978 resultados para Pyrrolo[3,2-d]pyrimidines


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The synthesis and the photophysical properties of the complex [Ru(TTF-dppz)(2)(Aqphen)](2+) (TTF = tetrathiafulvalene, dppz = dipyrido-[3,2-a:2',3'-c]phenazine, Aqphen = anthraquinone fused to phenanthroline via a pyrazine bridge) are described. In this molecular triad excitation into the metal ligand charge transfer bands results in the creation of a long-lived charge separated state with TTF acting as electron donor and anthraquinone as terminal acceptor. The lifetime of the charge-separated state is 400 ns in dichloromethane at room temperature. A mechanism for the charge separation involving an intermediate charge-separated state is proposed based on transient absorption spectroscopy.

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A tetrathiafulvalene donor has been annulated to the bay region of perylenediimide through a 1H-benzo-[d]pyrrolo[1,2-a]imidazol-1-one spacer affording an extended pi-conjugated molecular dyad (TTF-PDI). To gain insight into its ground- and excited-state electronic properties, the reference compound Ph-PDI has been prepared via a direct Schiff-base condensation of N,N'-bis(1-octylnonyl) benzoperylene-1',2':3,4:9,10-hexacarboxylic-1',2'-anhydride-3,4:9,10-bis (imide) with benzene-1,2-diamine. Both the experimental and the computational (DFT) results indicate that TTF-PDI exhibits significant intramolecular electronic interactions giving rise to an efficient photoinduced charge-separation process. Free-energy calculations verify that the process from TTF to the singlet-excited state of PDI is exothermic in both polar and nonpolar solvents. Fast adiabatic electron-transfer processes of a compactly fused, pi-conjugated TTF-PDI dyad in benzonitrile, 2-methyltetrahydrofuran, anisole and toluene were observed by femtosecond transient absorption spectral measurements. The lifetimes of radical-ion pairs slightly increase with decreasing the solvent polarities, suggesting that the charge-recombination occurs in the Marcus inverted region. By utilizing the nanosecond transient absorption technique, the intermolecular electron-transfer process in a mixture of has been observed via the triplet excited PDI for the first time.

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PURPOSE: The aim of this study was to evaluate [(99m)Tc]Demotate 2 ([(99m)Tc-N(4) (0-1),Asp(0),Tyr(3)]octreotate) as a candidate for in vivo imaging of sst(2)-positive tumours and to compare it with [(111)In]DOTA-tate ([(111)In-DOTA(0),Tyr(3)]octreotate). METHODS: Labelling of Demotate 2 with (99m)Tc was performed at room temperature using SnCl(2) as reductant in the presence of citrate at alkaline pH. Radiochemical analysis involved ITLC and HPLC methods. Peptide conjugate affinities for sst(2) were determined by receptor autoradiography on rat brain cortex sections using [DOTA(0),(125)I-Tyr(3)]octreotate as the radioligand. The affinity profile of Demotate 2 for human sst(1)-sst(5) was studied by receptor autoradiography in cell preparations using the universal somatostatin radioligand [(125)I][Leu(8),(D: )Trp(22),Tyr(25)]somatostatin-28. The internalisation rates of [(99m)Tc]Demotate 2 and [(111)In]DOTA-tate were compared in sst(2)-positive and -negative control cell lines. Biodistribution of radiopeptides was studied in male Lewis rats bearing CA20948 tumours. RESULTS: Peptide conjugates showed selectivity and a high affinity binding for sst(2) (Demotate 2 IC(50)=3.2 nM and DOTA-tate IC(50)=5.4 nM). [(99m)Tc]Demotate 2, like [(111)In]DOTA-tate, internalised rapidly in all sst(2)-positive cells tested, but not in sst(2)-negative control cells. After injection in CA20948 tumour-bearing rats both radiopeptides showed high and specific uptake in the sst(2)-positive organs and in the implanted tumour and rapid excretion from non-target tissues via the kidneys. CONCLUSION: [(99m)Tc]Demotate 2, similarly to the known sst(2)-targeting agent [(111)In]DOTA-tate, showed promising biological qualities for application in the scintigraphy of sst(2)-positive tumours.

