Dust aerosols over India and adjacent continents retrieved using METEOSAT infrared radiance Part II: quantification of wind dependence and estimation of radiative forcing

Long-range transport of continental dust makes these particles a significant constituent even at locations far from their sources. It is important to study the temporal variations in dust loading over desert regions and the role of meteorology, in order to assess its radiative impact. In this paper, infrared radiance (10.5-12.5 mu m), acquired by the METEOSAT-5 satellite (similar to 5-km resolution) during 1999 and 2003 was used to quantify wind dependence of dust aerosols and to estimate the radiative forcing. Our analysis shows that the frequency of occurrence of dust events was higher during 2003 compared to 1999. Since the dust production function depends mainly on the surface wind speed over regions which are dry and without vegetation, the role of surface wind on IDDI was examined in detail. It was found that an increase of IDDI with wind speed was nearly linear and the rate of increase in IDDI with surface wind was higher during 2003 compared to 1999. It was also observed that over the Indian desert, when wind speed was the highest during monsoon months (June to August), the dust production rate was lower because of higher soil moisture (due to monsoon rainfall). Over the Arabian deserts, when the wind speed is the highest during June to August, the dust production rate is also highest, as soil moisture is lowest during this season. Even though nothing can be said precisely on the reason why 2003 had a greater number of dust events, examination of monthly mean soil moisture at source regions indicates that the occurrence of high winds simultaneous with high soil moisture could be the reason for the decreased dust production efficiency in 1999. It appears that the deserts of Northwest India are more efficient dust sources compared to the deserts of Saudi Arabia and Northeast Africa (excluding Sahara). The radiative impact of dust over various source regions is estimated, and the regionally and annually averaged top of the atmosphere dust radiative forcing (short wave, clear-sky and over land) over the entire study region (0-35 degrees N; 30 degrees-100 degrees E) was in the range of -0.9 to +4.5 W m(-2). The corresponding values at the surface were in the range of -10 to -25 W m(-2). Our studies demonstrate that neglecting the diurnal variation of dust can cause errors in the estimation of long wave dust forcing by as much as 50 to 100%, and nighttime retrieval of dust can significantly reduce the uncertainties. A method to retrieve dust aerosols during nighttime is proposed. The regionally and annually averaged long wave dust radiative forcing was +3.4 +/- 1.6 W m(-2).

Ferrocene-Conjugated Copper(II) Complexes of L-Methionine and Phenanthroline Bases: Synthesis, Structure, and Photocytotoxic Activity

Ferrocene-conjugated reduced Schiff base (Fc-metH) copper(II) complexes of L-methionine and phenanthroline bases, namely, Cu(Fc-met)(B)](NO3), where B is 1,10-phenanthroline (phen in 1), dipyrido3,2-d:2',3'-f]quinoxaline (dpq in 2), dipyrido3,2-a:2',3'-c]phenazine (dppz in 3), and 2-(naphthalen-1-yl)-1H-imidazo4,5-f]1,10]phenanthroline (nip in 4), were prepared and characterized and their photocytotoxicity studied (Fc = ferrocenyl moiety). Complexes Cu(Ph-met)(B)](NO3) of the reduced Schiff base from benzaldehyde and L-methionine (Ph-metH) and B (phen in 5, dppz in 6) were prepared and used as control species. Complexes 1 and 5 were structurally characterized by X-ray crystallography. Complex 1 as a discrete monomer has a CuN3OS core with the thiomethyl group as the axial ligand. Complex 5 has a polymeric structure with a CuN3O2 core in the solid state. Complexes 5 and 6 are formulated as Cu(Ph-met)(B)(H2O)] (NO3) in an aqueous phase based on the mass spectral data. Complexes 1-4 showed the Cu(II)-Cu(I) and Fc(+)-Fc redox couples at similar to 0.0 and similar to 0.5 V vs SCE, respectively, in DMF-0.1 M (Bu4N)-N-n](ClO4). A Cu(II)-based weak d-d band near 600 nm and a relatively strong ferrocenyl band at similar to 450 nm were observed in DMF-Tris-HCl buffer (1:4 v/v). The complexes bind to calf thymus DNA, exhibit moderate chemical nuclease activity forming (OH)-O-center dot radical species, and are efficient photocleavers of pUC19 DNA in visible light of 454, 568, and 647 rim, forming (OH)-O-center dot radical as the reactive oxygen species. They are cytotoxic in HeLa (human cervical cancer) and MCF-7 (human breast cancer) cells, showing an enhancement of cytotoxicity upon visible light irradiation. Significant change in the nuclear morphology of the HeLa cells was observed with 3 in visible light compared to the nonirradiated sample. Confocal imaging using 4 showed its nuclear localization within the HeLa cells.

