Resonant X-ray photoelectron spectroscopy: identification of atomic contributions to valence states.

Valence electronic structure is crucial for understanding and predicting reactivity. Valence non-resonant X-ray photoelectron spectroscopy (NRXPS) provides a direct method for probing the overall valence electronic structure. However, it is often difficult to separate the varying contributions to NRXPS; for example, contributions of solutes in solvents or functional groups in complex molecules. In this work we show that valence resonant X-ray photoelectron spectroscopy (RXPS) is a vital tool for obtaining atomic contributions to valence states. We combine RXPS with NRXPS and density functional theory calculations to demonstrate the validity of using RXPS to identify atomic contributions for a range of solutes (both neutral and ionic) and solvents (both molecular solvents and ionic liquids). Furthermore, the one-electron picture of RXPS holds for all of the closed shell molecules/ions studied, although the situation for an open-shell metal complex is more complicated. The factors needed to obtain a strong RXPS signal are investigated in order to predict the types of systems RXPS will work best for; a balance of element electronegativity and bonding type is found to be important. Additionally, the dependence of RXPS spectra on both varying solvation environment and varying local-covalent bonding is probed. We find that RXPS is a promising fingerprint method for identifying species in solution, due to the spectral shape having a strong dependence on local-covalency but a weak dependence on the solvation environment.

Clinical utility of liver biopsies in dogs undergoing splenectomy.

OBJECTIVE: To determine the prevalence of neoplasia detected on liver biopsy obtained at the time of splenectomy in dogs with splenic masses. MATERIALS AND METHODS: Retrospective study of medical records of dogs with splenic masses from which liver biopsies were taken following splenectomy. RESULTS: Malignant splenic neoplasia was detected in 50 of 113 (44.2%) of the dogs undergoing splenectomy. Neoplastic liver disease was detected on biopsy from 1 of 40 (2.5%) dogs with a grossly normal liver and from 20 of 69 (28.9%) dogs with a grossly abnormal liver. Dogs with a grossly abnormal liver had a ~ 16 times (95% CI: 2.5-170) higher chance of being diagnosed with liver neoplasia on biopsy. Haemoabdomen was also associated with an increased likelihood of liver neoplasia on biopsy at the time of splenectomy. CLINICAL SIGNIFICANCE: A liver biopsy taken from grossly normal liver is a low-yield diagnostic test but liver biopsy is recommended following splenectomy if the liver appears abnormal at surgery.

Structure and stress of Re(1121); chiral terraces at a racemic surface.

The surface structure and morphology of the clean Re(1121) surface has been investigated through combined low energy electron diffraction intensity analysis of data taken at multiple angles of incidence, scanning tunneling microscopy, and first-principles density functional calculations. The results show how this globally racemic surface terminates in two chirally distinct terraces, which show large-scale out-of-plane atomic relaxations and in-plane lateral movement of the uppermost atoms. We further identify and discuss the initial stages of step bunching upon adsorption of oxygen that leads ultimately to the large-scale faceting of the surface. Finally, we present calculations of surface stress and the response to applied surface strain, which suggest routes to the exertion of control over the expression of chirality at the surface.

[Septic peritonitis: treatment and prognosis]. / Therapie und Prognose der septischen Peritonitis.

Septic peritonitis is an inflammatory condition of the peritoneum that has a wide variety of clinical courses. The etiology and pathophysiology of this condition and its diagnosis in small animals are reviewed in a companion article. This article addresses the treatment of septic peritonitis and prognosis in small animals.

[Septic peritonitis: etiology, pathophysiology, and diagnosis]. / Ätiologie, Pathophysiologie und Diagnose der septischen Peritonitis.

Septic peritonitis is an inflammatory condition of the peritoneum that occurs secondary to microbial contamination. This clinically important condition has a wide variety of clinical courses as well as high morbidity and mortality due to secondary multiorgan dysfunction. This article reviews the etiology and pathophysiology of this condition and its diagnosis in small animals; a companion article addresses treatment and prognosis.

The use of megavoltage radiation therapy in the treatment of thymomas in rabbits: 19 cases.

