Direct insight into insulin aggregation by 2D NMR complemented by PFGSE NMR.

The aggregation of Zn(II)-bound and zinc-free human insulin was studied in solution using the H(beta)-CH(3) crosspeaks of threonine residues in 2D COSY, TOCSY, and NOESY NMR spectra which allow viewing of the oligomers in equilibrium. This is complemented by PFGSE measurements of the translational diffusion coefficient, D(i), used for monitoring the changes in equilibrium composition of aggregates on dilution of both insulins in physiological medium. The back calculation of the dilution isotherm allows establishing the association constants for oligomeric equilibria in solution and discussion of the models of association.

Synthesis of zinc chlorophyll materials for dye-sensitized solar cell applications.

To design sensitizers for dye sensitized solar cells (DSSCs), a series of zinc chlorins with different substituents were synthesized. Novel zinc methyl 3-devinyl-3-hydroxymethyl-20-phenylacetylenylpyropheophorbide-a (ZnChl-1), zinc methyl 20-bromo-3-devinyl-3-hydroxymethylpyropheophorbide-a (ZnChl-2), zinc methyl 3-devinyl-3-hydroxymethyl-pyropheophorbide-a (ZnChl-3), zinc propyl 3-devinyl-3-hydroxymethyl-pyropheophorbide-a (ZnChl-4) were synthesized and their photovoltaic performances were evaluated in dye-sensitized solar cells. Photoelectrodes with a 7 µm thick nanoporous layer and a 5 µm thick light-scattering layer were used to fabricate dye sensitized solar cells. The best efficiency was obtained with ZnChl-2 sensitizer. ZnChl-2 gave a Jsc of 3.5 mA/cm(2), Voc of 412 mV, FF of 0.56 and an overall conversion efficiency of 0.81 at full sun (1000 W m(-2)).

Self-assembling corroles.

trans-A2B-corroles bearing -OCH2CONHR groups at the ortho position of the meso-phenyl substituent undergo self-organization both in the solid state as well as in solution. The lack of additional donor atoms induces sheet formation, but if the pyridine unit is present in the structure, more complex helical forms are formed.

Latrogenic complications due to the nasogastric and rectal cannula in neonates.

BACKGROUND: An abnormal position of nasogastric and rectal tubes can be the cause of iatrogenic injuries Most often it can happen in neonates and premature infants. MATERIAL/METHODS: From 1982 through 2003, we observed 9 neonates (8 premature infants) with perforation of the alimentary tract. RESULTS: In most of these patients the only radiological sign was displacement of the nasogastric tube. In 5 children the tube was outside the esophagus, in 3 outside the stomach, and in 1 case perforation was caused by the rectal cannula. Neonates with esophageal perforation were treated conservatively with good effects. Surgical treatment was performed in four children with gastric and rectal perforation - two of whom died. CONCLUSIONS: Evaluation of the position of nasogastric tube on the plain chest and abdominal x-ray is a very important diagnostic Consideration. Any deviation from the normal course of the tube should be suggestive of alimentary tract injury, even in the absence of any other signs of perforation.

A nanoscale bio-inspired light-harvesting system developed from self-assembled alkyl-functionalized metallochlorin nano-aggregates.

Self-assembled supramolecular organization of nano-structured biomimetic light-harvesting modules inside solid-state nano-templates can be exploited to develop excellent light-harvesting materials for artificial photosynthetic devices. We present here a hybrid light-harvesting system mimicking the chlorosomal structures of the natural photosynthetic system using synthetic zinc chlorin units (ZnChl-C6, ZnChl-C12 and ZnChl-C18) that are self-aggregated inside the anodic aluminum oxide (AAO) nano-channel membranes. AAO nano-templates were modified with a TiO2 matrix and functionalized with long hydrophobic chains to facilitate the formation of supramolecular Zn-chlorin aggregates. The transparent Zn-chlorin nano-aggregates inside the alkyl-TiO2 modified AAO nano-channels have a diameter of ∼120 nm in a 60 µm length channel. UV-Vis studies and fluorescence emission spectra further confirm the formation of the supramolecular ZnChl aggregates from monomer molecules inside the alkyl-functionalized nano-channels. Our results prove that the novel and unique method can be used to produce efficient and stable light-harvesting assemblies for effective solar energy capture through transparent and stable nano-channel ceramic materials modified with bio-mimetic molecular self-assembled nano-aggregates.

An unusual oesophageal foreign body in neonate - case report.

BACKGROUND: Foreign bodies in the esophagus in children are usually swallowed accidentally during play. An oesophageal foreign body in neonate is rare and thus the diagnostic work-up may be difficult. CASE REPORT: We present a case of an 8-day-old baby with symptoms of oesophageal obstruction. An unusual foreign body was found. CONCLUSIONS: Foreign bodies in neonate's esophagus are rare; non-accidental action should be suspected. Atypical clinical and radiological symptoms may cause diagnostic difficulties.

Structure of human insulin monomer in water/acetonitrile solution.

Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H2O/CD3CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 degrees C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the program CYANA, two different molecular dynamics simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER_VC), or including a generalized Born solvent model (AMBER_GB).

NMR structure of biosynthetic engineered human insulin monomer B31(Lys)-B32(Arg) in water/acetonitrile solution. Comparison with the solution structure of native human insulin monomer.

A solution NMR-derived structure of a new long -acting, B31(Lys)-B32(Arg) (LysArg), engineered human insulin monomer, in H(2)O/CD(3)CN, 65/35 vol %, pH 3.6, is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Smith, et al., Acta Crystallogr D 2003, 59, 474) and with NMR structure of human insulin in the same solvent (Bocian, et al., J Biomol NMR 2008, 40, 55-64). Detailed analysis using PFGSE NMR (Pulsed Field Gradient Spin Echo NMR) in dilution experiments and CSI analysis prove that the structure is monomeric in the concentration range 0.1-3 mM. The presence of long-range interstrand NOEs in a studied structure, relevant to the distances found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Therefore the results suggest that this solvent system is a suitable medium for studying the native conformation of the protein, especially in situations (as found for insulins) in which extensive aggregation renders structure elucidations in water difficult or impossible. Starting from the structures calculated by the program CYANA, two different molecular dynamics (MD) simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER_VC), or including a generalized Born solvent model (AMBER_GB). Here we present another independent evidence to the one presented recently by us (Bocian et al., J Biomol NMR 2008, 40, 55-64), that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions.