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X-ray spectroscopy studies of potassium intercalated metal-free phthalocyanine multilayers adsorbed on Al(110) have been undertaken. Photoelectron spectroscopy measurements show the presence of several charge states of the molecules upon K intercalation, due to a charge transfer from the alkali. In addition, the comparison of valence band photoemission spectra with the density functional theory calculations of the density of states of the H(2)Pc(-) anion indicates a filling of the formerly lowest unoccupied molecular orbital by charge transfer from the alkali. This is further confirmed by x-ray absorption spectroscopy (XAS) studies, which show a decreased density of unoccupied states. XAS measurements in different experimental geometries reveal that the molecules in the pristine film are standing upright on the surface or are only slightly tilted away from the surface normal but upon K intercalation, the molecular orientation is changed in that the tilt angle of the molecules increases.

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Differential scanning calorimetry (DSC), thermogravimetry (TG) and Fourier-transform infra-red spectroscopy (FT-IR) analyses were performed to investigate changes in the physico-chemical properties of botryosphaerans, a family of exopolysaccharides (EPS) produced by the fungus Botryosphaeria rhodina MAMB-05 grown on glucose (EPS(GLC)), sucrose (EPS(SUC)) and fructose (EPS(FRU)). A slight endothermic transition and small mass loss attributable to the removal of water of hydration were observed in the DSC and TG analyses, respectively, for the three EPS samples. The FT-IR spectra confirmed no structural changes occurred during thermal treatment. Viscometry was utilized to obtain information on the rheological behaviour of the EPS in aqueous solutions. The Power Law and Cross Equations determined the natural pseudoplastic characteristics of the EPS. Comparatively, results obtained for EPS produced when B. rhodina MAMB-05 was grown on each of the three carbohydrate sources demonstrated similar apparent viscosity values for EPS(GLC) and EPS(SUC), while EPS(FRU) displayed the lowest apparent viscosity of the three botryosphaerans, suggesting a higher degree of ramification and lower Mw. EPS(GLC) and EPS(SUC) possessed similar degrees of ramification. The slight differences found in their viscosities can be explained by the differences in the type of branching among the three botryosphaerans, thus varying the strength of intermolecular interactions and consequently, consistency and viscosity. The physico-chemical studies of botryosphaerans represent the originality of this work, and the knowledge of these properties is an important criterion for potential applications.

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Botryosphaeran (EPS(FRU)), an exopolysaccharide of the beta-(1-->3,1-->6)-d-glucan type with 31% branching at C-6, is produced by the fungus Botryosphaeria rhodina MAMB-05 when grown on fructose as carbon source. Botryosphaeran was derivatized by sulfonation to induce anticoagulant activity. The effectiveness of the sulfonation reaction by chlorosulfonic acid in pyridine was monitored by the degree of substitution and FT-IR analysis of the sulfonated EPS(FRU) (once sulfonated, EPS(FRUSULF); and re-sulfonated, EPS(FRURESULF)). Activated partial thromboplastin time (APTT) and thrombin time (TT) tests of EPS(FRURESULF) indicated significant in vitro anticoagulant activity that was dose-dependent. EPS(FRU) did not inhibit any of the coagulation tests.

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Surface modification of reactive oxide substrates to obtain a less strongly interacting template for dye adsorption may be a way to enhance performance in dye-sensitized solar cells. In this work, we have investigated the electronic and structural properties of 4,4(')-bipyridine (bipy) as modifier adsorbed on the TiO(2)(110) surface. The modified surface is then coated with iron phthalocyanine (FePc) and the properties of this heterostructure are investigated with synchrotron based photoelectron spectroscopy, x-ray absorption spectroscopy, and scanning tunneling microscopy. We find that a saturated monolayer consisting of standing bipy molecules with one nitrogen atom pointing outward is formed on the oxide surface. FePc adsorb in molecular chains along the [001] direction on top of bipy and ordered in a tilted arrangement with adjacent molecules partially overlapping. Already from the first layer, the electronic properties of FePc resemble those of multilayer films. FePc alone is oxidized on the TiO(2)(110) surface, but preadsorbed bipy prevents this reaction. The energy level lineup at the interface is clarified.

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Four exopolysaccharides (EPS) obtained from Botryosphaeria rhodina strains isolated from rotting tropical fruit (graviola, mango, pinha, and orange) grown on sucrose were purified on Sepharose CL-4B. Total acid hydrolysis of each EPS yielded only glucose. Data from methylation analysis and (13)C NMR spectroscopy indicated that the EPS from the graviola isolate consisted of a main chain of glucopyranosyl (1-->3) linkages substituted at O-6 as shown in the putative structure below: [carbohydrate structure: see text]. The EPS of the other fungal isolates consisted of a linear chain of (1-->6)-linked glucopyranosyl residues of the following structure: [carbohydrate structure: see text]. FTIR spectra showed one band at 891 cm(-1), and (13)C NMR spectroscopy showed that all glucosidic linkages were of the beta-configuration. Dye-inclusion studies with Congo Red indicated that each EPS existed in a triple-helix conformational state. beta-(1-->6)-d-Glucans produced as exocellular polysaccharides by fungi are uncommon.