An overall median survival time (MST) and prognostic factors in rabbits with thymomas treated with megavoltage radiation therapy (RT) were determined in this multi-institutional retrospective case analysis. Medical records for 19 rabbits with suspected or confirmed thymomas treated with RT were evaluated for data including signalment, haematological and serum biochemistry abnormalities, presence of pleural effusion, radiation plan, body weight, total radiation dose and institution administering RT. Statistical significance of these factors related to overall survival was assessed. An overall MST for all 19 rabbits was 313 days; exclusion of 3 rabbits that died acutely during the first 14 days of RT yielded a MST of 727 days. The only factor associated with a significantly decreased survival time was having a body weight lower than mean body weight of 1.57 kg. Radiation treatment-associated complications were infrequent and included radiation-induced myocardial failure, radiation pneumonitis and alopecia.

Surface and interstitial Ti diffusion at the rutile TiO(2)(110) surface.

Diffusion of Ti through the TiO(2)(110) rutile surface plays a key role in the growth and reactivity of TiO(2). To understand the fundamental aspects of this important process, we present an analysis of the diffusion of Ti ad-species at the stoichiometric TiO(2)(110) surface using complementary computational methodologies of density functional theory corrected for on-site Coulomb interactions (DFT + U) and a charge equilibration (QEq) atomistic potential to identify minimum energy pathways. We find that diffusion of Ti from the surface to subsurface (and vice versa) follows an interstitialcy exchange mechanism, involving exchange of surface Ti with the 6-fold coordinated Ti below the bridging oxygen rows. Diffusion in the subsurface between layers also follows an interstitialcy mechanism. The diffusion of Ti is discussed in light of continued attempts to understand the re-oxidation of non-stoichiometric TiO(2)(110) surfaces.

New insights on growth mechanisms of protein clusters at surfaces: an AFM and simulation study.

Despite its relevance to a wide range of technological and fundamental areas, a quantitative understanding of protein surface clustering dynamics is often lacking. In inorganic crystal growth, surface clustering of adatoms is well described by diffusion-aggregation models. In such models, the statistical properties of the aggregate arrays often reveal the molecular scale aggregation processes. We investigate the potential of these theories to reveal hitherto hidden facets of protein clustering by carrying out concomitant observations of lysozyme adsorption onto mica surfaces, using atomic force microscopy, and Monte Carlo simulations of cluster nucleation and growth. We find that lysozyme clusters diffuse across the substrate at a rate that varies inversely with size. This result suggests which molecular scale mechanisms are responsible for the mobility of the proteins on the substrate. In addition the surface diffusion coefficient of the monomer can also be extracted from the comparison between experiments and simulations. While concentrating on a model system of lysozyme-on-mica, this 'proof of concept' study successfully demonstrates the potential of our approach to understand and influence more biomedically applicable protein-substrate couples.

Mechanisms and dynamics of protein clustering on a solid surface.

A methodology for discovering the mechanisms and dynamics of protein clustering on solid surfaces is presented. In situ atomic force microscopy images are quantitatively compared to Monte Carlo simulations using cluster statistics to differentiate various models. We study lysozyme adsorption on mica as a model system and find that all surface-supported clusters are mobile, not just the monomers, with diffusion constant inversely related to cluster size. The surface monomer diffusion constant is measured to be D(1) approximately 9 x 10(-16) cm(2) s(-1), such a low value being difficult to measure using other techniques.

Spectroscopy of ultrathin epitaxial rutile TiO(2)(110) films grown on W(100).

Epitaxial ultrathin titanium dioxide films of 0.3 to approximately 7 nm thickness on a metal single crystal substrate have been investigated by high resolution vibrational and electron spectroscopies. The data complement previous morphological data provided by scanned probe microscopy and low energy electron diffraction to provide very complete characterization of this system. The thicker films display electronic structure consistent with a stoichiometric TiO(2) phase. The thinner films appear nonstoichiometric due to band bending and charge transfer from the metal substrate, while work function measurements also show a marked thickness dependence. The vibrational spectroscopy shows three clear phonon bands at 368, 438, and 829 cm(-1) (at 273 K), which confirms a rutile structure. The phonon band intensity scales linearly with film thickness and shift slightly to lower frequencies with increasing temperature, in accord with results for single crystals.

