A novel three-component reaction for the diastereoselective synthesis of 2H-pyrimido[2,1-a]isoquinolines via 1,4-dipolar cycloaddition

[reaction: see text] The 1,4-dipole derived from isoquinoline and DMAD has been shown to react readily with N-tosylimines resulting in the diastereoselective synthesis of 2H-pyrimido[2,1-a]isoquinoline derivatives.     

Gas Hydrate Formation in Reversed Micelles

We describe a technique to modify protein solubility and optimize enzyme activity in reversed micellar solutions. The technique is based on the ability of hydrates of natural gas to form in the micro-aqueous phase. Clathrate hydrates are crystalline inclusions of water and gas, and their formation in bulk water has traditionally been studied with relevance to natural gas recovery. We have found that hydrates can form in the environment of the microaqueous pools of reversed micelles, and that their extent of formation can be well controlled through the thermodynamic variables of temperature and pressure. Additionally, formation of hydrates affects the size and aggregation number of the micelles, and thus influences the solubility and conformation of encapsulated proteins. We demonstrate how the concept can be used in two applications: (i) protein extraction into reversed micelles and subsequent recovery, and (ii) optimization of enzyme activity in reversed micelles.     

Length dependent folding kinetics of phenylacetylene oligomers: structural characterization of a kinetic trap

Using simulation to study the folding kinetics of 20-mer poly-phenylacetylene (pPA) oligomers, we find a long time scale trapped kinetic phase in the cumulative folding time distribution. This is demonstrated using molecular dynamics to simulate an ensemble of over 100 folding trajectories. The simulation data are fit to a four-state kinetic model which includes the typical folded and unfolded states, along with an intermediate state, and most surprisingly, a kinetically trapped state. Topologically diverse conformations reminiscent of alpha helices, beta turns, and sheets in proteins are observed, along with unique structures in the form of knots. The nonhelical conformations are implicated, on the basis of structural correlations to kinetic parameters, to contribute to the trapped kinetic behavior. The strong solvophobic forces which mediate the folding process and produce a stable helical folded state also serve to overstabilize the nonhelical conformations, ultimately trapping them. From our simulations, the folding time is predicted to be on the order of 2.5-12.5 mus in the presence of the trapped kinetic phase. The folding mechanism for these 20-mer chains is compared with the previously reported folding mechanism for the pPA 12-mer chains. A linear scaling relationship between the chain length and the mean first passage time is predicted in the absence of the trapped kinetic phase. We discuss the major implications of this discovery in the design of self-assembling nanostructures.     

Adhesion and debonding of soft elastic films: crack patterns, metastable pathways, and forces

We study the phenomenon of debonding in a thin soft elastic film sandwiched between two rigid plates as one of the plates is brought into intimate contact and then pulled away from contact proximity by application of a normal force. Nonlinear simulations based on minimization of total energy (composed of stabilizing elastic strain energy and destabilizing adhesive interaction energy) are employed to address the problems of contact hysteresis, cavitation, crack morphology, variation of contact area, snap-off distance, pull-off force, work done, and energy loss. Below a critical distance (d(c)) upon approach, simulations show the formation of columnar structures and nonrandom, regularly arranged nanocavities at the soft interface at a length scale of approximately 3h (h being the thickness of the film). The persistence of such instability upon withdrawal (distance >d(c)) indicates a contact hysteresis, which is caused by an energy barrier that separates the metastable states of the patterned configuration and the global minimum state of the flat film. The energy and the pull-off force are found to be nonequilibrium and nonunique properties depending on the initial contact, defects, noise, etc. Three broad pathways of debonding leading to adhesive failure of the interface, depending on the stiffness of the film, step size of withdrawal, and the imposed noise, are identified: a catastrophic column collapse mode, a peeling mode involving a continuous decrease in the contact area, and a column splitting mode. The first two modes are caused by a very high stress concentration near the cavity edges. These metastable patterned configurations engender pull-off forces that are orders of magnitude smaller than that required to separate two flat surfaces from contact.     