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Ninety strains of a collection of well-identified clinical isolates of gram-negative nonfermentative rods collected over a period of 5 years were evaluated using the new colorimetric VITEK 2 card. The VITEK 2 colorimetric system identified 53 (59%) of the isolates to the species level and 9 (10%) to the genus level; 28 (31%) isolates were misidentified. An algorithm combining the colorimetric VITEK 2 card and 16S rRNA gene sequencing for adequate identification of gram-negative nonfermentative rods was developed. According to this algorithm, any identification by the colorimetric VITEK 2 card other than Achromobacter xylosoxidans, Acinetobacter sp., Burkholderia cepacia complex, Pseudomonas aeruginosa, and Stenotrophomonas maltophilia should be subjected to 16S rRNA gene sequencing when accurate identification of nonfermentative rods is of concern.

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Volcán de Colima has been continuously erupting since the onset of dome growth in 1998. This period of unrest has had 4 prominent periods; 1998-1999, 2003, 2004-2005, and the current dome growth that began in February of 2007. Each of these episodes was marked by lava extrusion forming a dome and lava flows, followed by explosions that destroyed the dome. The Correlation Spectrometer (COSPEC) was used to determine SO2 emission rates on 164 days from May 2003 to February 2007, using both stationary ground based scans and some flight traverses. Scans were separated into the categories of explosive degassing and passive, or background degassing. These scans show variation in the SO2 flow rate from below detection limit (~3 t/d depending on environmental conditions) during background, passive emissions to a peak of 2949 t/d (34 kilograms/second) during an explosion on 9 October, 2004. Both passive and explosive degassing increased when there was lava extrusion in 2004 and with the increased explosive activity in 2005. These two different processes of degassing wax with each other when activity increases and wane together as well, indicating a parallel cyclicity in the volcanic eruption and degassing rates, where the conduit partially seals (pressurizes) between explosions. Colima’s gas and eruptive behavior is compared to similar systems such as Santiaguito and Soufrière Hills, Montserrat. About 2/3 of Colima’s SO2 degassing, amounting to 1.3 x 105 tonnes in 3.74 yrs has come in short lived small (VEI=0-1) vertical explosions that occurred at the rate of 100-3000explosions/ month, and the remaining third has occured in continuous passive degassing. Colima emits sulfur at a rate equivalent to about 0.04 to 0.08 wt % S, similar to other andesitic convergent plate boundary volcanoes. There has been an explosive destruction of the dome in every cycle for that past 5 years, and it is assumed that the current dome which began growth in February, 2007 (just at the end of this study) will be destroyed. Higher emission rates seen in the quiescence of 2006 may have eased the pressure at the time, resulting in the slow effusion of the current dome and lack of explosivity.

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Herman Stein, President of the International Association of Schools of Social Work from 1968 - 1976, has for more than sixty years excelled as an educator, scholar, internationalist, university administrator, and leader in a variety of professional associations. From almost the beginning of his career, the world has been the stage on which he has played those many roles, all of them with an abundance of talent. In fact, while he was in the graduate program of what is now the Columbia University School of Social Work, he had to decide whether to become a social worker or an actor. As an undergraduate he became involved in student theatrical productions, where he teamed up with the famous comedian, Danny Kaye, who became a life-long companion and friend. At the end of Steins first year in the social work program, he was invited to join an off-Broadway variety show that helped to launch Kaye on his meteoric rise on both stage and screen. "If I´d joined," Stein has said, "the theater probably was going to be where I would make my career as a character actor." Fortunately for social work and social work education, he chose instead to continue his studies at the School of Social Work, from which he received his master's degree in 1941 and the doctoral degree in 1958. While the world has been his stage, education has been at the heart of his manifold activities. Following a period of direct service practice as a caseworker in a well-known private agency in New York City, he was recruited by the Columbia School of Social Work in 1945 as a faculty member. With an interruption for a significant overseas assignment from 1947 to 1950, he continued at Columbia for another fourteen years, rising through all professorial ranks to Professor and Director of the School's Research Center.