Structure of adsorbed organometallic rhodium: model single atom catalysts.

We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)2Cl] molecule adsorbed on the TiO2(110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarbonyl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site.

Direct evidence for the role of centrosomally localized p53 in the regulation of centrosome duplication.

Abnormal amplification of centrosomes is the major cause of mitotic defects and chromosome instability in cancer cells. Centrosomes duplicate once in each cell cycle, and abrogation of the regulatory mechanism underlying centrosome duplication leads to centrosome amplification. p53 tumor suppressor protein is involved in the regulation of centrosome duplication: loss of p53 as well as expression of certain p53 mutants result in deregulated centrosome duplication and centrosome amplification. p53 at least in part depends on its transactivation function to control centrosome duplication, primarily via upregulation of p21 cyclin-dependent kinase (CDK) inhibitor, which prevents untimely activation of CDK2/cyclin E, a key initiator of centrosome duplication. However, numerous studies have shown the presence of p53 at centrosomes, yet the role of the centrosomally localized p53 in the regulation of centrosome duplication had been enigmatic. Here, we comparatively examined wild-type p53 and p53 mutants that are transactivation(+)/centrosome-binding(-), transactivation(-)/centrosome-binding(+) and transactivation(-)/centrosome-binding(-) for their abilities to control centrosome duplication. We found that the transactivation(+)/centrosome-binding(-) and transactivation(-)/centrosome-binding(+) mutants suppress centrosome duplication only partially compared with wild-type p53. Moreover, the transactivation(-)/centrosome-binding(-) mutant almost completely lost the ability to suppress centrosome duplication. These observations provide direct evidence for the centrosomally localized p53 to participate in the regulation of centrosome duplication in a manner independent of its transactivation function in addition to its transactivation-dependent regulation of centrosome duplication.

Key role of a downstream specificity protein 1 site in cell cycle-regulated transcription of the AP endonuclease gene APE1/APEX in NIH3T3 cells.

Abasic (apurinic/apyrimidinic or AP) sites are a frequent type of DNA damage that threatens genetic stability. The predominant mammalian enzyme initiating repair of AP sites is the Ape1 AP endonuclease (also called Apex or Hap1), which also facilitates DNA binding by several transcription factors (Ref1 activity). We found that expression of the APE1 gene was coordinated with the cell cycle in murine NIH3T3 cells: APE1 mRNA levels rose after the G(1)-S transition and peaked approximately 4-fold higher in early to mid-S phase. The increased APE1 mRNA was the result of transcriptional activation rather than increased mRNA stability. Fusions of various APE1 promoter fragments to the chloramphenicol acetyltransferase CAT reporter gene indicated that APE1 expression depends on two transcription factor Sp1 binding sites within the promoter region. Mutation of these sites or of two CCAAT elements within the APE1 promoter, in conjunction with protein binding studies, demonstrated their specific roles. The Sp1 site upstream of the transcription start, together with an adjacent CCAAT element, establishes a protein-DNA complex required for basal transcription of APE1. The Sp1 site downstream of the transcription start was required for the response to cell growth. Because Ape1 is a dual function enzyme, its cell cycle-dependent expression might affect both DNA repair and the activity of various transcription factors as a function of the cell cycle.

Plasma concentration of ionized calcium in healthy iguanas.

OBJECTIVE: To measure plasma concentration of ionized calcium in healthy green iguanas. DESIGN: Prospective study. ANIMALS: 9 juvenile and 21 (10 male, 11 female) adult iguanas. PROCEDURE: Blood samples were obtained from each iguana, and plasma calcium, glucose, phosphorus, uric acid, total protein, albumin, globulin, potassium, and ionized calcium concentrations, aspartate transaminase (AST) activity, and pH were measured. Heparinized blood was used for measurement of ionized calcium concentration and blood pH. A CBC was also performed to assess the health of the iguanas. RESULTS: Significant differences were not detected among the 3 groups (juveniles, males, and females) with regard to ionized calcium concentration. Mean ionized calcium concentration measured in blood was 1.47 +/- 0.105 mmol/L. Significant differences were detected between juveniles and adults for values of phosphorus, glucose, total protein, albumin, globulin, and AST activity. CONCLUSIONS AND CLINICAL RELEVANCE: Ionized calcium concentration provides a clinical measurement of the physiologically active calcium in circulation. Evaluation of physiologically active calcium in animals with suspected calcium imbalance that have total plasma calcium concentrations within reference range or in gravid animals with considerably increased total plasma calcium concentrations is vital for determining a therapeutic plan. Accurate evaluation of calcium status will provide assistance in the diagnosis of renal disease and seizures and allow for better evaluation of the health status of gravid female iguanas.

