Bacteriochlorophylls modified at position C-3

[3-Vinyl]-bacteriochlorophyll a and related pigments modified at C-3 and/or C-132 have been synthesized from bacteriochlorophyll a. The reactivity at C-3 is strongly influenced by the C-132 substituent, and vice versa. Spectroscopical data and comparison among derivatives modified at the isocyclic ring indicate that this interaction is related to formation of an intermediate enol(ate) structure. The possible role of enol(ate) formation in (bacterio)chlorophylls in nature is discussed

Effects of Base Cavity Depth on a Free Spinning Wrap-Around Fin Missile Configuration

This study investigated the role base cavity depth plays in altering the overall subsonic aerodynamic forces on a free spinning axisymmetric body with wrap around fins. Wind tunnel usage allowed the forces to be monitored for varying base cavity depths and angles of attack. A base cavity depth analysis was also performed on a non-spinning axisymmetric body for comparison. Oil visualizations were conducted on the non-spinning configuration to further describe airflow patterns around the body and within the cavity. Results revealed that the aerodynamic forces, mostly drag, changed with increasing cavity depth but not to the extent previously believed. The force results, in conjunction with the flow visualizations, suggested that base cavities have very similar effects on spinning and non-spinning configurations

Modified bacterial reaction centers

Pigments of borohydride-treated reaction centers of Rhodobacter sphaeroides R 26 and Rhodopseudomonas viridis were analyzed by HPLC with polychromatic detection. In both species, pigment composition and contents were unchanged. Reaction centers from Rhodobacter sphaeroides R26 were prepared in which bacteriochlorophylls (BA,B) and bacteriopheophytins (HA,B) were exchanged with their potential borohydride products reduced at C-31. [3-Hydroxyethyl]-BChl a exchanges selectively into the BA,B pockets, and 31-OH-BPh a to the HA,B pockets. Stable reaction centers are obtained in both cases. A comparison of the absorption and circular dichroism spectra of reaction centers after exchange with 31-OH pigments, and of borohydride-modified reaction centers, reveal distinct differences. It is concluded that during borohydride reduction none of the pigments is chemically modified or extracted from the reaction centers

Circulating Biologically Active Adrenomedullin Predicts Organ Failure and Mortality in Sepsis

BACKGROUND: Sepsis is a life-threatening organ dysfunction caused by a dysregulated host response to infection. Biologically active adrenomedullin (bio-ADM) is an emerging biomarker for sepsis. We explored whether bio-ADM concentration could predict severity, organ failure, and 30-day mortality in septic patients. METHODS: In 215 septic patients (109 patients with sepsis; 106 patients with septic shock), bio-ADM concentration was measured at diagnosis of sepsis, using sphingotest bio-ADM (Sphingotec GmbH, Hennigsdorf, Germany) and analyzed in terms of sepsis severity, vasopressor use, and 30-day mortality. The number of organ failures, sequential (sepsis-related) organ failure assessment (SOFA) score, and 30-day mortality were compared according to bio-ADM quartiles. RESULTS: Bio-ADM concentration was significantly higher in patients with septic shock, vasopressor use, and non-survivors than in patients with solitary sepsis, no vasopressor use, and survivors, respectively (all P<0.0001). Bio-ADM quartiles were associated with the number of organ failures (P<0.0001), as well as SOFA cardiovascular, renal, coagulation, and liver subscores (all P<0.05). The 30-day mortality rate showed a stepwise increase in each bio-ADM quartile (all P<0.0001). Bio-ADM concentration and SOFA score equally predicted the 30-day mortality (area under the curve: 0.827 vs 0.830). CONCLUSIONS: Bio-ADM could serve as a useful and objective biomarker to predict severity, organ failure, and 30-day mortality in septic patients

EPR, ENDOR, and TRIPLE resonance studies of modified bacteriochlorophyll cation radicals

A series of substituted bacteriochlorophyll molecules, all used in reconstitution experiments of reaction centers of Rhodobacter sphaeroides (Struck et al. Biochim. Biophys. Acta 1991, 1060, 262-270), were characterized by EPR, electron-nuclear double (ENDOR), and electron-nuclear-nuclear triple (TRIPLE) resonance spectroscopy in their monomeric radical cation states. Effects of different substituents at position 3 in the porphyrin macrocycle were considered, especially for two «crosslinks» between plant and bacterial chlorophylls. These are 3-vinylbacteriochlorophyll where the «bacteria» acetyl group at position 3 was substituted by vinyl and 3-acetylchlorophyll where the «plant» vinyl group was substituted by acety