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The anionic cluster Pt-19(CO)(22)](4-) (1), of pentagonal symmetry, reacts with CO and AuPPh3+ fragments. Upon increasing the Au:Pt-19, molar ratio, different species are sequentially formed, but only the last two members of the series could be characterized by X-ray diffraction, namely, Pt-19(CO)(24)(mu(4)-AuPPh3)(3)](-) (2) and Pt-19(CO)(24){mu(4)-Au-2(PPh3)(2)}(2)] (3).The metallic framework of the starting cluster is completely modified after the addition of CO and AuL+, and both products display the same platinum core of trigonal symmetry, with closely packed metal atoms. The three AuL+ units cap three different square faces in 2, whereas four AuL+ fragments are grouped in two independent bimetallic units in the neutral cluster 3. Electrochemical and spectroelectrochemical studies on 2 showed that its redox ability is comparable with that of the homometallic 1.

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Three-dimensional oxalate-based {[Ru(bpy)3][Cu2xNi2(1-x)(ox)3]}n (0≤ x ≤ 1, ox = C2O42-, bpy = 2,2‘bipyridine) were synthesized. The structure was determined for x = 1 by X-ray diffraction on single crystal. The compound crystallizes in the cubic space group P4132. It shows a three-dimensional 10-gon 3-connected (10,3) anionic network where copper(II) has an unusual tris(bischelated) environment. X-ray powder diffraction patterns and their Rietveld refinement show that all the compounds along the series are isostructural and single-phased. According to X-ray absorption spectroscopy, copper(II) and nickel(II) have an octahedral environment, respectively elongated and trigonally distorted. As shown by natural circular dichroism, the optically active forms of {[Ru(bpy)3][CuxNi2(1-x)(ox)3]}n are obtained starting from resolved Δ- or Λ-[Ru(bpy)3]2+. The Curie−Weiss temperatures range between −55 (x = 1) and −150 K (x = 0). The antiferromagnetic exchange interaction thus decreases when the copper contents increases in agreement with the crystallographic structure of the compounds and the electronic structure of the metal ions. At low temperature, the compounds exhibit complex long-range ordered magnetic behavior.

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In monocotyledonous plants, 1,4-benzoxazin-3-ones, also referred to as benzoxazinoids or hydroxamic acids, are one of the most important chemical barriers against herbivores. However, knowledge about their behavior after attack, mode of action and potential detoxification by specialized insects remains limited. We chose an innovative analytical approach to understand the role of maize 1,4-benzoxazin-3-ones in plant–insect interactions. By combining unbiased metabolomics screening and simultaneous measurements of living and digested plant tissue, we created a quantitative dynamic map of 1,4-benzoxazin-3-ones at the plant–insect interface. Hypotheses derived from this map were tested by specifically developed in vitro assays using purified 1,4-benzoxazin-3-ones and active extracts from mutant plants lacking 1,4-benzoxazin-3-ones. Our data show that maize plants possess a two-step defensive system that effectively fends off both the generalist Spodoptera littoralis and the specialist Spodoptera frugiperda. In the first step, upon insect attack, large quantities of 2-β-d-glucopyranosyloxy-4,7-dimethoxy-1,4-benzoxazin-3-one (HDMBOA-Glc) are formed. In the second step, after tissue disruption by the herbivores, highly unstable 2-hydroxy-4,7-dimethoxy-1,4-benzoxazin-3-one (HDMBOA) is released by plant-derived β-glucosidases. HDMBOA acts as a strong deterrent to both S. littoralis and S. frugiperda. Although constitutively produced 1,4-benzoxazin-3-ones such as 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA) are detoxified via glycosylation by the insects, no conjugation of HDMBOA in the insect gut was found, which may explain why even the specialist S. frugiperda has not evolved immunity against this plant defense. Taken together, our results show the benefit of using a plant–insect interface approach to elucidate plant defensive processes and unravel a potent resistance mechanism in maize.

