Practical synthesis of 2-keto-3-deoxy-D-glycero-D-galactononulosonic acid (KDN)

Reaction of propargylmagnesium bromide with 2,3;5,6-di-O-isopropylidene-D-mannonolactone followed by highly stereoselective reduction of the so-formed lactol with sodium borohydride gives a syn-diol from which practical syntheses of 2-keto-3-deoxy-D-glycero-D-galactononulosonic acid (KDN) and various partially protected derivatives have been achieved all of which feature the oxidative unmasking of the α-keto acid moiety from the alkyne.     

A high-throughput microfluidic assay to study neurite response to growth factor gradients

Studying neurite guidance by diffusible or substrate bound gradients is challenging with current techniques. In this study, we present the design, fabrication and utility of a microfluidic device to study neurite guidance under chemogradients. Experimental and computational studies demonstrated the establishment of a steep gradient of guidance cue within 30 min and stable for up to 48 h. The gradient was found to be insensitive to external perturbations such as media change and movement of device. The effects of netrin-1 (0.1-10 μg mL(-1)) and brain pulp (0.1 μL mL(-1)) were evaluated for their chemoattractive potential on neurite turning, while slit-2 (62.5 or 250 ng mL(-1)) was studied for its chemorepellant properties. Hippocampal or dorsal root ganglion (DRG) neurons were seeded into a micro-channel and packed onto the surface of a 3D collagen gel. Neurites grew into the matrix in three dimensions, and a gradient of guidance cue was created orthogonal to the direction of neurite growth to impact guidance. The average turning angle of each neurite was measured and averaged across multiple devices cultured under similar conditions to quantify the effect of guidance cue gradient. Significant positive turning towards gradient was measured in the presence of brain pulp and netrin-1 (1 μg mL(-1)), relative to control cultures which received no external guidance cue (p < 0.001). Netrin-1 released from transfected fibroblasts had the most positive turning effect of all the chemoattractive cues tested (p < 0.001). Slit-2 exhibited strong chemorepellant characteristics on both hippocampal and DRG neurite guidance at 250 ng mL(-1) concentration. Slit-2 also showed similar behavior on DRG neuron invasion into 3D collagen gel (p < 0.01 relative to control cultures). Taken together, the results suggest the utility of this microfluidic device to generate stable chemogradients for studying neurobiology, cell migration and proliferation, matrix remodeling and co-cultures with other cell lines, with potential applications in cancer biology, tissue engineering and regenerative medicine.     

Structural characteristics of some metallo-organic discogens

We have recently analysed the crystal and molecular structures of six metalloorganic discogens with substituted β-diketone ligands. The molecules consist of a rigid 11 atom core and a fringe made up of four phenyl rings substituted with alkyl/alkoxy chains. In complex (i), with four octyloxy chains, there are four oxygen atoms around the core. Complex (ii) is asymmetrically substituted with two heptyloxy and two heptyl chains and therefore has two oxygen atoms and complexes (iii) to (vi) have only alkyl chains and hence no oxygen atoms around the core. The metal atom used for coordination has been chosen as Cu/Pd/Ni. Determination of the crystal and molecular structures of these discogens has led to the identification of the following similarities: (1) All the six discogens crystallize in the triclinic space group P1. The recurrence of the space group may be correlated with the structural requirements for efficient packing of the molecules in the crystal lattice. (2) The coordination around the metal atom is square planar. (3) The 11 atom core is only nearly planar. (4) The phenyl rings and the chains are tilted with respect to the core. (5) The molecular conformation in the crystal confers a nearly rectangular shape to these discogens. (6) The chains are fully extended in an all trans conformation. (7) The molecular arrangement is tilted columnar except for the crystal structure of complex (ii).

In addition to the similarities, distinct differences in the crystal structural characteristics have also been observed. For example, when oxygen atoms are present in the fringe, the molecules have no crystallographic symmetry and they tend to pair. In the crystal structure of (i) where the repeat unit along the column is a molecular pair, the metal atoms are distributed in a zig-zag fashion. In the other crystals with columnar arrangement, the metal atoms are stacked one over another. Complex (ii) has a layer-like molecular arrangement in the crystalline phase.     

EPR and optical studies on transition metal doped LiRbB4O7 glasses

Electron paramagnetic resonance and optical investigations of copper and chromium doped LiRbB₄O₇ glasses are carried out. From the results and discussions, it is predicted that both the transition metal ions exhibit octahedral environment. In the case of Cr³⁺, the site symmetry is near octahedral, whereas in the case of Cu²⁺, it is tetragonally distorted octahedral environment. Crystal field, spin-Hamiltonian and bonding parameters are evaluated. The bonding parameters are suggesting ionic.     

Oxygen stability in YBa2Cu3O7−x

The highT _c superconductor YBa₂Cu₃O_7?x has been found to lose appreciable amount of oxygen in a surprisingly low temperature range (～425–630 K), which drastically degrades the superconducting property. Accompanying this oxygen loss, the resistance behaviour has also been found to change from metallic to semiconducting.     

Stannoxanes and phosphonates: New approaches in organometallic and transition metal assemblies

Phosphonate ligands, [RPO₃]^2-, are extremely versatile in the assembly of multi-tin and multi-copper architectures. We have used organostannoxane cores for supporting multi-ferrocene and multi-porphyrin peripheries. The copper-metalated multi-porphyrin compound is an excellent reagent for facile cleavage of DNA, even in the absence of a co-oxidant. Reaction oft-BuPO₃H₂ with Cu(C10₄)₂. 6H₂O in the presence of 2-pyridylpyrazole (2-Pypz) leads to the synthesis of a decanuclear copper (II) assembly.     

Picosecond time-resolved laser emission of coumarin 102: Solvent relaxation

The time-resolved laser emission of coumarin 102 was investigated in various aprotic and protic solvents at picosecond resolution by frequency upconversion technique. The spectral shift of the transient emission spectrum is attributed to solvent reorientation and the results are discussed.     

NDDO MO calculations: isotropic hyperfine coupling constants and nuclear spin-spin coupling constants

The nonempirical NDDO MO method in its unrestricted form has been used to evaluate isotropic hyperfine coupling constants and nuclear spin-spin coupling constants. Satisfactory agreement with INDO and experimental results is obtained.