Schiff base complexes of dioxouranium(VI). VII. Dioxouranium(VI) acetate complexes with monobasic bidentate and bibasic tridentateSchiff bases

11 and 12 molar reactions of dioxouranium(VI) acetate dihydrate with the monobasic bidentateSchiff bases,o-HOC₆H₄CH=NR oro-HOC₁₀H₆CH=NR (R=C₂H₅,n-C₃H₇,n-C₄H₉ or C₆H₅) and bibasic tridentateSchiff bases,o-HOC₆H₄CH=NR(OH) oro-HOC₁₀H₆CH=NR(OH) (R=–CH₂CH(CH₃)- or —CH₂CH₂CH₂–) have been studied and derivates of the type UO₂(OAc)₂(SBH), UO₂(OAc)₂(SBH)₂, UO₂(OAc)₂(SBH ₂) and UO₂(OAc)₂(SBH ₂)₂ (whereSBH andSBH ₂ represent monobasic bidentate and bibasic tridentateSchiff base molecules respectively) have been isolated. These have been characterized by elemental analysis, conductance measurements and IR spectral studies.

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UO₂ ²⁺-Komplexe von Schiff-Basen. VII. Uranylacetat-Komplexe mit monobasischen zweizähnigen und bibasischen dreizähnigen Schiff-Basen

Zusammenfassung Es wurden in 1:1- und 1:2-molaren Reaktionen von UO₂(OAc)₂·2H₂O mitSchiff-Basen (L) Komplexe des Typs UO₂(OAc)₂ L bzw. UO₂(OAc)₂ L ₂ isoliert. Die Komplexe wurden mittels Elementaranalyse, Leitfähigkeitsmessungen und IR-Spektren untersucht.

     

Fermentation of “Quick Fiber” produced from a modified corn-milling process into ethanol and recovery of corn fiber oil

Approximately 9% of the 9.7 billion bushels of corn harvested in the United States was used for fuel ethanol production in 2002, half of which was prepared for fermentation by dry grinding. The University of Illinois has developed a modified dry grind process that allows recovery of the fiber fractions prior to fermentation. We report here on conversion of this fiber (Quick Fiber [QF]) to ethanol. QF was analyzed and found to contain 32%wt glucans and 65%wt total carbohydrates. QF was pretreated with dilute acid and converted into ethanol using either ethanologenic Escherichia coli strain FBR5 or Saccharomyces cerevisiae. For the bacterial fermentation the liquid fraction was fermented, and for the yeast fermentation both liquid and solids were fermented. For the bacterial fermentation, the final ethanol concentration was 30 g/L, a yield of 0.44 g ethanol/g of sugar(s) initially present in the hydrolysate, which is 85% of the theoretical yield. The ethanol yield with yeast was 0.096 gal/bu of processed corn assuming a QF yield of 3.04 lb/bu. The residuals from the fermentations were also evaluated as a source of corn fiber oil, which has value as a nutraceutical. Corn fiber oil yields were 8.28%wt for solids recovered following prtetreatment.     

Cycloadditions of 8,8-dicyanoheptafulvene to styrenes: manifestation of dual reactivity modes

A facile cycloaddition reaction of 8,8-dicyanoheptafulvene with styrenes leading to the corresponding [8+2] and [4+2] adducts in excellent yields is described.     

Cerium(IV) ammonium nitrate-mediated oxidative rearrangement of cyclobutanes and oxetanes

A facile CAN-mediated oxidative rearrangement of alkoxyaryl cyclobutanes and oxetanes is described.     

HPTLC Method for Quantification of Apigenin in the Dried Root Powder of Gmelina arborea Linn.

JPC – Journal of Planar Chromatography – Modern TLC - A sensitive high-performance thin-layer chromatographic method has been established for quantification of apigenin in dried root...     

Foldamer simulations: novel computational methods and applications to poly-phenylacetylene oligomers

We apply several methods to probe the ensemble kinetic and structural properties of a model system of poly-phenylacetylene (pPA) oligomer folding trajectories. The kinetic methods employed included a brute force accounting of conformations, a Markovian state matrix method, and a nonlinear least squares fit to a minimalist kinetic model used to extract the folding time. Each method gave similar measures for the folding time of the 12-mer chain, calculated to be on the order of 7 ns for the complete folding of the chain from an extended conformation. Utilizing both a linear and a nonlinear scaling relationship between the viscosity and the folding time to correct for a low simulation viscosity, we obtain an upper and a lower bound for the approximate folding time within the range 70 ns相似文献