Pretreatment of yellow poplar sawdust by pressure cooking in water

The pretreatment of yellow poplar wood sawdust using liquid water at temperatures above 220°C enhances enzyme hydrolysis. This paper reviews our prior research and describes the laboratory reactor system currently in use for cooking wood sawdust at temperatures ranging from 220 to 260°C. The wood sawdust at a 6–6.6% solid/liquid slurry was treated in a 2 L, 304 SS, Parr reactor with three turbine propeller agitators and a proportional integral derivative (PID) controller, which controlled temperature within ±1°C. Heat-up times to the final temperatures of 220, 240, or 260°C were achieved in 60–70 min. Hold time at the final temperature was less than 1 min. A serpentine cooling coil, through which tap water was circulated at the completion of the run, cooled the reactor’s contents within 3 min after the maximum temperature was attained. A bottoms port, as well as ports in the reactor’s head plate, facilitated sampling of the slurry and measuring the pH, which changes from an initial value of 5 before cooking to a value of approx 3 after cooking. Enzyme hydrolysis gave 80–90% conversion of cellulose in the pretreated wood to glucose. Simultaneous saccharification and fermentation of washed, pretreated lignocellulose gave an ethanol yield that was 55% of theoretical. Untreated wood sawdust gave less than 5% hydrolysis under the same conditions.     

Convergent stereocontrol in peterson olefinations. Application to the synthesis of (+/-)-3-hydroxybakuchiol and corylifolin

The iron-catalyzed Kirmse reaction was used to generate neopentyl alpha-silyl thioethers that were elaborated to meroterpenes using two complementary routes: one route involved a sila-Pummerer rearrangement, and the other route involved a Peterson olefination. While severe eclipsing interactions undermined the efficiency of the stereospecific sila-Pummerer rearrangement, they made it possible to stereoselectively generate E olefins without isolation or separation of syn- and anti-beta-silyl alkoxides. Addition of a neopentyl alpha-silyl alkyllithium intermediate to an aryl aldehyde generated a mixture of syn- and anti-beta-silyl alkoxides. The syn-beta-silyl alkoxide eliminated stereospecifically at -78 degrees C to give an E olefin, whereas the anti-beta-silyl alkoxide was unreactive. The reaction mixture was then acidified and heated to induce stereospecific elimination of the anti isomer to give the same E olefin via a complementary cationic pathway. This route was used to complete the first synthesis of the meroterpene (+/-)-3-hydroxybakuchiol. In addition, we synthesized another meroterpene corresponding to the natural product corylifolin and offer evidence that the structure of corylifolin was misassigned.     

Limit linear series: Basic theory

In this paper we introduce techniques for handling the degeneration of linear series on smooth curves as the curves degenerate to a certain type of reducible curves, curves of compact type. The technically much simpler special case of 1-dimensional series was developed by Beauville [2], Knudsen [21–23], Harris and Mumford [17], in the guise of “admissible covers”. It has proved very useful for studying the Moduli space of curves (the above papers and Harris [16]) and the simplest sorts of Weierstrass points (Diaz [4]). With our extended tools we are able to prove, for example, that:

1. The Moduli spaceM _g of curves of genusg has general type forg≧24, and has Kodaira dimension ≧1 forg=23, extending and simplifying the work of Harris and Mumford [17] and Harris [16].
2. Given a Weierstrass semigroup Γ of genusg and weightw≦g/2 (and in a somewhat more general case) there exists at least one component of the subvariety ofM _g of curves possessing a Weierstrass point of semigroup Γ which has the “expected” dimension 3g-2?w (and in particular, this set is not empty).
3. The fundamental group of the space of smooth genusg curves having distinct “ordinary” Weierstrass points acts on the Weierstrass points by monodromy as the full symmetric group.
4. Ifr andd are chosen so that $$\rho : = g - (r + 1)(g - d + r) = 0,$$ then the general curve of genusg has a certain finite number ofg _d ^r’ s [15, 20]. We show that the family of all these, allowing the curve to vary among general curves, is irreducible, so that the monodromy of this family acts transitively. If4=1, we show further that the monodromy acts as the full symmetric group.
5. Ifr andd are chosen so that $$\rho = - 1,$$ then the subvariety ofM _g consisting of curves posessing ag _d ^r has exactly one irreducible component of codimension 1.
6. For anyr, g, d such that ρ≦0, the subvariety ofM _g consisting of curves possessing ag _d ^r has at least one irreducible component of codimension—ρ so long as $$\rho \geqq \left\{ \begin{gathered} - g + r + 3 (r odd) \hfill \\ - \frac{r}{{r + 2}}g + r + 3 (r even). \hfill \\ \end{gathered} \right.$$

In this paper we present the basic theory of “limit linear series” necessary for proving these results. The results themselves will be taken up in our forthcoming papers [8-12]. Simpler applications, not requiring the tools developed in this paper but perhaps clarified by them, have already been given in our papers [5-7].     

2.2](4,4′) benzophenono (2,6) naphthalenophane: synthesis,structure, and spectroscopic study

The synthesis of [2.2](4,4′) benzophenono (2,6) naphthalenophane (1), the parent member of a series of stacked sensitizer-acceptor cyclophanes, is reported along with its x-ray structure and the absorption and emission spectra.     

