the encapsulated porphyrins (pK(H2P-Glu)(OH)(4) = 6.2 and pK(H2TBP)-Nw(1)OH = 6.3) were found to be strongly influenced by the dendrimers, revealing significant electrostatic shielding of the cores by the peripheral charges. The titration curves obtained by differential excitation using the mixtures of the dendrimers were shown to be identical to those determined for the dendrimers individually. Due to their peripheral carboxylates and nanometric molecular size, porphyrin dendrimers cannot penetrate through phospholipid membranes. Dendrimer 1 was captured inside phospholipid liposomes, which were suspended in a solution containing dendrimer 2. No response from 1 was detected upon pH changes in the bulk solution, while the response from 2 was predictably strong. When proton channels were created in the liposome walls, both compounds responded equally to the bulk pH changes. These results suggest that porphyrin dendrimers can be used as fluorescent pH indicators for proton gradient measurements.

Chromo- and fluorogenic Organometallic Sensors

Compounds that change their absorption and/or emission properties in the presence of a target ion or molecule have been studied for many years as the basis for optical sensing. Within this group of compounds, a variety of organometallic complexes have been proposed for the detection of a wide range of analytes such as cations (including H+), anions, gases (e.g. O2, SO2, organic vapours), small organic molecules, and large biomolecules (e.g. proteins, DNA). This chapter focuses on work reported within the last few years in the area of organometallic sensors. Some of the most extensively studied systems incorporate metal moieties with intense long-lived metal-to-ligand charge transfer (MLCT) excited states as the reporter or indicator unit, such as fac-tricarbonyl Re(I) complexes, cyclometallated Ir(III) species, and diimine Ru(II) or Os(II) derivatives. Other commonly used organometallic sensors are based on Pt-alkynyls and ferrocene fragments. To these reporters, an appropriate recognition or analyte-binding unit is usually attached so that a detectable modification on the colour and/or the emission of the complex occurs upon binding of the analyte. Examples of recognition sites include macrocycles for the binding of cations, H-bonding units selective to specific anions, and DNA intercalating fragments. A different approach is used for the detection of some gases or vapours, where the sensor's response is associated with changes in the crystal packing of the complex on absorption of the gas, or to direct coordination of the analyte to the metal centre.

Examination of the Silver Colloid Binding Behavior of Disulfide-Tethered Bipyridine Ligands and Their fac-Tricarbonylrhenium(I) Complexes

The syntheses of 2,2'-bipyridin-5-ylmethyl-5-(1,2-dithiolan-3-yl)pentanoate (L1) and N-(2,2'-bipyridin-5-ylmethyl)-5-(1,2-dithiolan-3-yl)pentanamide (L2) and their neutral fac carbonylrhenium(I) complexes [Re(L1)(CO)(3)Br] and [Re(L2)(CO)(3)Br] are reported. The. electronic absorption and emission spectra of the complexes are similar to the spectrum of the reference compound [Re(bipy)(CO)(3)Br] and correlate well with the density functional theory calculations undertaken. The surface-enhanced Raman spectroscopy (SERS) spectra (excited at both 532 and 785 nm) of the ligands and complexes were examined and compared to the spectrum of ethyl 5-(1,2-dithiolan-3-yl)pentanoate (L3), revealing that there is very little contribution to the spectra of these species from the dithiolated alkyl chains. The spectra are dominated by the characteristic peaks of a metalated 2,2'-bipyridyl group,arising from the silver colloid/ion complexation, and the rhenium center. The rhenium complexes show weak SERS bands related to the CO stretches and a broad band at 510 cm(-1) assigned to Re-CO stretching. Concentration dependent studies, measured by the relative intensity of several assigned peaks, indicate that, as the surface coverage increases, the bipyridine moiety lifts off the surface In the case of L1 and L2, this gives rise to complexes with silver at low concentration, enhancing the signals observed, while for the tricarbonylbromorhenium complexes of these ligands, the presence of the disulfide tether allows an enhancement in the limits of detection of these surface-borne species of 20 times in the case of [ReL2(CO)(3)Br] over [Re(bipy)(CO)(3)Br].