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Three D-glucans were isolated from the mycelium of the fungus Botryosphaeria rhodina MAMB-05 by sequential extraction with hot-water and hot aqueous KOH (2% w/v) followed by ethanol precipitation. Following their purification by gel permeation chromatography on Sepharose CL-4B, the structural characteristics of the D-glucans were determined by FT-IR and 13C NMR spectroscopy and, after methylation, by GC-MS. The hot-water extract produced a fraction designated Q1A that was a beta-(1-->6)-D-glucan with the following structure: [Formula: see text] The alkaline extract, when subjected to repeated freeze-thawing, yielded two fractions: K1P (insoluble) that comprised a beta-(1-->3)-D-glucan with beta-D-glucose branches at C-6 with the structure: [Formula: see text] and K1SA (soluble) consisting of a backbone chain of alpha-(1-->4)-linked D-glucopyranosyl residues substituted at O-6 with alpha-D-glucopyranosyl residues: [Formula: see text]

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The electronic structure of a vapor-sublimated thin film of metal-free phthalocyanine (H2Pc) is studied experimentally and theoretically. An atom-specific picture of the occupied and unoccupied electronic states is obtained using x-ray-absorption spectroscopy (XAS), core- and valence-level x-ray photoelectron spectroscopy (XPS), and density-functional theory (DFT) calculations. The DFT calculations allow for an identification of the contributions from individual nitrogen atoms to the experimental N1s XAS and valence XPS spectra. This comprehensive study of metal-free phthalocyanine is relevant for the application of such molecules in molecular electronics and provides a solid foundation for identifying modifications in the electronic structure induced by various substituent groups.

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A new administration form of the nasal decongestant oxymetazoline and the effect on patency of the maxillary ostium was investigated in five healthy volunteers. Registration and comparison of the equivalent diameter after administration of placebo spray and oxymetazoline spray, placebo solution and oxymetazoline solution were performed. It is our impression that administration of solution with the new spring-bellows container compared to spray oxymetazoline, is a more effective way of increasing the equivalent diameter of the maxillary ostium.

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This case conference is one of a series presented at the annual meeting of the American College of Sports Medicine, Dallas, May 1988.

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Two glycolipid fractions, isolated in 1975 from blood group A1 erythrocytes and shown on the basis of direct-inlet mass spectrometry to contain eight- and nine-sugar A-type sequences, have been reinvestigated by fast-atom-bombardment mass spectrometry and overlay analysis with selected monoclonal anti-A antibodies. The presence of three separate glycolipids was concluded, consistent with a common paragloboside backbone [beta-D-Galp-(1----4)-beta-D-GlcpNAc-(1----3)-beta-D-Galp-(1----4)-D-Glc] and a typical erythrocyte ceramide component (sphingosine, and 22-, 23-, 24-, and 25-carbon nonhydroxy fatty acids). It is proposed that they carry A determinants based on Type 1 [beta-D-Galp-(1----3)-beta-D-GlcpNAc], Type 2 [beta-D-Galp-(1----4)-beta-D-GlcpNAc], and Type 3 [beta-D-Galp-(1----3)-alpha-D-GalpNAc] chains, respectively. The Type 1 (eight sugars) and Type 3 (nine sugars) glycolipids appeared in mixtures of both the native and the acetylated form. The existence of Type 1 glycolipid, which appears to be a genuine erythrocyte glycolipid as concluded from the ceramide composition, had been predicted earlier by other workers.

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An understanding of the cellular response to injury helps to explain overuse trauma. Tendons, bursae, cartilage, bone and nerves all can break down owing to the repetitive forces from sporting activities. A precise diagnosis and thoughtful use of medication and modalities in a complete rehabilitation program help to minimize disability.

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Nonacid glycosphingolipids with 4 to 10 sugar residues isolated from pooled erythrocytes of blood group O donors have been efficiently separated as peracetylated derivatives on silicic acid. This procedure enabled a quantitative estimate of individual compounds and also revealed several GalNAc beta 1----3 terminated structures. The structural characterization of these glycolipids with 1H-NMR spectroscopy, direct inlet mass spectrometry, gas chromatography, and gas chromatography-mass spectrometry identified the compounds as GalNAc beta 1----3Gal alpha 1----4Gal beta 1----4Glc beta 1----1-N-acetyl sphingosine and GalNAc beta 1----3Gal alpha 1----4Gal beta 1----4Glc beta 1----1-N-acetyl phytosphingosine, GalNAc beta 1----3GalNAc beta 1----3Gal alpha 1----4Gal beta 1----4Glc beta 1----1 ceramide, and GalNAc beta 1----3Gal beta 1----4GlcNAc beta 1----3Gal beta 1----4Glc beta 1----1 ceramide.

