Endothelial cell migration on surface-density gradients of fibronectin, VEGF, or both proteins

Cell migration is essential to many physiological processes, including angiogenesis, which is critical to the success of implanted biomaterials and tissue-engineered constructs. Gradients play an important role in cell migration. Previous work on cell migration has been mostly executed either in the concentration gradients of stimuli (e.g., VEGF) in bulk or hydrogels or on the surface-density gradients of ECM proteins (e.g., fibronectin) or small ligands (e.g., RGD). Little work has been done to investigate how cell migration responds to the surface-density gradients of growth factors. No work has been done to study how the surface gradients of both adhesive proteins and growth factors influence cell migration. In this work, we studied the effect of the surface-density gradients of fibronectin (FN), VEGF, or both proteins on endothelial cell migration. Gradients with different slopes were prepared to study how the gradient slope affects cell migration. The gradients were generated by first forming a counter-propagating C15COOH/C11OH self-assembled monolayer (SAM) gradient using a surface electrochemistry approach, followed by activating the -COOH moieties and covalently immobilizing proteins onto the surface. Fourier transform infrared spectra and X-ray photoelectron spectroscopy were used to characterize the SAM and protein gradients, respectively. A free cell migration assay using bovine aortic endothelial cells was performed on various gradient surfaces or on surfaces with uniform protein density. Results showed that cells on the surface-density gradients of FN, VEGF, or both proteins moved faster along the gradient direction than on the respective uniform control surface after 24-h cell culture. It is also shown that for each protein or protein combination, the directional cell displacement was not statistically different between two gradients with different slopes. Results show that the directional cell migration was increased by about 2-fold on the VEGF gradient as compared to the FN gradient and was further increased by another 2-fold on the combined gradients of both proteins as compared to the VEGF gradient alone. This is the first work to create surface-density gradients of VEGF and the first study to generate a combined surface gradient of growth factor and ECM protein to investigate their effect on cell migration on surfaces. This work broadens our understanding of the directional movement of endothelial cells. Our findings provide useful information for directing cell migration into tissue-engineered constructs and can be potentially used for those applications where cell migration is critical, such as angiogenesis.     

A computational study of physical and biological characterization of common UV sources and filters,and their relevance for substituting sunlight

Sunlight is the most important environmental UV source, affecting not only human health but also the whole terrestrial ecosystem. The use of artificial sources is advantageous since it is independent of geographical location and seasonal variations, however, in some photobiological/photochemical studies the choice of a specific UV source in relation to the biological end-point studied is sometimes questionable. Furthermore, it is often difficult to compare the results obtained in different laboratories due to 'slight' differences in the physical characteristics of the UV sources used. In an attempt to address these issues we calculated and compared the physical characteristics and the biological efficiency in UV-B and UV-A regions for two biological end-points (CPD and Fpg-sensitive sites formation) for frequently used UV-B, UV-A sources and solar light simulators (SLS). Our calculation shows that FS20 lamp is appropriate for studying the biological effects of UV-B radiation although differences in spectral characteristics of the associated filters may lead to at least 2-fold yields in CPD production. Furthermore, the use of a SLS with a Kodacel filter alone is inadequate for studying environmental UV effects. A metal-halide source with a Schott WG345 filter is appropriate for studies on biological effects due to UV-A region. Relative exposure duration was calculated to achieve equal amount of CPD or Fpg-sensitive sites, provided equal, total UV-(A+B) irradiance for the different UV sources.     

Two isostructural triboluminescent lanthanide complexes

(4‐Di­methyl­amino­pyridine)­tris(2,2,6,6‐tetra­methyl­heptane‐3,5‐dionato)­terbium(III), [Tb(C₁₁H₁₉O₂)₃(C₇H₁₀N₂)], and its samarium analogue, [Sm(C₁₁H₁₉O₂)₃(C₇H₁₀N₂)], are isostructural. Their polar space group is consistent with observed second harmonic generation and with the involvement of piezoelectric charging in their intense triboluminescence properties, which are of interest for the development of damage sensors in composite materials. The metals display irregular seven‐coordination by one substituted pyridine and three chelating diketonate ligands, bond lengths to Tb being shorter than those to Sm.     

Einige Untersuchungsbefunde von getrockneter grüner Minze

Analytical and Bioanalytical Chemistry -     

Biomimetic Strain-Stiffening Self-Assembled Hydrogels

Supramolecular structures with strain-stiffening properties are ubiquitous in nature but remain rare in the lab. Herein, we report on strain-stiffening supramolecular hydrogels that are entirely produced through the self-assembly of synthetic molecular gelators. The involved gelators self-assemble into semi-flexible fibers, which thereby crosslink into hydrogels. Interestingly, these hydrogels are capable of stiffening in response to applied stress, resembling biological intermediate filaments system. Furthermore, strain-stiffening hydrogel networks embedded with liposomes are constructed through orthogonal self-assembly of gelators and phospholipids, mimicking biological tissues in both architecture and mechanical properties. This work furthers the development of biomimetic soft materials with mechanical responsiveness and presents potentially enticing applications in diverse fields, such as tissue engineering, artificial life, and strain sensors.     