Alkynyl-Bridged Ruthenium(II) 4 '-Diferroceny1-2,2 ':6 ',2 ''-terpyridine Electron Transfer Complexes: Synthesis, Structures, and Electrochemical and Spectroscopic Studiese

The novel ligand 4'-diferrocenylallcyne-2,2':6',2 ''-terpyridine (7; Fc-C C-Fc-tpy; tpy = terpyridyl; Fc = ferrocenyl) and its Ru2+ complexes 8-10 have been synthesized and characterized by single-crystal X-ray diffraction, cyclic voltammetry, and UV-vis and luminescence spectroscopy. Electrochemical data and UV absorption and emission spectra indicate that the insertion of an ethynyl group causes delocalization of electrons in the extended pi* orbitals. Cyclic voltammetric measurements of 7 show two successive reversible one-electron-oxidation processes with half-wave potentials of 0.53 and 0.78 V. The small variations of the E-1/2 values for the Fe2+/Fe3+ redox couples after the coordination of the Ru2+ ion suggest a weak interaction between the Ru2+ and Fe2+ centers. After insertion of an ethynyl group, UV-vis absorption spectra show a red shift of the absorption peak of the (1)[(d(pi)(Fe))(6)]->(1)[(d(pi)(Fe))(5)(pi*(Ru)(tpy))(1)] MMLCT of the Ru2+ complexes. The Ru2+ complex 8 exhibits the strongest luminescence intensity (lambda(em)(max) 712 nm, Phi(em) = 2.63 x 10(-4), tau = 323 ns) relative to analogous ferrocene-based terpyridine Ru(II) complexes in H2O/CH3CN (4/1 v/v) solution.

Using low and high prepulses to enhance the J=0-1 transition at 19.6 nm in the Ne-like germanium XUV laser

We report a study of the effect of prepulses on XUV lasing of Ne-like germanium for an irradiation geometry where approximate to 20 mm long germanium slab targets were irradiated at approximate to 1.6 x 10(13) W cm(-2) using approximate to 0.7 ns (1.06 mu m) pulses from the VULCAN glass laser. Prepulses were generated at fractional power levels of approximate to 2 x 10(-4) (low) and approximate to 2 x 10(-2) (high) and arrived on target 5 and 3.2 ns respectively in advance of the main heating pulse, For both the low and high prepulses the output of the 3p-3s, J = 0-1, line at 19.6 nm was enhanced such that the peak radiant density (J/st) for this line became greater than that for the normally stronger J = 2-1 lines at 23.2 and 23.6 nm. The J = 0-1 line, whose FWHM duration was reduced from approximate to 450 ps to approximate to 100 ps, delivered approximate to 6 x more power (W) than the average for the combined J = 2-1 lines, whose FWHM duration was approximate to 500 ps for both levels of prepulse, The higher prepulse was more effective, yielding approximate to 2 x more radiant density and approximate to 7 x more power on both the J = 0-1 and J = 2-1 transitions compared to the low prepulse case, The most dramatic observation overall was the approximate to 40 x increase of power in the J = 0-1 line for the high prepulse (approximate to 2%) case compared with the zero prepulse case. These observations, coupled with measurements of beam divergence and beam deviation through refractive bending, as well as general agreement with modelling, lead us to conclude that, for germanium, the main influence of the prepulse is (a) to increase the energy absorbed from the main pulse, (b) to increase the volume of the gain zone and (c) to relax the plasma density gradients, particularly in the J = 0-1 gain zone.

COHERENCE AND DOUBLE-PASS AMPLIFICATION IN GE SOFT-X-RAY LASER

From measurements of spatial coherence and beam divergence of Ge soft x-ray laser at a far field, the x-ray laser beam has been characterized as a partially coherent Gaussian beam. Double-pass amplification will improve spatial and temporal coherence, spectral brightness and efficiency. Close to 100% geometrical coupling efficiency has been obtained in double pass amplification in Ge. Transient loss of feedback is attributed to mirror structure damage within the build-up time of the x-ray laser. Prospect for generation of coherent x-ray laser beam is discussed.

