Assessing corn stover composition and sources of variability via NIRS

Corn stover, the above-ground, non-grain portion of the crop, is a large, currently available source of biomass that potentially could be collected as a biofuels feedstock. Biomass conversion process economics are directly affected by the overall biochemical conversion yield, which is assumed to be proportional to the carbohydrate content of the feedstock materials used in the process. Variability in the feedstock carbohydrate levels affects the maximum theoretical biofuels yield and may influence the optimum pretreatment or saccharification conditions. The aim of this study is to assess the extent to which commercial hybrid corn stover composition varies and begin to partition the variation among genetic, environmental, or annual influences. A rapid compositional analysis method using near-infrared spectroscopy/partial least squares multivariate modeling (NIR/PLS) was used to evaluate compositional variation among 508 commercial hybrid corn stover samples collected from 47 sites in eight Corn Belt states after the 2001, 2002, and 2003 harvests. The major components of the corn stover, reported as average (standard deviation) % dry weight, whole biomass basis, were glucan 31.9 (2.0), xylan 18.9 (1.3), solubles composite 17.9 (4.1), and lignin (corrected for protein) 13.3 (1.1). We observed wide variability in the major corn stover components. Much of the variation observed in the structural components (on a whole biomass basis) is due to the large variation found in the soluble components. Analysis of variance (ANOVA) showed that the harvest year had the strongest effect on corn stover compositional variation, followed by location and then variety. The NIR/PLS rapid analysis method used here is well suited to testing large numbers of samples, as tested in this study, and will support feedstock improvement and biofuels process research.     

Photoactive Analogs of Farnesyl Pyrophosphate Containing Benzoylbenzoate Esters: Synthesis and Application to Photoaffinity Labeling of Yeast Protein Farnesyltransferase

Farnesyl pyrophosphate (FPP) is involved in a large number of cellular processes including the prenylation of transforming mutants of Ras proteins implicated in cancer. Photoactive analogs could provide useful information about enzyme active sites that bind farnesyl pyrophosphate; however, the availability of such compounds is extremely limited. Molecules that incorporate benzophenone moieties are attractive photoaffinity labeling reagents because of their useful photochemical properties. Here, the syntheses of two compounds, 3a and 3b, containing para- and meta-substituted benzoylbenzoates are described. Compounds 3a and 3b are competitive inhibitors (with respect to FPP) of yeast protein farnesyltransferase (PFTase) with K(i) values of 910 and 380 nM, respectively. Both compounds inactivate PFTase upon photolysis, resulting in as much as 44% inactivation of enzyme activity. Photolysis of PFTase in the presence of [(32)P]3a or of [(32)P]3b results in preferential labeling of the beta subunit, suggesting that this subunit is involved in prenyl group recognition. These compounds should be valuable tools for studying enzymes that utilize FPP as a substrate.     

The system HCl+InCl3+H2O from 5 to 55°C: Application of Harned's rule

Electromotive-force measurements of cells containing hydrochloric acid and indium chloride have been made to determine the variation of the log of the activity coefficient of hydrochloric acid with change in the amount of indium chloride in the solution. The simpler Harned equations have been used to fit the data. The quadratic terms in the Harned equations for the activity coefficients of HCl in the salt mixtures are required for a good fit of the 968 experimental emf data points at all the experimental ionic strengths and temperatures. The more convenient Pitzer ion-interaction treatment of the data will be reported in a separate publication which will include the values of the Pitzer parameters for pure InCl₃(aq), and mixing parameters for H⁺–In⁺³ and H⁺–In⁺³–Cl^–. A comprehensive investigation on the mixed electrolyte solutions at 11 different constant total ionic strengths ranging from 0.05 to 3.5 mol-kg^–1 was made at 11 temperatures from 5 to 55°C using the cell without liquid junction of the type: Pt,H₂(g, 1 atm)|HCl(m _A)+InCl₃(m _B)+H₂O|AgCl,AG (A).     

Biomimetic nanostructures: creating a high-affinity zinc-binding site in a folded nonbiological polymer

One of the long-term goals in developing advanced biomaterials is to generate protein-like nanostructures and functions from a completely nonnatural polymer. Toward that end, we introduced a high-affinity zinc-binding function into a peptoid (N-substituted glycine polymer) two-helix bundle. Borrowing from well-understood zinc-binding motifs in proteins, thiol and imidazole moieties were positioned within the peptoid such that both helices must align in close proximity to form a binding site. We used fluorescence resonance energy transfer (FRET) reporter groups to measure the change of the distance between the two helical segments and to probe the binding of zinc. We systematically varied the position and number of zinc-binding residues, as well as the sequence and size of the loop that connects the two helical segments. We found that certain peptoid two-helix bundles bind zinc with nanomolar affinities and high selectivity compared to other divalent metal ions. Our work is a significant step toward generating biomimetic nanostructures with enzyme-like functions.     

Solution structure of a DNA duplex containing a guanine-difluorotoluene pair: a wobble pair without hydrogen bonding?