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Changes in (1→3,1→4)-β-D-glucan endohydrolase (EC 3.2.1.73) protein levels were investigated in segments from second leaves of wheat (Triticum aestivum L.). The abundance of the enzyme protein markedly increased when leaf segments were incubated in the dark whereas the enzyme rapidly disappeared when dark-incubated segments were illuminated or fed with sucrose. Addition of cycloheximide (CHI) to the incubation medium led to the disappearance of previously synthesized (1→3,1→4)-β-glucanase and suppressed the dark-induced accumulation indicating that the enzyme was rather unstable. The degradation of (1→3,1→4)-β-glucanase was analyzed without the interference of de-novo synthesis in intercellular washing fluid (IWF). The loss of the enzyme protein during incubation of IWF (containing naturally present peptide hydrolases) indicated that the stability increased from pH 4 to pH 7 and that an increase in the temperature from 25 to 35 °C considerably decreased the stability. Chelating divalent cations in the IWF with o-phenanthroline also resulted in a lowered stability of the enzyme. A strong temperature effect in the range from 25 to 35 °C was also observed in wheat leaf segments. Diurnal changes in (1→3,1→4)-β-glucanase activity were followed in intact second leaves from young wheat plants. At the end of the dark period, the activity was high but constantly decreased during the light phase and remained low if the light period was extended. Activity returned to the initial level during a 10-h dark phase. During a diurnal cycle, changes in (1→3,1→4)-β-glucanase activity were associated with reciprocal changes in soluble carbohydrates. The results suggest that the synthesis and the proteolytic degradation of an apoplastic enzyme may rapidly respond to changing environmental conditions.

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A (1→3,1→4)‐β‐D‐glucan endohydrolase [(1→3,1→4)‐β‐glucanase, EC 3.2.1.73] was detected in wheat (Triticum aestivum L.) leaves by Western analyses and activity measurements. This enzyme is able to degrade the (1→3,1→4)‐β‐glucans present in the cell walls of cereals and other grass species. In wheat, enzyme levels clearly increased during leaf development, reaching maximum values at full expansion and then decreasing upon leaf ageing. To test whether the abundance of (1→3,1→4)‐β‐glucanase might be controlled by the carbohydrate status, environmental and nutritional conditions capable of altering the leaf soluble sugar contents were used. Both the activity and enzyme protein levels rapidly and markedly increased when mature leaves were depleted of sugars (e.g. during extended dark periods), whereas elevated carbohydrate contents (e.g. following continuous illumination, glucose supply in the dark or nitrogen deficiency during a light/dark cycle) caused a rapid decrease in (1→3,1→4)‐β‐glucanase abundance or prevented its accumulation in the leaves. The physiological significance of (1→3,1→4)‐β‐glucanase accumulation under sugar depletion remains to be elucidated.