Support for Integrated Ecosystem Assessments of NOAA’s National Estuarine Research Reserves System (NERRS), Volume II: Assessment of Ecological Condition and Stressor Impacts in Subtidal Waters of the North Carolina NERRS

A study was conducted to assess the status of ecological condition and potential human-health risks in subtidal estuarine waters throughout the North Carolina National Estuarine Research Reserve System (NERRS) (Currituck Sound, Rachel Carson, Masonboro Island, and Zeke’s Island). Field work was conducted in September 2006 and incorporated multiple indicators of ecosystem condition including measures of water quality (dissolved oxygen, salinity, temperature, pH, nutrients and chlorophyll, suspended solids), sediment quality (granulometry, organic matter content, chemical contaminant concentrations), biological condition (diversity and abundances of benthic fauna, fish contaminant levels and pathologies), and human dimensions (fish-tissue contaminant levels relative to human-health consumption limits, various aesthetic properties). A probabilistic sampling design permitted statistical estimation of the spatial extent of degraded versus non-degraded condition across these estuaries relative to specified threshold levels of the various indicators (where possible). With some exceptions, the status of these reserves appeared to be in relatively good to fair ecological condition overall, with the majority of the area (about 54%) having various water quality, sediment quality, and biological (benthic) condition indicators rated in the healthy to intermediate range of corresponding guideline thresholds. Only three stations, representing 10.5% of the area, had one or more of these indicators rated as poor/degraded in all three categories. While such a conclusion is encouraging from a coastal management perspective, it should be viewed with some caution. For example, although co-occurrences of adverse biological and abiotic environmental conditions were limited, at least one indicator of ecological condition rated in the poor/degraded range was observed over a broader area (35.5%) represented by 11 of the 30 stations sampled. In addition, the fish-tissue contaminant data were not included in these overall spatial estimates; however, the majority of samples (77% of fish that were analyzed, from 79%, of stations where fish were caught) contained inorganic arsenic above the consumption limits for human cancer risks, though most likely derived from natural sources. Similarly, aesthetic indicators are not reflected in these spatial estimates of ecological condition, though there was evidence of noxious odors in sediments at many of the stations. Such symptoms reflect a growing realization that North Carolina estuaries are under multiple pressures from a variety of natural and human influences. These data also suggest that, while the current status of overall ecological condition appears to be good to fair, long-term monitoring is warranted to track potential changes in the future. This study establishes an important baseline of overall ecological condition within NC NERRS that can be used to evaluate any such future changes and to trigger appropriate management actions in this rapidly evolving coastal environment. (PDF contains 76 pages)

Randomized Phase II trial of nintedanib, afatinib and sequential combination in castration-resistant prostate cancer

AIMS: The aim of this article was to evaluate afatinib (BIBW 2992), an ErbB family blocker, and nintedanib (BIBF 1120), a triple angiokinase inhibitor, in castration-resistant prostate cancer patients.

PATIENTS & METHODS: Patients were randomized to receive nintedanib (250 mg twice daily), afatinib (40 mg once daily [q.d.]), or alternating sequential 7-day nintedanib (250 mg twice daily) and afatinib (70 mg q.d. [Combi70]), which was reduced to 40 mg q.d. (Combi40) due to adverse events. The primary end point was progression-free rate at 12 weeks.

RESULTS: Of the 85 patients treated 46, 20, 16 and three received nintedanib, afatinib, Combi40 and Combi70, respectively. At 12 weeks, the progression-free rate was 26% (seven out of 27 patients) for nintedanib, and 0% for afatinib and Combi40 groups. Two patients had a ≥50% decline in PSA (nintedanib and the Combi40 groups). The most common drug-related adverse events were diarrhea, nausea, vomiting and lethargy.

CONCLUSION: Nintedanib and/or afatinib demonstrated limited anti-tumor activity in unselected advanced castration-resistant prostate cancer patients.

Studies On Supported Cobalt (Ii), Nickel (Ii) and Copper (Ii) Complexes Of O-Phenylenediamine and Schiff Bases Derived from 3-Hydroxyquinoxaline-2-Carboxaldehyde

The thesis deals with the synthesis, characterization and catalytic activity studies of supported cobalt(ii), nickel(II) and copper(II) complexes of O-phenylenediamine and Schiff bases derived from 3-hydroxyquinoxaline -2-carboxaldehyde. Zeolite encapsulation and polymer anchoring was employed for supporting the complexes. The characterization techniques proved that the encapsulation as well as polymer supporting has been successfully achieved. The catalytic activity studies revealed that the activities of the simple complexes are improved upon encapsulation. Various characterization techniques are used such as, chemical analysis, EPR, magnetic measurements, FTIR studies, thermal analysis, electronic spectra, XRD, SEM, surface area, and GC.The present study indicated that the that the mechanism of oxidation of catechol and DTBC by hydrogen peroxide is not altered by the change in the coordination sphere around the metal ion due to encapsulation. This fact suggests outer sphere mechanism for the reactions. The catalytic activity by zeolite encapsulated complex was found to be slower than that by the neat complex. The slowing down of the reaction in the zeolite case is probably due to the constraint imposed by the zeolite framework. The rate of DTBC ( 3,5-di-tert-butylchatechol)oxidation was found to be greater than the rate of catechol oxidation. This is obviously due to the presence of electron donating tertiary butyl groups.

