Secondary Interactions or Ligand Scrambling? Subtle Steric Effects Govern the Iridium(I) Coordination Chemistry of Phosphoramidite Ligands

The like and unlike isomers of phosphoramidite (P*) ligands are found to react differently with iridium(I), which is a key to explaining the apparently inconsistent results obtained by us and other research groups in a variety of catalytic reactions. Thus, the unlike diastereoisomer (aR,S,S)‐[IrCl(cod)( 1 a )] ( 2 a ; cod=1,5‐cyclooctadiene, 1 a =(aR,S,S)‐(1,1′‐binaphthalene)‐2,2′‐diyl bis(1‐phenylethyl)phosphoramidite) forms, upon chloride abstraction, the monosubstituted complex (aR,S,S)‐[Ir(cod)(1,2‐η‐ 1 a ,κP)]⁺ ( 3 a ), which contains a chelating P* ligand that features an η² interaction between a dangling phenyl group and iridium. Under analogous conditions, the like analogue (aR,R,R)‐ 1 a′ gives the disubstituted species (aR,R,R)‐[Ir(cod)( 1 a′ ,κP)₂]⁺ ( 4 a′ ) with monodentate P* ligands. The structure of 3 a was assessed by a combination of X‐ray and NMR spectroscopic studies, which indicate that it is the configuration of the binaphthol moiety (and not that of the dangling benzyl N groups) that determines the configuration of the complex. The effect of the relative configuration of the P* ligand on its iridium(I) coordination chemistry is discussed in the context of our preliminary catalytic results and of apparently random results obtained by other groups in the iridium(I)‐catalyzed asymmetric allylic alkylation of allylic acetates and in rhodium(I)‐catalyzed asymmetric cycloaddition reactions. Further studies with the unlike ligand (aS,R,R)‐(1,1′‐binaphthalene)‐2,2′‐diyl bis{[1‐(1‐naphthalene‐1‐yl)ethyl]phosphoramidite} ( 1 b ) showed a yet different coordination mode, that is, the η⁴‐arene–metal interaction in (aS,R,R)‐[Ir(cod)(1,2,3,4‐η‐ 1 b ,κP)]⁺ ( 3 b ).     

Vibrational spectroscopy differentiates between multipotent and pluripotent stem cells

Over the last few years, there has been an increased interest in the study of stem cells in biomedicine for therapeutic use and as a source for healing diseased or injured organs/tissues. More recently, vibrational spectroscopy has been applied to study stem cell differentiation. In this study, we have used both synchrotron based FTIR and Raman microspectroscopies to assess possible differences between human pluripotent (embryonic) and multipotent (adult mesenchymal) stem cells, and how O(2) concentration in cell culture could affect the spectral signatures of these cells. Our work shows that infrared spectroscopy of embryonic (pluripotent) and adult mesenchymal (multipotent) stem cells have different spectral signatures based on the amount of lipids in their cytoplasm (confirmed with cytological staining). Furthermore, O(2) concentration in cell culture causes changes in both the FTIR and Raman spectra of embryonic stem cells. These results show that embryonic stem cells might be more sensitive to O(2) concentration when compared to mesenchymal stem cells. While vibrational spectroscopy could therefore be of potential use in identifying different populations of stem cells further work is required to better understand these differences.     

Macromolecular Diffusion in Self-Assembling Biodegradable Thermosensitive Hydrogels

Hydrogel formation triggered by a change in temperature is an attractive mechanism for in situ gelling biomaterials for pharmaceutical applications such as the delivery of therapeutic proteins. In this study, hydrogels were prepared from ABA triblock polymers having thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) flanking A-blocks and hydrophilic poly(ethylene glycol) B-blocks. Polymers with fixed length A blocks (~22 kDA) but differing PEG-midblock lengths (2, 4 and 10 kDa) were synthesized and dissolved in water with dilute fluorescein isothiocyanate (FITC)-labeled dextrans (70 and 500 kDA). Hydrogels encapsulating the dextrans were formed by raising the temperature. Fluorescence recovery after photobleaching (FRAP) studies showed that diffusion coefficients and mobile fractions of the dextran dyes decreased upon elevating temperatures above 25 °C. Confocal laser scanning microscopy and cryo-SEM demonstrated that hydrogel structure depended on PEG block length. Phase separation into polymer-rich and water-rich domains occurred to a larger extent for polymers with small PEG blocks compared to polymers with a larger PEG block. By changing the PEG block length and thereby the hydrogel structure, mobility of FITC-dextran could be tailored. At physiological pH the hydrogels degraded over time by ester hydrolysis, resulting in increased mobility of the encapsulated dye. Since diffusion can be controlled according to polymer design and concentration, plus temperature, these biocompatible hydrogels are attractive as potential in situ gelling biodegradable materials for macromolecular drug delivery.     