Focal points and bargaining

This is a contribution to the growing experimental literature on how trial-and-error adjustment processes can establish a convention for coordination on an equilibrium in a game. A simple bargaining game introduced by Nash is used for this purpose. Subjects are conditioned in different treatments to use four different bargaining solutions. The stability of the conditioning is then studied as the bargaining game is played over an extended period. The data obtained is unusually sharp. In the long run, the median subject behaves as though optimizing often down to a fraction of a penny. The results are therefore not supportive of the view that strategic considerations in such situations can be neglected in favor of a study of fairness norms. Indeed, the equilibrium actually achieved in a session turns out to be a very good predictor of what the median subject says is fair in the game after play is over.We are grateful to the National Science Foundation for funding the experiments reported in this paper under Grant NSF-SES-8821521. We also gratefully acknowledge funding from the University of Michigan to set up the Michigan Economics Laboratory, where the experiments were conducted. We would also like to thank Richard Stallman and the Free Software Foundation for developing EMACS, Luke Tierney for developing LISPSTAT, and Hal Varian for showing us how to use both.     

Effect of surface charge of carbonate-containing aluminum hydroxide on particle interactions in aqueous suspensions

The area under the curve (AUC) of the modified Lorentzian power spectrum as determined by fiber optic Doppler anemometry (FODA) is directly related to the number of freely diffusing particles in suspension. The initiation of particle interactions is characterized by deviation from a linear volume fraction-AUC relationship. The AUC approaches zero when an extensive particle network forms which dampens the random motion of particles. The rheological behavior supports this conclusion as a yield value was first noted when the AUC approached 0. The ability of AUC to monitor particle interactions was confirmed by a decrease in AUC when a latex dispersion was flocculated by NaCl, CaCl₂, or AlCl₃. Both the volume fraction at which particle interactions were initiated, φ_d, and the volume fraction at which particle random motion was dampened, φ_c, decreased when the pH of an aluminum hydroxide suspension was adjusted closer to the point of zero charge. The AUC was useful in studying the disaggregation of an aluminum hydroxide suspension by shear. Shear was found to also produce aggregation under specific conditions of surface charge and volume fraction. The reversibility of shear-induced changes in particle interactions was studied and the conditions of surface charge and volume fraction which control the reversibility of the particle structures were defined.     

Comparison of dodecoxycarbonylvaline microemulsion, solvent-modified micellar and micellar pseudostationary phases for the chiral analysis of pharmaceutical compounds

A direct comparison of dodecoxycarbonylvaline (DDCV) microemulsion, micellar and butanol-modified micellar aggregate systems was performed employing both 2 and 4% DDCV. With respect to either DDCV concentration, use of the micellar system provided the largest elution range, followed by the butanol-modified micellar system and ultimately the microemulsion. Using 2% DDCV, all three aggregate analyses yielded similar values for enantioselectivity, resolution and retention factors that were slightly better using the micellar phase, but efficiencies were consistently better using either the microemulsion or butanol-modified micellar phases. Largely, the microemulsion and butanol-modified micellar phases behaved fairly similar, although use of the butanol-modified micelle provided resolution and efficiency that were slightly better for all but two of the compounds. While reasonable separations were achieved using 2% DDCV, the results using 4% DDCV for the microemulsion system were far superior. Analyses using analogous micellar and butanol-modified micellar aggregates were unstable, making them unsuitable for use at that surfactant concentration.     

Structurally Diverse Boron–Nitrogen Heterocycles from an N2O23− Formazanate Ligand

Five new compounds comprised of unprecedented boron–nitrogen heterocycles have been isolated from a single reaction of a potentially tetradentate N₂O₂³⁻ formazanate ligand with BF₃⋅OEt₂ and NEt₃. Optimized yields for each product were obtained through variation of experimental conditions and rationalized in terms of relative Gibbs free energies of the products as determined by electronic structure calculations. Chemical reduction of two of these compounds resulted in the formation of a stable anion, radical anion, and diradical dianion. Structural and electronic properties of this new family of redox-active heterocycles were characterized using UV/vis absorption spectroscopy, cyclic voltammetry and X-ray crystallography.     

Synthesis of structurally diverse biflavonoids

Synthetic biflavonoids are associated with interesting biological activities, yet they remain poorly explored within drug discovery. Recent years have witnessed a growing interest in synthetic approaches that can provide access to structurally novel biflavonoids so that the biological usefulness of this compound class can be more fully investigated. Herein, we report upon the exploration of strategies based around Suzuki-Miyaura cross-coupling and alcohol methylenation for the synthesis of two classes of biflavonoids: (i) rare ‘hybrid’ derivatives containing flavonoid monomers belonging to different subclasses, and (ii) homodimeric compounds in which the two flavonoid monomers are linked by a methylenedioxy group. Application of these strategies enabled the preparation of a structurally diverse collection of novel biflavonoids from readily-available starting materials, thereby facilitating the probing of uncharted regions of biologically interesting chemical space.     

Artificial Rydberg atom

We analyze bound states of an electron in the field of a positively charged nanoshell. We find that the binding and excitation energies of the system decrease when the radius of the nanoshell increases. We also show that the ground and the first excited states of this system have remarkably the same properties of the highly excited Rydberg states of a hydrogen-like atom, i.e., a high sensitivity to the external perturbations and long radiative lifetimes.