Anion-pi, Lone-Pair-pi, pi-pi and Hydrogen-Bonding Interactions in a Cu-II Complex of 2-Picolinate and Protonated 4,4 '-Bipyridine: Crystal Structure and Theoretical Studies

A Cu-II complex of protonated 4,4'-bipyridine (Hbyp) and 2-picolinate (pic), [Cu-2(pic)(3)(Hbyp)(H2O)(ClO4)(2)], has been synthesised and characterised by single-crystal X-ray analysis. The structure consists of two copper atoms that have different environments, bridged by a carboxylate group. The equatorial plane is formed by the two bidentate picolinate groups in one Cu-II, and one picolinate, one monodentate 4,4'-bipyridyl ligand and a water molecule in the other. Each copper atom is also weakly bonded to a perchlorate anion in an axial position. One of the coordinated perchlorate groups displays anion-pi interaction with the coordinated pyridine ring. The noncoordinated carboxylate oxygen is involved in lone-pair (l.p.)-pi interaction with the protonated pyridine ring. In addition there are pi-pi and H-bonding interactions in the structure. Bader's theory of "atoms in molecules" (AIM) is used to characterise the anion-pi and l.p.-pi interactions observed in the solid state. A high-level ab initio study (RI-MP2/aug-cc-pVTZ level of theory) has been performed to analyse the anion-pi binding affinity of the pyridine ring when it is coordinated to a transition metal and also when the other pyridine ring of the 4,4'-bipyridine moiety is protonated. Theoretical investigations support the experimental findings of an intricate network of intermolecular interactions, which is characterised in the studied complex, and also indicate that protonation as well as coordination to the transition metal have important roles in influencing the pi-binding properties of the aromatic ring. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Syntheses, characterization and X-ray crystal structures of Ni(II) complexes of tridentate monocondensed and tetradentate dicondensed Schiff bases

Two octahedral complexes [Ni(HL1)(2)](ClO4)(2) (1) and [Ni(HL2)(2)](ClO4)(2) (2) and a square planar complex [Ni(HL3)]ClO4 (3) have been prepared, where [HL1 = 3-(2-amino-ethylimino)-butan-2-one oxime, HL2 = 3-(2-amino-propylimino)butan-2-one oxime] and H2L3 = 3-[2-(3-hydroxy-1-methyl-but-2-enylideneamino)-1-methyl-ethylimino]-buta n-2-one oxime. All the complexes have been characterized by elemental analyses, spectral studies and room temperature magnetic moment measurements. The molecular structures of all three compounds were elucidated on the basis of X-ray crystallography: complexes 1 and 2 are seen to be the met isomers. (C) 2008 Elsevier Ltd. All rights reserved.

Palliative in-patient cancer treatment in an anthroposophic hospital: II. Quality of life during and after stationary treatment, and subjective treatment benefits

BACKGROUND: There is an increasing demand for comprehensive forms of palliative cancer care, meeting physical as well as emotional, cognitive, spiritual and social needs. Therapy programs of anthroposophic hospitals are aimed at improving health and quality of life (QoL) at these levels. However, data on the influence of these programs on QoL of patients with advanced cancer are scarce. PATIENTS AND METHODS: 144 in-patients with advanced epithelial cancers were treated at the anthroposophic Lukas Klinik, Arlesheim, Switzerland. QoL was assessed upon admission, discharge and after 4 months, using 20 functional scales from the questionnaires EORTC QLQ-C30, HADS and SELT-M. Statistical testing was performed with the Wilcoxon signed rank test. At month 4, subjectively perceived benefits from anthroposophic medicine (AM) and conventional cancer therapy (CCT) were assessed by telephone. OBJECTIVE: The aim was to provide an account of global, physical, emotional, cognitive-spiritual and social QoL developments in advanced cancer patients, during and after in-patient AM treatment, and to investigate subjective benefits from AM and CCT. RESULTS: QoL improvements were observed in all 20 dimensions (12 significant). Compared to related studies, improvements were fairly high. At month 4, QoL scores had decreased but were still above baseline in all 20 dimensions. Both AM and CCT were perceived as beneficial. CONCLUSION: Our data provide evidence that in-patient therapy at an anthroposophic hospital can lead to significant QoL improvements, especially in emotional, but also global, physical, cognitive-spiritual and social aspects. Benefits of AM were experienced on the physical, emotional, cognitive- spiritual and social level. Benefits of CCT were tumor-focused.