Accuracy of the multipole expansion applied to a sphere in a creeping flow parallel to a wall

An example system is studied to discuss precision of the multipoleexpansion, applied to determine forces exerted on particlesby a viscous low-Reynolds-number fluid flow. A single spherein an ambient flow (pure shear, quadratic, and modulated shear)parallel to a close plane wall is considered. Forces and torquesexerted by the ambient flow on a motionless sphere are evaluated.Their precision is determined and related to a multipole orderof the truncation. Similar analysis is performed for a movingsphere with no ambient flow and for a freely moving sphere.Relative motion of the sphere with respect to the wall givesrise to strong lubrication interactions. It is analysed howthese interactions affect accuracy of the pure multipole expansion,and what are the smallest distances where it becomes insufficient.An alternative precise method is applied, in which lubricationexpressions are subtracted from the hydrodynamic forces andtorques, and the residue is evaluated as a fast-convergent seriesof inverse powers of the distance between the sphere centreand the wall. The accuracy of this procedure is carefully analysed.     

Direct probe of iron vibrations elucidates NO activation of heme proteins

We use nuclear resonance vibrational spectroscopy (NRVS) to identify the Fe-NO stretching frequency in the NO adduct of myoglobin (MbNO) and in the related six-coordinate porphyrin Fe(TPP)(1-MeIm)(NO). Frequency shifts observed in MbNO Raman spectra upon isotopic substitution of Fe or the nitrosyl nitrogen confirm and extend the NRVS results. In contrast with previous assignments, the Fe-NO frequency of these six-coordinate complexes lies 70-100 cm-1 lower than in the analogous five-coordinate nitrosyl complexes, indicating a significant weakening of the Fe-NO bond in the presence of a trans imidazole ligand. This result supports proposed mechanisms for NO activation of heme proteins and underscores the value of NRVS as a direct probe of metal reactivity in complex biomolecules.     

Optical production of ultracold polar molecules

We demonstrate the production of ultracold polar RbCs molecules in their vibronic ground state, via photoassociation of laser-cooled atoms followed by a laser-stimulated state transfer process. The resulting sample of X1Sigma+ (nu = 0) molecules has a translational temperature of approximately 100 microK and a narrow distribution of rotational states. With the method described here it should be possible to produce samples even colder in all degrees of freedom, as well as other bialkali species.     

nσ* and πσ* excited states in aryl halide photochemistry: a comprehensive study of the UV photodissociation dynamics of iodobenzene

A recent review (Ashfold et al., Phys. Chem. Chem. Phys., 2010, 12, 1218) highlighted the important role of dissociative excited states formed by electron promotion to σ* orbitals in establishing the photochemistry of many molecular hydrides. Here we extend such considerations to molecular halides, with a particular focus on iodobenzene. Two experimental techniques (velocity mapped ion imaging (VMI) and time resolved infrared (IR) diode laser absorption) and electronic structure calculations have been employed in a comprehensive study of the near ultraviolet (UV) photodissociation of gas phase iodobenzene molecules. The VMI studies yield the speeds and angular distributions of the I((2)P(3/2)) and I*((2)P(1/2)) photofragments formed by photolysis in the wavelength range 330 ≥λ≥ 206 nm. Four distinct dissociation channels are observed for the I((2)P(3/2)) atom products, and a further three channels for the I*((2)P(1/2)) fragments. The phenyl (Ph) radical partners formed via one particular I* product channel following excitation at wavelengths 305 ≥λ≥ 250 nm are distributed over a sufficiently select sub-set of vibrational (v) states that the images allow resolution of specific I* + Ph(v) channels, identification of the active product mode (ν(10), an in-plane ring breathing mode), and a refined determination of D(0)(Ph-I) = 23,390 ± 50 cm(-1). The time-resolved IR absorption studies allow determination of the spin-orbit branching ratio in the iodine atom products formed at λ = 248 nm (?(I*) = [I*]/([I] + [I*]) = 0.28 ± 0.04) and at 266 nm (?(I*) = 0.32 ± 0.05). The complementary high-level, spin-orbit resolved ab initio calculations of sections (along the C-I bond coordinate) through the ground and first 19 excited state potential energy surfaces (PESs) reveal numerous excited states in the energy range of current interest. Except at the very shortest wavelength, however, all of the observed I and I* products display limiting or near limiting parallel recoil anisotropy. This encourages discussion of the fragmentation dynamics in terms of excitation to states of A(1) total symmetry and dissociation on the 2A(1) and 4A(1) (σ* ← n/π) PESs to yield, respectively, I and I* products, or via non-adiabatic coupling to other σ* ← n/π PESs that correlate to these respective limits. Similarities (and differences) with the available UV photochemical data for the other aryl halides, and with the simpler (and more thoroughly studied) iodides HI and CH(3)I, are summarised.