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"Über Lenin, 'Materialismus und Empiriokritizismus" (GS 11, S. 171-188), Wintersemester 1928/29, a) Typoskript, 17 Blatt, b) Typoskript mit eigenhändigen Korrekturen, 17 Blatt (unterzeichnet mit "H. Möller (Berlin)", c) Manuskript, 1 Heft, 18 Blatt, davon 3 leer, d) Entwurf, Typoskript mit eigenhändigen Korrekturen, 11 Blatt; Friedrich Pollock: Kollegheft zum Seminar von Max Horkheimer über Geschichtsphilosophie, Wintersemester 1928/29 (enthält: Kollegheft 23.11.1928 - 15.02.1929, eigenhändige Notizen, 1 Heft, 16 Blatt und 4 zusätzliche Blätter; Kolegheft 22.02.1929, eigenhändige Notizen, 1 Heft, 16 Blatt, davon 9 leer); Friedrich Pollock: Notizen zu einem Vortrag von Hans Cornelius über 'Klassenphilosophie und reine Philosophie', und Mitschrift von Diskussionsbeiträgen , u.a. von Max Horkheimer, 26.01.1929, eigenhändige Notizen, 1 Heft, 12 Blatt und 1 zusätzliches Blatt sowie eigenhändige Notizen von Max Horkheimer; "Kant und die Philosophie der Gegenwart", Vorlesung 1929 (enthält: Vorlesungsmanuskript und Friedrich Pollock: Kolleghefte zur Vorlesung, eigenhändige Notizen); "Hegel", Übung Sommersemester 1929 (enthält: 1 Notizheft, 28 Blatt mit eigenhändigen Notizen zur Übung, 5 Blatt und eigenhändigen Notizen über Vorgeschichte und Anfänge der Soziologie, 5 Blatt; Friedrich Pollock: eigenhändige Notizen zur Übung von Max Horkheimer, 1 Heft, 28 Blatt, davon 4 leer, und 3 zusätzliche Blätter); "Wissensoziologie oder Historischer Materialismus" Einleitung: Soziologie der Soziologie" (GS 11, S. 189-195), Wintersemester 1929/30 (enthält: Manuskript, teils von Max Horkheimer, teils von Friedrich Polock, datiert: 10.09.1929, 1 Heft, 10 Blatt und 2 zusätzliche Blätter; Manuskript, datiert Wintersemester 1929/30, 1 Heft, 4 Blatt, davon 1 leer);

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The basaltic rocks of Hole 794D drilled during Leg 128 are strongly altered. Microprobe analyses and XRD spectra on small quantities of matter extracted from thin sections show that primary minerals and glassy zones of the groundmass are totally or partially replaced by clay minerals with chlorite/saponite mixed-layer composition whatever the rock sample considered. This mixed-layer was also identified in veins and vesicles where it crystallizes in spheroidal aggregates. The largest veins and vesicles are filled by a zoned deposit: the chlorite/saponite mixed-layer always occupies the central part and is rimmed by pure saponite. Calcite crystallizes in secondary fractures which crosscut the clayey veins and vesicles. Chemographic analysis based on the M+-4Si-3R2+ projection shows that the chemical composition of the saponite component in the mixed-layer is identical to that of the free saponite. This indicates that the clay mineral crystallization was controlled by the chemical composition of the alteration fluids. From petrographic evidence, it is suggested that both chlorite/saponite mixed-layer and free saponite belong to the same hydrothermal event and are produced by a temperature decrease. This is supported by the stable isotopic data. The isotopic data show very little variation: d18O saponite ranges from 13.1 per mil to 13.5 per mil, and dD saponite from -73.6 per mil to -70.0 per mil. d18O calcite varies from +19.7 per mil to +21.9 per mil vs SMOW and d13C from -3.2 per mil to +0.4 per mil vs. PDB. These values are consistent with seawater alteration of the basalt. The formation of saponite took place at 150°-180°C and the formation of calcite at about 65°C.

