Nitro- and fluoropolyformals. III. Copolyformals from mixtures of fluoro- and nitro-α,ω-diols

Polyformals of fluoro-, nitramine-, and C-nitrodiols show widely differing properties with respect to glass transition temperature, melting transition, and solubility. Polymers with desirable combinations of these properties, e.g., low T_g, high nitro content, and good solubility in polar solvents, were expected to result from acid-promoted copolycondensation of appropriate mixtures of diols with formaldehyde. A series of such condensations were carried out and the polymers obtained from binary mixtures of fluoro- and nitrodiols, different nitrodiols, and fluoro- or nitrodiols and carboranediols, were characterized by GPC, ¹H-NMR, and DSC analysis.     

Cellulose synthesis in maize: isolation and expression analysis of the cellulose synthase (CesA) gene family

Stalk lodging in maize results in significant yield losses. We have determined that cellulose per unit length of the stalk is the primary determinant of internodal strength. An increase in cellulose concentration in the wall might allow simultaneous improvements in stalk strength and harvest index. Cellulose formation in plants can be perturbed by mutations in the genes involved in cellulose synthesis, post-synthetic cellulose alteration or deposition, N-glycosylation, and some other genes with as yet unknown functions. We have isolated 12 members of the cellulose synthase (CesA) gene family from maize. The genes involved in primary wall formation appear to have duplicated relatively independently in dicots and monocots. The deduced amino acid sequences of three of the maize genes, ZmCesA10–12, cluster with the Arabidopsis CesA sequences that have been shown to be involved in secondary wall formation. Based on their expression patterns across multiple tissues, these three genes appear to be coordinately expressed. The remaining genes show overlapping expression to varying degrees with ZmCesA1, 7, and 8 forming one group, ZmCesA3 and 5 a second group, and ZmCesA2 and 6 exhibiting independent expression of any other gene. This suggests that the varying levels of coexpression may just be incidental except in the case of ZmCesA10–12, which may interact with each other to form a functional enzyme complex. Isolation of the expressed CesA genes from maize and their association with primary or secondary wall formation has made it possible to test their respective roles in cellulose synthesis through mutational genetics or transgenic approaches. This information would be useful in improving stalk strength.     

Characterization of etched electrochemical detection for electrophoresis in micron inner diameter capillaries

An enhanced etched electrochemical (EC) detection technique has been developed for CE in micron inner diameter capillaries. The design improvements allow for better alignment between the capillary bore and the electrode. This new method involves utilizing a carbon fiber microelectrode and etching both the carbon fiber and the detection end of a micrometer-sized inner diameter capillary to limit dead volume and analyte diffusion at the amperometric EC detector. To understand the factors affecting enhanced detector efficiency, a detailed examination of the relationship between detector design and performance has been completed by exploring the effects of varying electrode diameter, tip shape, and size, in addition to the etch length of the capillary outlet. The enhanced detection provides peak efficiencies as high as 75000 theoretical plates and estimated detection limits as low as 40 nM for dopamine. This etched detection method should further facilitate volume-limited sample analysis by CE.     

Separation of polar and non-polar analytes using dimethyl sulfoxide-modified subcritical water

Separations using methanol–water or acetonitrile–water mixtures at different temperatures have been well investigated in reversed-phase liquid chromatography. However, reversed-phase separation with dimethyl sulfoxide (DMSO)–water mixtures is much less studied. In this work, separations of polyhydroxybenzenes, phenol derivatives, benzene, toluene, ethylbenzene, and xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs) with DMSO-modified subcritical water were performed at several temperatures to evaluate the effect of temperature on the elution strength of DMSO–water mixtures. The column efficiency obtained by using DMSO-modified subcritical water was also studied. Finally, the resolution of ethylbenzene and p-xylene was investigated.     

Trace element analysis of some shaving powders commonly marketed in Nigeria using instrumental neutron activation analysis

Instrumental neutron activation analysis (INAA) technique has been employed viak ₀ approximation method to determine elemental composition of five shaving powders commonly marketed in Nigeria. Fe displayed the highest concentrations in the range 1000–2000 g·g^–1. Na and Zn concentrations were established in the range 200–400 g·g^–1. Heavy elements like Ga, La, Cr, Co, Ag, Ce and Nd concentrations were noted in the lower range of 1–10 g·g^–1 Br, As, Sb, Sm, Eu, W, Cs, Tb, Yb, Hf, Ta, Th and U concentrations were established in even lower traces in the <1 g·g^–1 range. Results obtained for a certified reference material, CANMET BL-1 and CERT (in house) Kaolin standard compared favourably with the literature values thus establishing the results presented for the shaving powders.     