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Amenorrheic athletes have been found to have a lower vertebral bone mineral density (BMD) than matched groups of eumenorrheic athletes. This study reports changes in BMD over a 15.5 month period in athletes who regained menses, athletes who remained amenorrheic, and athletes with regular cycles. The BMD was measured at two sites on the radius and at the lumbar vertebrae (L-1 through L-4), using single- and dual-photon densitometry, respectively. Changes in vertebral BMD were significant for the amenorrheic group (+6.3%), but not for cyclic women (-0.3%). A slight increase in radial density at S-1 and S-2 was not significant for either group. Two athletes who remained amenorrheic during this period continued to lose bone (-3.4%). We conclude that resumption of menses was the primary factor for the significant increase in the vertebral BMD of the formerly amenorrheic athletes.

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This study was designed to determine whether the hypoestrogenic status of 14 amenorrheic athletes was associated with a decrease in regional bone mass relative to that of 14 of their eumenorrheic peers. The two groups of athletes were matched for age, height, weight, sport, and training regimens. Bone mass was measured by dual-photon and single-photon absorptiometry at the lumbar vertebrae (L1 to L4) and at two sites on the radius. Vertebral mineral density was significantly lower in the amenorrheic group (mean, 1.12 g per square centimeter) than in the eumenorrheic group (mean, 1.30 g per square centimeter). There was no significant difference at either radial site. Radioimmunoassay confirmed a lower mean estradiol concentration (amenorrheic group, 38.58 pg per milliliter; eumenorrheic group, 106.99 pg per milliliter) and progesterone peak (amenorrheic group, 1.25 ng per milliliter; eumenorrheic group, 12.75 ng per milliliter) in the amenorrheic women, in four venous samples drawn at seven-day intervals. A three-day dietary history showed no significant differences in nutritional intake, including calcium with and without supplements. The two groups were similar in percentage of body fat, age at menarche, years of athletic participation, and frequency and duration of training but differed in number of miles run per week (amenorrheic group, 41.8 miles [67.3 km]; eumenorrheic group, 24.9 miles [40.1 km]). We conclude that the amenorrhea that is observed in female athletes may be accompanied by a decrease in mineral density of the lumbar vertebrae.

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We studied the effect of 2 weeks of iron therapy on exercise performance and exercise-induced lactate production in trained women athletes: six control subjects with normal parameters of iron status and nine with mild iron-deficiency anemia defined by low Fe/TIBC, ferritin, and minimally decreased Hgb values. Iron therapy improved the abnormal measures of iron status and low Hgb in the second group to normal. Exercise performance in a progressive work-exercise protocol on a bicycle ergometer to exhaustion was unchanged after iron therapy in both groups; however, blood lactate levels at maximum exercise in the iron-deficient group decreased significantly from 10.3 +/- 0.6 mmol/L before therapy to 8.42 +/- 0.7 after therapy (p less than 0.03). The control subjects did not significantly alter lactate levels after maximal exercise on iron compared to placebo: 8.3 +/- 0.8 mmol/L vs. 8.5 +/- 0.7. Although there was not a significant difference in maximum exercise performance after iron therapy, these data support animal experiments implying that iron may play a role in oxidative metabolism and that minimal decreases in Hgb may impair arterial oxygen content enough to affect aerobic metabolism. In addition, these findings may have important implications for competitive women athletes in whom mild iron deficiency may go unnoticed.

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Twenty-four different supplies of fresh Mozzarella cheese whey were pasteurized. Twenty-one were evaporated into seven condensed whey product (CWP) categories; three were not evaporated. Each whey and whey product was subsequently manufactured into Ricotta cheese. Average total solids (TS) content ranged from 6.70 to 35.90%. The Ricotta cheeses manufactured from five of the eight categories were judged to be acceptable for the market. Average TS (%) of the acceptable categories were 6.70, 10.31, 14.87, 18.02 and 20.86. Ricotta cheeses manufactured with CWP of average TS contents of 25.10, 28.67 and 35.90% were not acceptable. Flavor defects for Ricotta cheeses that were unacceptable included coarse, unnatural and unclean; body and texture defects included grainy and mealy. We recommend the manufacture of whey Ricotta cheese with approximately 21% CWP. Yield based on total weight for CWP with 20.86 TS averaged 21.32%, more than four times greater than the noncondensed whey. Ricotta cheese from CWP of 20.86% TS tested 69.75% moisture, 7.55% protein, 13.37% lactose, 4.30% fat and 0.72% salt. Large amounts of protein and lactose remained in the Ricotta cheese whey and must be handled properly to prevent pollution.

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Two antifungal agents, pimaricin and mycostatin, added to Cottage cheese through the wash water at concentrations of 20, 50, or 100 mug/ml of wash water or added through the cheese dressing at 1, 2, or 5 mug/g retarded the growth of Aspergillus niger and Saccharomyces cerevisiae and improved the shelf-life of the cheese. In general, cheese with highest concentration of antifungal agent and stored at lowest temperature had best keeping quality. Pimaricin was slightly more effective than mycostatin in inhibiting fungi; inhibition was greater if the antifungal agents were added to the cheese dressing and the cheese was stored at low temperature; and A. niger was more sensitive to the inhibitors than S. Cerevisiae.

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