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Early Oligocene siliceous microfossils were recovered in the upper c. 193 m of the CRP-3 drillcore. Although abundance and preservation are highly variable through this section, approximately 130 siliceous microfossil taxa were identified, including diatoms, silicoflagellates, ebridians, chrysophycean cysts, and endoskeletal dinoflagellates. Well-preserved and abundant assemblages characterize samples in the upper c. 70 m and indicate deposition in a coastal setting with water depths between 50 and 200 m. Abundance fluctuations over narrow intervals in the upper c. 70 mbsf are interpreted to reflect environmental changes that were either conducive or deleterious to growth and preservation of siliceous microfossils. Only poorly-preserved (dissolved, replaced, and/or fragmented) siliceous microfossils are present from c. 70 to 193 mbsf. Diatom biostratigraphy indicates that the CRP-3 section down to c. 193 mbsf is early Oligocene in age. The lack of significant changes in composition of the siliceous microfossil assemblage suggests that no major hiatuses are present in this interval. The first occurrence (FO) of Cavitatus jouseanus at 48.44 mbsf marks the base of the Cavitatus jouseanus Zone. This datum is inferred to be near the base of Subchron C12n at c. 30.9 Ma. The FO of Rhizosolenia antarctica at 68.60 mbsf marks the base of the Rhizosolenia antarctica Zone. The FO of this taxon is correlated in deep-sea sections to Chron C13 (33.1 to 33.6 Ma). However, the lower range of R. antarctica is interpreted as incomplete in the CRP-3 drillcore, as it is truncated at an underlying interval of poor preservation: therefore, an age of c. 33.1 to 30.9 Ma is inferred for interval between c. 70 and 50 mbsf. The absence of Hemiaulus caracteristicus from diatom-bearing interval of CRP-3 further indicates an age younger than c. 33 Ma (Subchron C13n) for strata above c. 193 mbsf. Siliceous microfossil assemblages in CRP-3 are significantly different from the late Eocene assemblages reported CIROS-1 drillcore. The absence of H. caracteristicus, Stephanopyxis splendidus, and Pterotheca danica, and the ebridians Ebriopsis crenulata, Parebriopsis fallax, and Pseudoammodochium dictyoides in CRP-3 indicates that the upper 200 m of the CRP-3 drillcore is equivalent to part of the stratigraphic interval missing within the unconformity at c. 366 mbsf in CIROS-1.

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An intense diatom bloom developed within a strong meridional silicic acid gradient across the Antarctic Polar Front at 61°S, 170°W following stratification of the water column in late October/early November 1997. The region of high diatom biomass and the silicic acid gradient propogated southward across the Seasonal Ice Zone through time, with the maximum diatom biomass tracking the center of the silicic acid gradient. High diatom biomass and high rates of silica production persisted within the silicic acid gradient until the end of January 1998 (ca. 70 d) driving the gradient over 500 km to the south of its original position at the Polar Front. The bloom consumed 30 to >40 µM Si(OH)4 in the euphotic zone between about 60 and 66°S leaving near surface concentrations <2.5 µM and occasionally <1.0 µM in its wake. Integrated biogenic silica concentrations within the bloom averaged 410 mmol Si/m**2 (range 162-793 mmol Si/m**2). Average integrated silica production on two consecutive cruises in December 1997 and January 1998 that sampled the bloom while it was well developed were 27.5±6.9 and 22.6±20 mmol Si/m**2/d, respectively. Those levels of siliceous biomass and silica production are similar in magnitude to those reported for ice-edge diatom blooms in the Ross Sea, Antarctica, which is considered to be among the most productive regions in the Southern Ocean. Net silica production (production minus dissolution) in surface waters during the bloom was 16-21 mmol Si/m**2/d, which is sufficient for diatom growth to be the cause of the southward displacement of the silicic acid gradient. A strong seasonal change in silica dissolution : silica production rate ratios was observed. Integrated silica dissolution rates in the upper 100-150 m during the low biomass period before stratification averaged 64% of integrated production. During the bloom integrated dissolution rates averaged only 23% of integrated silica production, making 77% of the opal produced available for export to depth. The bloom ended in late January apparently due to a mixing event. Dissolution : production rate ratios increased to an average of 0.67 during that period indicating a return to a predominantly regenerative system. Our observations indicate that high diatom biomass and high silica production rates previously observed in the marginal seas around Antarctica also occur in the deep ocean near the Polar Front. The bloom we observed propagated across the latitudinal band overlying the sedimentary opal belt which encircles most of Antarctica implying a role for such blooms in the formation of those sediments. Comparison of our surface silica production rates with new estimates of opal accumulation rates in the abyssal sediments of the Southern Ocean, which have been corrected for sediment focusing, indicate a burial efficiency of <=4.6% for biogenic silica. That efficiency is considerably lower than previous estimates for the Southern Ocean.