Morphologic and cytochemical characteristics of blood cells and hematologic and plasma biochemical reference ranges in green iguanas.

OBJECTIVE: To determine blood cell morphologic characteristics and hematologic and plasma biochemical reference ranges for iguanas housed in a warm indoor and outdoor environment with regular exposure to direct sunlight. DESIGN: Original study. ANIMALS: 51 clinically normal iguanas (18 males, 25 females, and 8 juveniles) housed in 3 Florida locations. PROCEDURE: Blood was collected from the coccygeal or ventral abdominal vein. Any samples that had obvious hemolysis or clot formation were not used. Leukocyte counts were determined manually; other hematologic values were obtained by use of a commercially available cell counter. Plasma biochemical values were determined by use of a spectrophotometric chemistry analyzer. Blood smears were stained with Wright-Giemsa and cytochemical stains for morphologic and cytochemical evaluation. RESULTS: Hematologic ranges were generally higher in this study than previously reported. Thrombocytes were variable in appearance between individuals and sometimes difficult to distinguish from lymphocytes on a Wright-Giemsa preparation. Concentrations of calcium, phosphorus, total protein, globulins, and cholesterol were significantly higher, and the albumin:globulin ratio was significantly lower, in healthy gravid females than in male or nongravid female iguanas. Nongravid females had significantly higher calcium and cholesterol concentrations, compared with males. The calcium:phosphorus ratio was > 1 in all iguanas. Gravid females had a calcium phosphorus product ranging between 210 and 800. Intracytoplasmic inclusions were identified within the erythrocytes of some iguanas. CONCLUSIONS AND CLINICAL RELEVANCE: Hematologic ranges for iguanas in this study are higher than those reported for iguanas. Sex and age of the iguana should be considered when evaluating biochemical values. Healthy ovulating and gravid females may have significantly increased electrolyte and protein concentrations, but maintain a calcium:phosphorus ratio > 1.

Spontaneous conception in the presence of stage IIIC endometrioid ovarian cancer.

OBJECTIVE: To describe a rare case of spontaneous conception in a patient with a preexisting metastatic ovarian cancer. DESIGN: Case report. SETTING: University hospital. PATIENT(S): A 39-year-old Asian woman who conceived while undergoing an evaluation for primary infertility and newly detected bilateral adnexal masses. INTERVENTION(S): Staging laparotomy and total abdominal hysterectomy and bilateral salpingo-oophorectomy. MAIN OUTCOME MEASURE(S): Anatomic pathology diagnosis. RESULT(S): Blighted ovum and stage IIIC endometrioid adenocarcinoma of ovary. CONCLUSION(S): Metastatic ovarian cancer does not prevent either spontaneous ovulation or spontaneous conception.

Detection of antibodies to a pathogenic mycoplasma in American alligators (Alligator mississippiensis), broad-nosed Caimans (Caiman latirostris), and Siamese crocodiles (Crocodylus siamensis).