The incorporation of synthetic nucleoside analogues into DNA duplexes provides a unique opportunity to probe both structure and function of nucleic acids. We used 1H and 19F NMR and molecular dynamics calculations to determine the solution structures of two similar DNA decamer duplexes, one containing a central G-T mismatched or "wobble" base pair, and one in which the thymine in this base pair is replaced by difluorotoluene (a thymine isostere) creating a G-F pair. Here, we show that the non-hydrogen-bonding G-F pair stacks relatively well into the helix and that the distortions caused by each non-Watson-Crick G-T or G-F base pair are quite localized to a three base pair site around the mismatch. A detailed structural analysis reveals that the absence of hydrogen bonding introduces more dynamic motion into the G-F pair relative to G-T and permits the G-F pair to exhibit stacking and conformational features characteristic of both a Watson-Crick base pair (on the guanine containing strand) and a wobble base pair (on the strand containing the difluorotoluene). We used these results to posit a rationale for recognition and repair of mismatch sites in DNA.     

A General Strategy for Stretchable Microwave Antenna Systems using Serpentine Mesh Layouts

Wireless functionality is essential for the implementation of wearable systems, but its adaptation in stretchable electronic systems has had limited success. In this paper, the electromagnetic properties of stretchable serpentine mesh‐based systems is studied, and this general strategy is used to produce high‐performance stretchable microwave systems. Stretchable mechanics are enabled by converting solid metallic sections in conventional systems to subwavelength‐scale serpentine meshes, followed by bonding to an elastomeric substrate. Compared to prior implementations of serpentine meshes in microwave systems, this conversion process is extended to arbitrary planar layouts, including those containing curvilinear shapes. A detailed theoretical analysis is also performed and a natural tradeoff is quantified between the stretching mechanics and microwave performance of these systems. To explore the translation of these concepts from theory to experiment, two types of stretchable microwave devices are fabricated and characterized: a stretchable far‐field dipole antenna for communications and a stretchable midfield phased surface for the wireless powering of biomedical implanted devices.     

A dynamic benchmarking system for assessing the recovery of inpatients: Evidence from the neurorehabilitation process

The shortage of medical resources (mainly beds) is a critical and increasingly prevalent problem affecting hospitals. Of the factors that contribute to these shortages, the ambiguity and insufficiency of the criteria used to identify whether an inpatient should be discharged are among the most detrimental. To address this issue, this study applies data envelopment analysis (DEA) on existing inpatient data from the Neurorehabilitation Center at Toronto’s Bridgepoint Hospital to create a dynamic benchmarking system to evaluate the health stage of an inpatient ready to be discharged. Unlike the more traditional parametric techniques, DEA provides non-subjective benchmarking that does not require any prior specification of the production function making it a more desirable choice for this application. The dynamic model categorizes the inpatient’s discharge status as rejected, under observation, or approved. This new approach not only allows managers to gain insight into the potential causes of medical resource shortages, but also allows clinicians to treat inpatients more effectively based on their discharge categories. For validation, the results of the dynamic model were compared with actual inpatient discharge assessments provided by the Bridgepoint Hospital.     

Activity Coefficients of Individual Ions from Titration Data

It is shown that the activity coefficients of the anions resulting from the dissociation of a weak polyprotic acid can be obtained from titration data. Activity coefficients are determined in terms of the activity coefficient of the undissociated acid. The extracted activity coefficients are also dependent on the pH scale adopted in the titration process and are considered as operational coefficients. The computational procedure uses an exact equation representing the titration curve and a nonlinear least-squares fitting procedure. As an illustration, the activity coefficients of the anions of succinic acid are determined. The method also allows study of the variation of the activity coefficients with the ionic strength in a straightforward manner.     

Location with acceleration–deceleration distance

In this paper we investigate a model where travel time is not necessarily proportional to the distance. Every trip starts at speed zero, then the vehicle accelerates to a cruising speed, stays at the cruising speed for a portion of the trip and then decelerates back to a speed of zero. We define a time equivalent distance which is equal to the travel time multiplied by the cruising speed. This time equivalent distance is referred to as the acceleration–deceleration (A–D) distance. We prove that every demand point is a local minimum for the Weber problem defined by travel time rather than distance. We propose a heuristic approach employing the generalized Weiszfeld algorithm and an optimal approach applying the Big Triangle Small Triangle global optimization method. These two approaches are very efficient and problems of 10,000 demand points are solved in about 0.015 seconds by the generalized Weiszfeld algorithm and in about 1 minute by the BTST technique. When the generalized Weiszfeld algorithm was repeated 1000 times, the optimal solution was found at least once for all test problems.     

Directional approach to gradual cover: a maximin objective

The objective of original cover location models is to cover demand within a given distance by facilities. Locating a given number of facilities to cover as much demand as possible is referred to as max-cover, and finding the minimum number of facilities required to cover all the demand is referred to as set covering. When the objective is to maximize the minimum cover of demand points, the maximin objective is equivalent to set covering because each demand point is either covered or not. The gradual (or partial) cover replaces abrupt drop from full cover to no cover by defining gradual decline in cover. Both maximizing total cover and maximizing the minimum cover are useful objectives using the gradual cover measure. In this paper we use a recently proposed rule for calculating the joint cover of a demand point by several facilities termed “directional gradual cover”. The objective is to maximize the minimum cover of demand points. The solution approaches were extensively tested on a case study of covering Orange County, California.