Valence and Rydberg states of protonated formaldehyde

MR-CISD and MR-CISD + Q calculations have been performed for the vertical excitations of protonated formaldehyde in comparison to formaldehyde. Singlet and triplet states have been investigated. It is shown that the protonation causes the Rydberg states to be shifted to higher energies by several eV. This finding is discussed by means of the Rydberg formula in terms of quantum defects for the two lowest vertical ionization energies. For protonated formaldehyde the pi-pi(*) valence state is energetically the second lowest state at 9.80 eV, about 1.50 eV below the first Rydberg n-3s state. This finding is in strong contrast to the case of formaldehyde where the pi-pi(*) state is embedded within a series of Rydberg states. (C) 2003 Elsevier Science B.V. All rights reserved

Influence of the Atlantic Multidecadal Oscillation on South American Atmosphere Dynamics and Precipitation

The Atlantic Multidecadal Oscillation (AMO) is coherently linked to climate variations over many parts of the globe. Despite recent achievements, the mechanism by which the AMO influences regional precipitation over South America is not well understood. In this study, we isolate the atmospheric response to the AMO using a water isotope-enabled version of the Community Earth System Model version 1.2 (iCESM1.2) and determine its influence on (sub)tropical South American regional precipitation and atmospheric circulation. The results suggest an interhemispheric seesaw in Hadley circulation strength and that the section of the Atlantic Hadley cell is marked by a stronger upward air component south of the equator during the cold AMO phase. We also find that the precipitation anomalies over (sub)tropical South America during AMO phases are mainly related to changes in the Atlantic Intertropical Convergence Zone (ITCZ) core strength, where in the cold (warm) AMO phase the core region strengthens (weakens) from February to July, while from July to November the core region weakens (strengthens). Our results stress the importance of acknowledging the dynamics of season- and regional-dependent ITCZ responses, as they are sufficient to produce observed AMO-related signals even in the absence of marked changes in the ITCZ position

Influence of the Atlantic Multidecadal Oscillation on South American Atmosphere Dynamics and Precipitation

The Atlantic Multidecadal Oscillation (AMO) is coherently linked to climate variations over many parts of the globe. Despite recent achievements, the mechanism by which the AMO influences regional precipitation over South America is not well understood. In this study, we isolate the atmospheric response to the AMO using a water isotope-enabled version of the Community Earth System Model version 1.2 (iCESM1.2) and determine its influence on (sub)tropical South American regional precipitation and atmospheric circulation. The results suggest an interhemispheric seesaw in Hadley circulation strength and that the section of the Atlantic Hadley cell is marked by a stronger upward air component south of the equator during the cold AMO phase. We also find that the precipitation anomalies over (sub)tropical South America during AMO phases are mainly related to changes in the Atlantic Intertropical Convergence Zone (ITCZ) core strength, where in the cold (warm) AMO phase the core region strengthens (weakens) from February to July, while from July to November the core region weakens (strengthens). Our results stress the importance of acknowledging the dynamics of season- and regional-dependent ITCZ responses, as they are sufficient to produce observed AMO-related signals even in the absence of marked changes in the ITCZ position

Superbasicity of a Bis-guanidino Compound with a Flexible Linker: A Theoretical and Experimental Study

The bis-guanidino compound H2C{hpp}(2) (I; hppH = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) has been converted to the monocation [I-H](+) and isolated as the chloride and tetraphenylborate salts. Solution-state spectroscopic data do not differentiate the protonated guanidinium from the neutral guanidino group but suggest intramolecular "-N-H center dot center dot center dot N=" hydrogen bonding to form an eight-membered C3N4H heterocycle. Solid-state CPMAS N-15 NMR spectroscopy confirms protonation at one of the imine nitrogens, although line broadening is consistent with solid-state proton transfer between guanidine functionalities. X-ray diffraction data have been recorded over the temperature range 50-273 K. Examination of the carbon-nitrogen bond lengths suggests a degree of "partial protonation" of the neutral guanidino group at higher temperatures, with greater localization of the proton at one nitrogen position as the temperature is lowered. Difference electron density maps generated from high-resolution X-ray diffraction studies at 110 K give the first direct experimental evidence for proton transfer in a poly(guanidino) system. Computational analysis of I and its conjugate acid [I-H](+) indicate strong cationic resonance stabilization of the guanidinium group, with the nonprotonated group also stabilized, albeit to a lesser extent. The maximum barrier to proton transfer calculated using the Boese-Martin for kinetics method was 2.8 kcal mol(-1), with hydrogen-bond compression evident in the transition state; addition of zero-point vibrational energy values leads to the conclusion that the proton transfer is barrierless, implying that the proton shuttles freely between the two nitrogen atoms. Calculations determining the gas-phase proton affinity and the pK(a) in acetonitrile both indicate that compound I should behave as a superbase. This has been confirmed by spectrophotometric titrations in MeCN using polyphosphazene references, which give an average pK(a) of 28.98 +/- 0.05. Triadic analysis indicates that the dominant term causing the high basicity is the relaxation energy

Ascites as First Atypical and Only Clinical Manifestation of De Novo Follicular Lymphoma

Follicular lymphoma is the most common indolent non-Hodgkin’s lymphoma and is usually initially detected in lymph nodes. Primary extranodal NHL is most commonly primarily localized in the gastrointestinal tract. We present one unusual case of ileum FL with ascites as the first clinical sign. The 73-year-old female patient was presented to the emergency department for evaluation of mild abdominal pain and abdominal swelling that had been going on for three days followed by bloating and occasional pain in the spine. The abdominal contrast-enhanced CT revealed the contrast stagnation in the distal part of the ileum. The ileum wall about 11 cm in length was thickened up to 2.9 cm and the tumor mass infiltrated all layers of ileum mesenteric lymphadenopathy up to 2 cm in diameter and significant ascites. On the upper ileum wall, the vegetative mass was described 3 cm in diameter. The patient had an emergent laparotomy with the ileocolic resection and latero-lateral ileocolic anastomosis. The microscopy finding of terminal ileum and the regional lymph nodes showed domination of cleaved cells with irregular nuclei which correspond to centrocytes. There were 0–15 large non-cleaved cells corresponding to centroblast in the microscopy high-power field. The final diagnosis was follicular lymphoma, the clinical stage 2E and histological grade by Berard and Mann criteria 1–2

Carbon Dioxide Activation by "Non-nucleophilic" Lead Alkoxides

A series of terminal lead alkoxides have been synthesized utilizing the bulky beta-diketiminate ligand [{N(2,6-(Pr2C6H3)-Pr-i)-C(Me)}(2)CH](-) (BDI). The nucleophilicities of these alkoxides have been examined, and unexpected trends were observed. For instance, (BDI)PbOR reacts with methyl iodide only under forcing conditions yet reacts readily, but reversibly, with carbon dioxide. The degree of reversibility is strongly dependent upon minor changes in the R group. For instance, when R = isopropyl, the reversibility is only observed when the resulting alkyl carbonate is treated with other heterocumulenes; however, when R = tert-butyl, the reversibility is apparent upon any application of reduced pressure to the corresponding alkyl carbonate. The differences in the reversibility of carbon dioxide insertion are attributed to the ground-state energy differences of lead alkoxides. The mechanism of carbon dioxide insertion is discussed