Synthesis and characterization of crystalline niobium and tantalum carbonyl complexes at room temperature.

A variety of homoleptic transition metal carbonyl complexes are known as bulk compounds for group 7-12 metals. These metals typically feature a maximum of 6 CO ligands to form complexes with 18 valence electrons. In contrast, group 3-5 metals, with fewer valence electrons, have been shown to form highly coordinated heptacarbonyl and octacarbonyl complexes-although they were only identified by gas-phase mass spectrometry and/or matrix isolation spectroscopy work. Now we have prepared heptacarbonyl cations of niobium and tantalum as crystalline salts that are stable at room temperature. The [M(CO)7]+ (M = Nb or Ta) complexes were formed by the oxidation of [M(CO)6]- with 2Ag+[Al(ORF)4]- (RF, C(CF3)3) under a CO atmosphere; their experimental characterization was supported by density functional theory calculations. Other unusual carbonyl compounds were also synthesized: two isostructural salts that contained the 84-valence-electron cluster cation [Ag6{Nb(CO)6}4]2+, the piano-stool complexes [(1,2-F2C6H4)M(CO)4]+ and two polymorphs of neutral Ta2(CO)12 with a long, unsupported Ta-Ta bond.

The Lewis superacid Al[N(C6F5)2]3 and its higher homolog Ga[N(C6F5)2]3 - structural features, theoretical investigation and reactions of a metal amide with higher fluoride ion affinity than SbF5.

Herein we present the synthesis of the two Lewis acids Al[N(C6F5)2]3 (ALTA) and Ga[N(C6F5)2]3 (GATA) via salt elimination reactions. The metal complexes were characterized by NMR-spectroscopic methods and X-ray diffraction analysis revealing the stabilization of the highly Lewis acidic metal centers by secondary metal-fluorine contacts. The Lewis acidic properties of Al[N(C6F5)2]3 and Ga[N(C6F5)2]3 are demonstrated by reactions with Lewis bases resulting in the formation of metallates accompanied by crucial structural changes. The two metallates [Cs(Tol)3]+[FAl(N(C6F5)2)3]- and [AsPh4]+[ClGa(N(C6F5)2)3]- contain interesting weakly coordinating anions. The reaction of Al[N(C6F5)2]3 with trityl fluoride yielded [CPh3]+[FAl(N(C6F5)2)3]- which could find application in the activation of metallocene polymerization catalysts. The qualitative Lewis acidity of Al[N(C6F5)2]3 and Ga[N(C6F5)2]3 was investigated by means of competition experiments for chloride ions in solution. DFT calculations yielded fluoride ion affinities in the gas phase (FIA) of 555 kJ mol-1 for Al[N(C6F5)2]3 and 472 kJ mol-1 for Ga[N(C6F5)2]3. Thus, Al[N(C6F5)2]3 can be considered a Lewis superacid with a fluoride affinity higher than SbF5 (493 kJ mol-1) whereas the FIA of the corresponding gallium complex is slightly below the threshold to Lewis superacidity.

Crystal structure determination of the nonclassical 2-norbornyl cation.

After decades of vituperative debate over the classical or nonclassical structure of the 2-norbornyl cation, the long-sought x-ray crystallographic proof of the bridged, nonclassical geometry of this prototype carbonium ion in the solvated [C7H11](+)[Al2Br7](-) • CH2Br2 salt has finally been realized. This achievement required exceptional treatment. Crystals obtained by reacting norbornyl bromide with aluminum tribromide in CH2Br2 undergo a reversible order-disorder phase transition at 86 kelvin due to internal 6,1,2-hydride shifts of the 2-norbornyl cation moiety. Cooling with careful annealing gave a suitably ordered phase. Data collection at 40 kelvin and refinement revealed similar molecular structures of three independent 2-norbornyl cations in the unit cell. All three structures agree very well with quantum chemical calculations at the MP2(FC)/def2-QZVPP level of theory.

Successful transplant outcomes using pediatric en bloc kidneys into adult recipients.

En bloc pediatric kidneys have been used in adult renal transplantation for over 30 years. Despite the duration of this experience, issues such as increased technical difficulties and associated complications, hyperfiltration injury, and ultimately a limited allograft half-life have limited the use of these organs at many centers. To date, however, the collected experience suggests that these organs may in fact be an excellent source of allografts for adult transplantation. The present paper was a retrospective review of the experience using en bloc kidneys for adult transplantation from two institutions. These results support the use of these kidneys. Actual patient and graft survival at 2 years was 97% and 94% respectively.

Crystallographic findings on the internally uncoupled and near-rigor states of myosin: further insights into the mechanics of the motor.