THE ROLE OF GAS-PHASE OXIDATION AND COMBINATION DURING LASER DEPOSITION OF YBA2CU3O7-X IN AMBIENT OXYGEN

Spectroscopic absorption and emission measurements have been used to study laser deposition of YBCO films. They show that >95% of the monatomic Y and Ba initially ablated from the target undergo gas-phase chemical combination before film deposition. In contrast, considerable monatomic Cu persists into the deposition region. in this region, equilibrated gas temperatures are of the order of 2700 K. It is suggested that this high temperature facilitates film crystallization and epitaxial growth. The survival of monatomic Cu in the plume to the site of deposition is a manifestation of its endothermic reaction with O-2.

Physical basis and biological mechanisms of gold nanoparticle radiosensitization

The unique properties of nanomaterials, in particular gold nanoparticles (GNPs) have applications for a wide range of biomedical applications. GNPs have been proposed as novel radiosensitizing agents due to their strong photoelectric absorption coefficient. Experimental evidence supporting the application of GNPs as radiosensitizing agents has been provided from extensive in vitro investigation and a relatively limited number of in vivo studies. Whilst these studies provide experimental evidence for the use of GNPs in combination with ionising radiation, there is an apparent disparity between the observed experimental findings and the level of radiosensitization predicted by mass energy absorption and GNP concentration. This review summarises experimental findings and attempts to highlight potential underlying biological mechanisms of response in GNP radiosensitization.

Transpupillary thermotherapy for choroidal melanoma:Tumor control and visual results in 100 consecutive cases

Objective: The authors evaluated the results of primary transpupillary thermotherapy for choroidal melanoma in 100 cases. Design: Prospective nonrandomized analysis of treatment method. Participants: One hundred patients with choroidal melanoma were studied. Main Outcome Measures: Tumor response, ocular side effects, and visual results. Results: Of 100 consecutive patients with choroidal melanoma treated with transpupillary thermotherapy, the mean tumor basal diameter was 7.1 mm and tumor thickness was 2.8 mm. The tumor margin touched the optic disc in 34 eyes (34%) and was beneath the fovea in 42 eyes (42%). Documented growth was present in 64 eyes (64%), and known clinical risks for growth were present in all of the remaining 36 eyes (36%), with an average of 4 of 5 statistical risk factors for growth per tumor. After a mean of three treatment sessions and 14 months of follow-up, the mean tumor thickness was reduced to 1.4 mm. Treatment was successful in 94 eyes (94%) and failed in 6 eyes (6%). Three patients with amelanotic tumors showed no initial response to thermotherapy, but subsequent intravenous indocyanine green administration during thermotherapy resulted in improved heat absorption and tumor regression to a flat scar. The six eyes classified as treatment failures included four eyes with tumors that showed partial or no response to thermotherapy, thus requiring plaque radiotherapy or enucleation, and two eyes with recurrence, subsequently controlled with additional thermotherapy. After treatment, the visual acuity was the same (within 1 line) or better than the pretreatment visual acuity in 58 eyes (58%) and worse in 42 eyes (42%). The main reasons for poorer vision included treatment through the foveola for subfoveal tumor (25 eyes), retinal traction (10 eyes), retinal vascular obstruction (5 eyes), optic disc edema (1 eye), and unrelated ocular ischemia (1 eye). Temporal location (versus nasal and superior, P = 0.02) and greater distance from the optic disc (P = 0.04) were risks for retinal traction. Conclusions: Transpupillary thermotherapy may be an effective treatment for small posterior choroidal melanoma, especially those near the optic disc and fovea. Despite satisfactory local tumor control, ocular side effects can result in decreased vision. Longer follow- up will be necessary to assess the impact of thermotherapy on ultimate local tumor control and metastatic disease.