Electric‐field‐controlled synthesis of HPMA hydrogels containing self‐organized arrays of micro‐channels

We report the synthesis of poly N‐(2‐hydroxypropyl)methacrylamide ordered arrays of fluid filled channels. The polymerization and crosslinking reactions are carried out under the influence of a constant electric field (60 V/cm). A charged comonomer, immobiline (pK 3.6), and porogen, polyethylene glycol (PEG) are added to the pregel solutions. Scanning electron microscopy reveals that the channels have a typical diameter of 2–25 μm and are oriented parallel to the electric field employed during synthesis. The self‐organization of channels occurs around an optimal PEG concentration of 8.6 wt/vol %, whereas significantly higher or lower concentrations yield random, isotropic pore structures. Moreover, tensile strength measurements show that the mechanical stability increases with decreasing concentration of PEG. Rheology experiments reveal that the swelling degree of these superabsorbant hydrogels increases with increasing PEG. Possible applications of these microstructured hydrogels as bidirectional scaffolds for regenerating neurons in the injured spinal cord are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2593–2600, 2007     

Cliques that are tolerance digraphs

In this paper, we study directed graph versions of tolerance graphs, in particular, the class of totally bounded bitolerance digraphs and several subclasses. When the underlying graph is complete, we prove that the classes of totally bounded bitolerance digraphs and interval catch digraphs are equal, and this implies a polynomial-time recognition algorithm for the former class. In addition, we give examples (whose underlying graphs are complete) to separate every other pair of subclasses, and one of these provides a counterexample to a conjecture of Maehara (1984).     

Single-crystal 55Mn NMR spectra of two Mn12 single-molecule magnets

The initial application is reported of single-crystal 55Mn NMR spectroscopy, and associated orientation dependence studies, to single-molecule magnets (SMMs). The studies were performed on two members of the Mn12 family of SMMs, [Mn12O12(O2CMe)16(H2O)4].2MeCO2H.4H2O (Mn12-Ac) and [Mn12O12(O2CCH2Br)16(H2O)4].4CH)Cl) (Mn12-BrAc). Single-crystal spectra give a dramatic improvement in the spectral resolution over oriented powder spectra, allowing the clear observation of quadrupolar splittings, the determination of quadrupole coupling parameters (e2qQ), and an assessment of the symmetry-lowering perturbation of the core of Mn12-Ac by hydrogen-bonding interactions with lattice solvate molecules of crystallization. The results emphasize the utility of single-crystal NMR studies to probe the cores of these magnetic molecules.     

Matrix screening of substituted N-aryl-1,8-naphthalimides reveals new dual fluorescent dyes and unusually bright pyridine derivatives

A 3 x 14 matrix of substituted N-aryl-1,8-naphthalimides was synthesized for the evaluation and discovery of dual fluorescence. Because of their unique photophysical properties, these dual fluorescent systems represent an exception to the widely studied TICT (Twisted Internal Charge Transfer) fluorescent dyes or tautomeric benzofluorescein class of two-color dyes. The matrix library was designed to investigate the effects of heterocycles, particularly pi-excessive and pi-deficient systems. Of the 42 compounds surveyed, five displayed well-resolved two-color emission in solvents as nonpolar as hexane. Based on the observed trends in fluorescence lambda(max) and quantum yield, a new model is proposed that predicts LW and SW emission for these systems. In addition, this model provides potential design features for the synthesis of new dual fluorescent species.     

Magnetic susceptibility and order parameter of the spin-glass-like phase of the double-exchange model

The magnetic susceptibility and Edwards-Anderson order parameter q of the spin-glass-like (SGL) phase of the double-exchange model are evaluated in the weak-coupling or RKKY limit. Dynamical mean-field theory is used to show that q = M(T/T(SGL))2, where M is the classical Brillouin function and T(SGL) is the SGL transition temperature. The correlation length of the SGL phase is determined by a correlation parameter Q that maximizes T(SGL) and minimizes the free energy. The magnetic susceptibility has a cusp at T(SGL) and reaches a nonzero value as T --> 0.     

Field asymmetric waveform ion mobility spectrometry studies of proteins: Dipole alignment in ion mobility spectrometry?

Approaches to separation and characterization of ions based on their mobilities in gases date back to the 1960s. Conventional ion mobility spectrometry (IMS) measures the absolute mobility, and field asymmetric waveform IMS (FAIMS) exploits the difference between mobilities at high and low electric fields. However, in all previous IMS and FAIMS experiments ions experienced an essentially free rotation; thus the separation was based on the orientationally averaged cross-sections Omega(avg) between ions and buffer gas molecules. Virtually all large ions are permanent electric dipoles that will be oriented by a sufficiently strong electric field. Under typical FAIMS conditions this will occur for dipole moments >400 D, found for many macroions including most proteins above approximately 30 kDa. Mobilities of aligned dipoles depend on directional cross-sections Omega(dir) (rather than Omega(avg)), which should have a major effect on FAIMS separation parameters. Here we report the FAIMS behavior of electrospray-ionization-generated ions for 10 proteins up to approximately 70 kDa. Those above 29 kDa exhibit a strong increase of mobility at high field, which is consistent with predicted ion dipole alignment. This effect expands the useful FAIMS separation power by an order of magnitude, allowing separation of up to approximately 10(2) distinct protein conformers and potentially revealing information about Omega(dir) and ion dipole moment that is of utility for structural characterization. Possible approaches to extending dipole alignment to smaller ions are discussed.     

Surface-assisted one-dimensional self-assembly of a perylene based semiconductor molecule

Chloroform-vapor annealing of thin films of propoxyethyl perylene tetracarboxylic diimide (PE-PTCDI, an n-type semiconductor) deposited on glass or mica leads to formation of well-defined one-dimensional self-assemblies (e.g. nanobelts), which show optically uniaxial properties as demonstrated by the linearly polarized emission.     

Microfluidic Device Using a Gold Pillar Array and Integrated Electrodes for On‐chip Endothelial Cell Immobilization,Direct RBC Contact,and Amperometric Detection of Nitric Oxide

We describe a microfluidic device that can be used to detect interactions between red blood cells (RBCs) and endothelial cells using a gold pillar array (created by electrodeposition) and an integrated detection electrode. Endothelial cells can release nitric oxide (NO) via stimulation by RBC‐derived ATP. These studies incorporate on‐chip endothelial cell immobilization, direct RBC contact, and detection of NO in a single microfluidic device. In order to study the RBC‐EC interactions, this work used a microfluidic device made of a PDMS chip with two adjacent channels and a polystyrene base with embedded electrodes for creating a membrane (via gold pillars) and detecting NO (at a glassy carbon electrode coated with platinum‐black and Nafion). RBCs were pharmacologically treated with treprostinil in the absence and presence of glybenclamide, and ATP release was determined as was the resultant NO release from endothelial cells. Treprostinil treatment of RBCs resulted in ATP release that stimulated endothelial cells to release on average 1.8±0.2 nM NO per endothelial cell (average±SEM, n=8). Pretreatment of RBCs with glybenclamide inhibited treprostinil‐induced ATP release and, therefore, less NO was produced by the endothelial cells (0.92±0.1 nM NO per endothelial cell, n=7). In the future, this device can be used to study interactions between many other cell types (both adherent and non‐adherent cell lines) and incorporate other detection schemes.