Mixed-metal hydride complexes containing ZrHA1 bridges. synthesis and relation to transition-metal-catalyzed reactions of aluminum hydrides

Dialkylaluminum hydrides and Cp₂ZrX₂ (Cp = π⁵-C₅H₅; X = Cl, H, alkyl) were found to react by aggregation to give mixed ZrAl trihydride complexes containing ZrHAl bridges. Reactions of these mixed-metal hydrides are discussed and structural parallels between them and known aluminum hydride complexes are drawn.     

Study of the thermal reactions of boric acid with polyols

The possibility of detecting the direction of reaction of boric acid with polyol and its intermediate stages by means of the data obtained with a Derivatograph is shown. An equation is given for determining the average monomer number in polymers with terminal H and OH groups from weight loss data. In the interaction of boric acid with hexitols and pentitols, polymeric esters are formed. It is found that formation of complex polyolboric acid is the intermediate stage of each interaction.

     

High resolution on a quadrupole ion trap mass spectrometer

By using a modified ion trap mass spectrometer, resolution in excess of 30,000 (FWHM) at m I z 502 is demonstrated. The method of increasing resolution in the ion trap mass spectrometer operated in the mass-selective instability mode depends on decreasing the rate of scanning the primary radio frequency amplitude as well as using resonance ejection at the appropriate frequency and amplitude. A theoretical basis for the method is introduced.     

Human neural stem cell growth and differentiation in a gradient-generating microfluidic device

This paper describes a gradient-generating microfluidic platform for optimizing proliferation and differentiation of neural stem cells (NSCs) in culture. Microfluidic technology has great potential to improve stem cell (SC) cultures, whose promise in cell-based therapies is limited by the inability to precisely control their behavior in culture. Compared to traditional culture tools, microfluidic platforms should provide much greater control over cell microenvironment and rapid optimization of media composition using relatively small numbers of cells. Our platform exposes cells to a concentration gradient of growth factors under continuous flow, thus minimizing autocrine and paracrine signaling. Human NSCs (hNSCs) from the developing cerebral cortex were cultured for more than 1 week in the microfluidic device while constantly exposed to a continuous gradient of a growth factor (GF) mixture containing epidermal growth factor (EGF), fibroblast growth factor 2 (FGF2) and platelet-derived growth factor (PDGF). Proliferation and differentiation of NSCs into astrocytes were monitored by time-lapse microscopy and immunocytochemistry. The NSCs remained healthy throughout the entire culture period, and importantly, proliferated and differentiated in a graded and proportional fashion that varied directly with GF concentration. These concentration-dependent cellular responses were quantitatively similar to those measured in control chambers built into the device and in parallel cultures using traditional 6-well plates. This gradient-generating microfluidic platform should be useful for a wide range of basic and applied studies on cultured cells, including SCs.     

Elucidating the initial dynamics of electron photodetachment from atoms in liquids using variably-time-delayed resonant multiphoton ionization

We study the photodetachment of electrons from sodium anions in room temperature liquid tetrahydrofuran (THF) using a new type of three-pulse pump-probe spectroscopy. Our experiments use two variably-time-delayed pulses for excitation in what is essentially a resonant 1+1 two-photon ionization: By varying the arrival time of the second excitation pulse, we can directly observe how solvent motions stabilize and trap the excited electron prior to electron detachment. Moreover, by varying the arrival times of the ionization (excitation) and probe pulses, we also can determine the fate of the photoionized electrons and the distance they are ejected from their parent Na atoms. We find that as solvent reorganization proceeds, the second excitation pulse becomes less effective at achieving photoionization, and that the solvent motions that stabilize the excited electron following the first excitation pulse occur over a time of approximately 450 fs. We also find that there is no spectroscopic evidence for significant solvent relaxation after detachment of the electron is complete. In combination with the results of previous experiments and molecular dynamics simulations, the data provide new insight into the role of the solvent in solution-phase electron detachment and charge-transfer-to-solvent reactions.     

Synthesis of dihydroxylated prolines and iminocyclitols from five-membered endocyclic enecarbamates. Total synthesis of the potent glycosidase inhibitor (2R,3R,4R,5R)-2,5-dihydroxymethyl-3,4-dihydroxypyrrolidine (DMDP)

cis- and trans-3,4-Dihydroxylated prolines and the iminocyclitol 1,4-dideoxy-1,4-imino ribitol were synthesized employing a strategy involving the Heck arylation of five-membered endocyclic enecarbamates with aryldiazonium salts followed by oxidative cleavage of the electron-rich aromatic ring. The total synthesis of the potent α- and β-glucosidase inhibitor (2R,3R,4R,5R)-2,5-hydroxymethyl-3,4-dihydroxypyrrolidine (DMDP) was also achieved by the same strategy in ten steps from a chiral five-membered enecarbamate in 12% overall yield.     

Scaling laws in simple and complex proteins: size scaling effects associated with domain number and folding class

The native states of the most compact globular proteins have been described as being in the so-called “collapsed-polymer regime,” characterized by the scaling law R _g ~ n ^ν, where R _g is radius of gyration, n is the number of residues, and ν ≈ 1/3. However, the diversity of folds and the plasticity of native states suggest that this law may not be universal. In this work, we study the scaling regimes of: (i) one to four-domain protein chains, and (ii) their constituent domains, in terms of the four major folding classes. In the case of complete chains, we show that size scaling is influenced by the number of domains. For the set of domains belonging to the all-α, all-β, α/β, and α?+?β folding classes, we find that size-scaling exponents vary between 0.3?≤?ν?≤?0.4. Interestingly, even domains in the same folding class show scaling regimes that are sensitive to domain provenance, i.e., the number of domains present in the original intact chain. We demonstrate that the level of compactness, as measured by monomer density, decreases when domains originate from increasingly complex proteins.