Biofuel Combustion Chemistry: From Ethanol to Biodiesel

Biofuels, such as bio‐ethanol, bio‐butanol, and biodiesel, are of increasing interest as alternatives to petroleum‐based transportation fuels because they offer the long‐term promise of fuel‐source regenerability and reduced climatic impact. Current discussions emphasize the processes to make such alternative fuels and fuel additives, the compatibility of these substances with current fuel‐delivery infrastructure and engine performance, and the competition between biofuel and food production. However, the combustion chemistry of the compounds that constitute typical biofuels, including alcohols, ethers, and esters, has not received similar public attention. Herein we highlight some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels. The discussion focuses on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions, with an emphasis on transportation fuels. New insights into the vastly diverse and complex chemical reaction networks of biofuel combustion are enabled by recent experimental investigations and complementary combustion modeling. Understanding key elements of this chemistry is an important step towards the intelligent selection of next‐generation alternative fuels.     

Signature of local motion in the microwave sky

For observers moving with respect to the cosmic rest frame, the microwave background temperature fluctuations will no longer be statistically isotropic. Aside from the familiar temperature dipole, an observer's velocity will also induce changes in the temperature angular correlation function and create nonzero off-diagonal correlations between multipole moments. We show that both of these effects should be detectable in future full-sky maps from the Planck satellite, and can constrain modifications of the standard cosmological model proposed to explain anomalous current observations.     

Increase of both order and disorder in the first hydration shell with increasing solute polarity

Monte?Carlo simulations of a small model solute in an aqueous solution are used to examine the effects of solute polarity on hydration structure. A judicious definition of the orientational order parameter leads to reinterpretation of the conventional picture of hydration. As the solute varies from hydrophobic to hydrophilic the ordered first shell water simultaneously fractionates into a more highly ordered and a more disordered component. The hydrogen-bond network rearranges such that the more ordered component relaxes to configurations of optimal intermolecular angles, the other fraction being released from the network.     

Determination of the Molar-Mass Averages of Random Poly(aspartate-co-lactide) Copolymers by Tuning the Ionic Strength of the Solvent

Water-soluble sodium poly(aspartate-co-lactide) (PALNa) copolymers with a molar ratio of aspartate-to-lactide units equal to 1:0.6, 1:1.0 and 1:1.5 were studied using NMR spectroscopy to determine the composition as well as SEC-MALS and static light-scattering measurements to determine the molar-mass characteristics of the copolymers. In the copolymer aqueous solutions, high-molar-mass species were detected, most probably due to the incomplete dissolution of the samples. The molar-mass averages determined in water with added simple electrolyte, i.e., NaCl, were much lower than the values determined in pure water. The concentration of the salt, which allows dissolution on a molecular level, and the separation predominantly according to a size-exclusion mechanism depend on the chemical composition of the PALNa copolymers. The optimal mobile phase for the PALNa-1/0.6 and the PALNa-1/1.0 copolymers was 0.1 M NaCl at pH 9, and for the PALNa-1/1.5 copolymer with a higher content of lactide units it was 0.05 M NaCl at pH 9. The molar-mass averages of the PALNa-1/1.0 copolymer, determined by SEC-MALS and static light-scattering measurements, were comparable.

     

On the estimation of optimal batch sizes in the analysis of simulation output

The estimation of the variance of point estimators is a classical problem of stochastic simulation. A more specific problem addresses the estimation of the variance of a sample mean from a steady-state autocorrelated process. Many proposed estimators of the variance of the sample mean are parameterized by batch size. A critical problem is to find an appropriate batch size that provides a good tradeoff between bias and variance. This paper proposes a procedure for determining the optimal batch size to minimize the mean squared error of estimators of the variance of the sample mean. This paper also presents the results of empirical studies of the procedure. The experiments involve symmetric two-state Markov chain models, first-order autoregressive processes, seasonal autoregressive processes, and queue-waiting times for several M/M/1 queueing models. The empirical results indicate that the estimation procedure works nearly as well as it would if the parameters of the processes were known.