Here we report a 2.3-A crystal structure of scallop myosin S1 complexed with ADP.BeF(x), as well as three additional structures (at 2.8-3.8 A resolution) for this S1 complexed with ATP analogs, some of which are cross-linked by para-phenyl dimaleimide, a short intramolecular cross-linker. In all cases, the complexes are characterized by an unwound SH1 helix first seen in an unusual 2.5-A scallop myosin-MgADP structure and described as corresponding to a previously unrecognized actin-detached internally uncoupled state. The unwinding of the SH1 helix effectively uncouples the converter/lever arm module from the motor and allows cross-linking by para-phenyl dimaleimide, which has been shown to occur only in weak actin-binding states of the molecule. Mutations near the metastable SH1 helix that disable the motor can be accounted for by viewing this structural element as a clutch controlling the transmission of torque to the lever arm. We have also determined a 3.2-A nucleotide-free structure of scallop myosin S1, which suggests that in the near-rigor state there are two conformations in the switch I loop, depending on whether nucleotide is present. Analysis of the subdomain motions in the weak actin-binding states revealed by x-ray crystallography, together with recent electron microscopic results, clarify the mechanical roles of the parts of the motor in the course of the contractile cycle and suggest how strong binding to actin triggers both the power stroke and product release.

Atomic structure of scallop myosin subfragment S1 complexed with MgADP: a novel conformation of the myosin head.

The crystal structure of a proteolytic subfragment from scallop striated muscle myosin, complexed with MgADP, has been solved at 2.5 A resolution and reveals an unusual conformation of the myosin head. The converter and the lever arm are in very different positions from those in either the pre-power stroke or near-rigor state structures; moreover, in contrast to these structures, the SH1 helix is seen to be unwound. Here we compare the overall organization of the myosin head in these three states and show how the conformation of three flexible "joints" produces rearrangements of the four major subdomains in the myosin head with different bound nucleotides. We believe that this novel structure represents one of the prehydrolysis ("ATP") states of the contractile cycle in which the myosin heads stay detached from actin.

Interaction of tetrandrine with slowly inactivating calcium channels. Characterization of calcium channel modulation by an alkaloid of Chinese medicinal herb origin.

Tetrandrine, a bis-benzylisoquinoline alkaloid derived from the Chinese medicinal herb Stephania tetrandra, is a putative Ca2+ entry blocker whose mechanism of action is unknown. To investigate this mechanism, the effects of tetrandrine were characterized on binding of three chemical classes of Ca2+ entry blockers in cardiac sarcolemmal membrane vesicles. In the range 25-37 degrees C, tetrandrine completely blocks diltiazem binding, partially inhibits D-600 binding, and markedly stimulates nitrendipine binding, with greatest enhancement occurring at 37 degrees C. The potency of tetrandrine is increased 10-fold as temperature is raised from 25 to 37 degrees C. Scatchard analyses indicate that inhibition of diltiazem binding and stimulation of nitrendipine binding result from changes in ligand affinities while inhibition of D-600 binding is due to both an increase in KD and decrease in Bmax of aralkylamine receptors. Ligand dissociation studies reveal that tetrandrine increases D-600 off-rates, decreases nitrendipine off-rates, but has no effect on diltiazem dissociation kinetics. In addition, tetrandrine reversibly blocks inward Ca2+ currents through L-type Ca2+ channels in GH3 anterior pituitary cells. These results indicate that tetrandrine interacts directly at the benzothiazepine-binding site of the Ca2+ entry blocker receptor complex and allosterically modulates ligand binding at other receptors in this complex. These findings suggest that tetrandrine is a structurally unique natural product Ca2+ entry blocker and provide a rationale explanation for the therapeutic effectiveness of this agent.

Theoretical studies on the electrical activity of pancreatic beta-cells as a function of glucose.

The electrical activity of pancreatic beta-cells, which has been closely correlated both with intracellular Ca2+ concentration and insulin release, is characterized by a biphasic response to glucose and bursts of spiking action potentials. Recent voltage clamp and single channel patch clamp experiments have identified several transmembrane ionic channels that may play key roles in the electrophysiological behavior of beta-cells. There is a hypothesis that Ca2+-activated K+ channels are responsible for both the resting potential during low glucose concentration and the silent phase during bursting. The discovery of the ATP-inactivated K+ channel raises the possibility that the current for this latter K+ channel may dominate the resting potential, while the Ca2+-activated K+ current dominates the silent phase potential between bursts. The recent discovery that Ca2+-activated K+ channels are pH sensitive raises an interesting possibility for the biphasic electrical response. In this paper, numerical methods are presented for evaluating these hypotheses against experimental evidence.

[Status of ultrasound and roentgen diagnosis in prenatal detection of osteochondrodysplasias]. / Zum Stellenwert der Ultraschall- und Röntgendiagnostik bei der pränatalen Erfassung letaler Osteochondrodysplasien.

Ultrasound and X-ray investigation have a specific but complementary importance within the prenatal recording of lethal osteochondrodysplasia. In the prenatal diagnoses of thanatophoric dysplasia, asphyxiating thoracic dysplasia, chondrodysplasia punctata and achondroplasia we present our procedure for the investigation. All pregnant women are examined by ultrasound. Where the sonographical findings--according to our previous definition for the above mentioned diseases--suggest that they may be present we recommend referral to an institution with highly-specialized diagnostic possibilities for further investigation. Already in the II. trimester of pregnancy it is possible to make such group diagnoses by ultrasound. To give further specificity to the findings prenatal X-ray investigation should be done preferably in the III. trimester. The importance of confirming the diagnosis by either postnatal or postmortem X-ray investigation should be emphasized.