Double silyl migration converting ORe[N(SiMe(2)CH(2)PCy(2))(2)] to NRe[O(SiMe(2)CH(2)PCy(2))(2)] substructures

The reaction of (R(2)PCH(2)SiMe(2))(2)NM (PNP(R)M; R = Cy; M = Li, Na, MgHal, Ag) with L(2)ReOX(3) [L(2) = (Ph(3)P)(2) or (Ph(3)PO)(Me(2)S); X = Cl, Br] gives (PNP(Cy))ReOX(2) as two isomers, mer,trans and mer,cis. These compounds undergo a double Si migration from N to O at 90 degrees C to form (POP(Cy))ReNX(2) as a mixture of mer,trans and fac,cis isomers. Additional thermolysis effects migration of CH(3) from Si to Re, along with compensating migration of halide from Re to Si. DFT calculations on various structural isomers support the greater thermodynamic stability of the POP/ReN isomer vs PNP/ReO and highlight the influence of the template effect on the reactivities of these species.     

Aromatic vs aliphatic C-H cleavage of alkyl-substituted pyridines by (PNPiPr)Re compounds

Both (PNP)Re(H)(4) and (PNP)ReH(cyclooctyne) (PNP(i)(Pr) = ((i)Pr(2)PCH(2)SiMe(2))(2)N) react with alkylpyridines NC(5)H(4)R to give first (PNP)ReH(2)(eta(2)-pyridyl) and cyclooctene and then, when not sterically blocked, (PNP)Re(eta(2)-pyridyl)(2) and cyclooctane. The latter are shown by NMR, X-ray diffraction, and DFT calculations to have several energetically competitive isomeric structures and pyridyl N donation in preference to PNP amide pi-donation. DFT studies support NMR solution evidence that the most stable bis pyridyl structure is one that is doubly eta(2)- with the pyridyl N donating to the metal center. When both ortho positions carry methyl substituents, cyclooctane and the carbyne complex (PNP)ReH(tbd1;C-pyridyl) are produced. Excess 2-vinyl pyridine reacts with (PNP)Re(H)(4) preferentially at the vinyl group, to give 2-ethyl pyridine and the sigma-vinyl complex (PNP)ReH[eta(2)-CH=CH(2-py)]. The DFT and X-ray structures show, by various comparisons, the ability of the PNP amide nitrogen to pi-donate to an otherwise unsaturated d(4) Re(III) center, showing short Re-N distances consistent with the presence of pi-donation.     

Capillary electrophoresis of single mammalian cells

Capillary electrophoresis (CE) has been established as powerful tool for single cell analysis. Newly developed sampling, separation and detection methods have allowed the investigation of single mammalian cells with CE despite their small size and complex composition. Advances in sample injection techniques include several novel methods for the injection of whole cells and sampling techniques for the study of cellular secretion. CE of single mammalian cells has been applied in a wide range of fields including protein analysis, neuroscience, and oncology. The development of new detection schemes in the analysis of single mammalian cells with CE has included studies of protein expression and the utilization of mass spectrometric and electrochemical detection. Subcellular mammalian cell analysis with CE also has been investigated.     

Effects of digestion,chemical separation,and deposition on Po-210 quantitative analysis

The purpose of this work was to determine polonium losses from a variety of sample types (soil, cotton fiber, and air filter) due to digestion technique, chemical separation, and deposition method for alpha energy analysis. Results demonstrated that yields from a perchloric acid wet-ash (87 ± 5 %) were similar to that from a microwave digestion (100 ± 7 %), but both were greater than the dry-ash procedure (38 ± 5 %). The polonium was separated from an SRM soil using an AG1X8 ion exchange column and deposited on a Ag disk with a recovery of 83 ± 7 % of polonium-209 (Po-209). Deposition yields without chemical separation averaged 90 ± 5 % of Po-209. The polonium-210 content was successfully measured in the three matrix types and quantitated using alpha spectroscopy.     

Would weighted-student funding enhance intra-district equity in Texas? A simulation using DEA

We use data envelopment analysis to model the educational production function, and then explore how a shift to weighted student funding using the student weights embedded in the Texas School Finance Formula would alter the allocation of inputs and potential outputs. School outputs are measured as value-added reading and math scores on standard achievement tests. We find that if school districts allocated their resources efficiently, then they would not allocate their resources to campuses according to the funding model weights. Policies that promote greater efficiency would also enhance equity in educational outcomes.