An epidemic of pneumonia with fibrinous polyserositis and multifocal arthritis emerged in captive American alligators (Alligator mississippiensis) in Florida, United States, in 1995. Mycoplasma alligatoris sp. nov. was cultured from multiple organs, peripheral blood, synovial fluid, and cerebrospinal fluid of affected alligators. In a subsequent experimental inoculation study, the Henle-Koch-Evans postulates were fulfilled for M. alligatoris as the etiological agent of fatal mycoplasmosis of alligators. That finding was remarkable because mycoplasmal disease is rarely fatal in animals. An enzyme-linked immunosorbent assay (ELISA) for the detection of antibodies produced by alligators in response to M. alligatoris exposure was developed by using plasma obtained from naturally infected alligators during the original epidemic. The assay was validated by using plasma obtained during an experimental dose-response study and applied to analyze plasma obtained from captive and wild crocodilian species. The ELISA reliably detected alligator seroconversion (P < 0.05) beginning 6 weeks after inoculation. The ELISA also detected seroconversion (P < 0.05) in the relatively closely related broad-nosed caiman Caiman latirostris and the relatively distantly related Siamese crocodile Crocodylus siamensis following experimental inoculation with M. alligatoris. The ELISA may be used to monitor exposure to the lethal pathogen M. alligatoris among captive, repatriated, and wild crocodilian species.

Experimental inoculation of broad-nosed caimans (Caiman latirostris) and Siamese crocodiles (Crocodylus siamensis) with Mycoplasma alligatoris.

An outbreak of mycoplasmosis caused by Mycoplasma alligatoris resulted in the death or euthanasia of 60 American alligators (Alligator mississippiensis) from a population of 74 captive bull alligators in Florida in 1995. The natural reservoir, routes of transmission, and host range of M. alligatoris are unknown. This study was undertaken to determine whether crocodilian species other than American alligators are susceptible to M. alligatoris. Six broad-nosed caimans (Caiman latirostris) and six Siamese crocodiles (Crocodylus siamensis) were experimentally inoculated with 10(6) colony forming units (CFU) of M. alligatoris instilled through the glottis. Two caimans and two crocodiles were used as negative controls. Six and four American alligators were used as positive and negative controls, respectively. Three of six (50%) inoculated caimans died within 10 wk postinoculation (PI) of severe mycoplasmosis. Gross necropsy, histopathologic, and culture results were similar for broad-nosed caimans and American alligators. None of the inoculated Siamese crocodiles developed mycoplasmosis, though M. alligatoris was isolated from the tonsils in three of six (50%) animals at necropsy. All the inoculated crocodilians that survived showed significant seroconversion by 6-8-wk PI (P < 0.05). The infective dose 50% (ID50) and lethal dose 50% (LD50) of M. alligatoris for the broad-nosed caiman are 10(6) CFU when instilled through the glottis, which is similar to that of the American alligator. Although the host range of M. alligatoris is not restricted to the American alligator, the organism does not appear to be pathogenic for Siamese crocodiles. Other species of crocodilians may be susceptible to infection with M. alligatoris, and this organism should be considered when the rapid onset of clinical signs of pneumonia, polyarthritis, pericarditis, and death occur.

Pathology of experimental mycoplasmosis in American alligators.

Mycoplasma alligatoris was the suspected etiology of an epidemic of acute multisystemic inflammatory disease which emerged in captive American alligators (Alligator mississippiensis) in Florida (USA) in 1995. In an experimental inoculation study conducted from April through October 1999, 18 alligators were inoculated with 10(2), 10(4), or 10(6) colony forming units (CFU) of M. alligatoris by instillation into the glottis. As early as 1 wk post-inoculation (PI), mycoplasma were cultured from blood of three of six alligators inoculated with 10(6) CFU. Two of those died and the third was euthanatized within 4 wk PI. Necropsy gross findings included fibrinous polyserositis and polyarthritis. Histopathologic changes in affected individuals included pulmonary edema, interstitial pneumonia, pericarditis, myocarditis, meningitis, and synovitis. Mycoplasma were cultured quantitatively in high numbers from trachea, lung, coelomic cavity, liver, spleen, interior of pericardial sac, heart, blood, brain, and limb joints. In alligators inoculated with 10(6) CFU, heterophilia and moderate hyperglycemia peaked about 4 wk PI, and seroconversion occurred by 6 to 8 wk PI. Necropsy gross and histologic findings were generally unremarkable for the surviving alligators inoculated with 10(6) CFU, alligators inoculated with 10(2) or 10(4) CFU, and four uninoculated control alligators. Mycoplasma were not cultured at any time point from those alligators. The findings confirm that M. alligatoris can cause fulminant inflammatory disease and rapid death of alligators.