Control of Chromophore Symmetry by Positional Isomerism of Peripheral Substituents

The first example of the control of porphyrinoid chromophore symmetry based on the positional isomerism of peripheral substituents has been achieved by preparing tetraazaporphyrins (TAPs) with C_4h, D_2h, C_2v, and C_s symmetry due to the relative arrangement of peripheral tert‐butylamino and cyano groups as push and pull substituents, respectively. The four structural isomers were successfully isolated and characterized by ¹H NMR spectroscopy and X‐ray crystallography. The band morphology in the Q‐band region varies depending on the molecular symmetry due to the significant perturbation introduced into the chromophore by the push and pull substituents. The C_4h and C_2v isomers exhibit a single Q band, whereas the Q bands of the D_2h and C_s isomers show a marked splitting. The magnetic circular dichroism spectra indicate that the push–pull TAPs retain the properties of the 16‐membered 18π‐electron perimeter generally observed for porphyrinoids. Theoretical calculations have demonstrated that the perturbation introduced by the substituents lowers the D_4h symmetry of the parent TAP π‐conjugated system, and this results in significant spectral changes. A novel approach to the fine‐tuning of the spectral properties of porphyrinoids based on changes in the chromophore symmetry is described.     

Antibacterial metal implant with a TiO2‐conferred photocatalytic bactericidal effect against Staphylococcus aureus

Photocatalysis with anatase Titanium dioxide (TiO₂) under ultraviolet A (UVA) has a well recognized bactericidal effect. There have been a few reports, however, on the effects of photocatalysis on bio‐implant‐related infections. The purpose of present study was to evaluate the photocatalytic bactericidal effects of anatase TiO₂ on Staphylococcus aureus (S. aureus) associated with surgical site infections. TiO₂ films were synthesized on commercially pure titanium substrates and SUS316 stainless steel using a plasma source ion implantation method followed by annealing. The chemical composition of the surface layers was determined using GXRD and XPS. The disks were seeded with cultured S. aureus and exposed to UVA illumination from black light. The bactericidal effect of the TiO₂ films was evaluated by counting the survived colonies statistically. A structural gradient anatase type TiO₂ layer formed on all substrates. The viability of the bacteria on the photocatalytic TiO₂ film coated on titanium was suppressed to 7.0% at 30 minutes and 5.5% at 45 minutes, whereas that on a similarly coated stainless steel was suppressed to 45.8% at 30 minute and 28.6% at 45 minutes (ANOVA: p < 0.05). Complete bacterial inactivation was achieved after 90 minutes on titanium and after 60 minutes on stainless steel. The photocatalytic bactericidal effect of TiO₂ is useful for sterilizing the contaminated surfaces of bioimplants. Copyright © 2008 John Wiley & Sons, Ltd.     

The Effects of Andrographolide on the Enhancement of Chondrogenesis and Osteogenesis in Human Suprapatellar Fat Pad Derived Mesenchymal Stem Cells

Andrographolide is a labdane diterpenoid herb, which is isolated from the leaves of Andrographis paniculata, and widely used for its potential medical properties. However, there are no reports on the effects of andrographolide on the human suprapatellar fat pad of osteoarthritis patients. In the present study, our goal was to evaluate the innovative effects of andrographolide on viability and Tri-lineage differentiation of human mesenchymal stem cells from suprapatellar fat pad tissues. The results revealed that andrographolide had no cytotoxic effects when the concentration was less than 12.5 µM. Interestingly, andrographolide had significantly enhanced, dose dependent, osteogenesis and chondrogenesis as evidenced by a significantly intensified stain for Alizarin Red S, Toluidine Blue and Alcian Blue. Moreover, andrographolide can upregulate the expression of genes related to osteogenic and chondrogenic differentiation, including Runx2, OPN, Sox9, and Aggrecan in mesenchymal stem cells from human suprapatellar fat pad tissues. In contrast, andrographolide suppressed adipogenic differentiation as evidenced by significantly diminished Oil Red O staining and expression levels for adipogenic-specific genes for PPAR-γ2 and LPL. These findings confirm that andrographolide can specifically enhance osteogenesis and chondrogenesis of mesenchymal stem cells from human suprapatellar fat pad tissues. It has potential as a therapeutic agent derived from natural sources for regenerative medicine.     

Catalytic hydrogenation of arenes with rhodium nanoparticles in a water-in-supercritical CO2 microemulsion

Rhodium nanoparticles dispersed by a CO2 microemulsion are effective catalysts for rapid hydrogenation of arenes in supercritical CO2.     

Novel family of low molecular weight hydrogelators based on L-lysine derivatives

New L-lysine derivatives with a positively charged terminal can gel water below 1 wt%; particularly, 1a and 2a form a hydrogel at 0.3 wt% corresponding to approximately 12,300 and 12,500 waters/gelator molecule, respectively.     

Synthesis of 1-azidocyclopropanecarboxylates from 2-azido-2alkenoates

Addition of diazomethane to 2-azido-2-alkenoates followed by pyrolysis of the resulting pyrazoline derivatives affords the title compounds.     

New oleanan-type triterpene and cincholic acid glycosides from Peruvian "Uña de Gato" (Uncaria tomentosa)

A new oleanan-type triterpene and three new cincholic acid glycosides were isolated from Peruvian "Una de Gato" (Cat's claw, plant of origin: Uncaria tomentosa), a traditional herbal medicine in Peru. Their structures were determined by spectroscopic analysis.     

A new 9-methoxyyohimbine-type indole alkaloid from Mitragyna africanus

A new yohimbine-type indole alkaloid (1). was isolated from the stem bark of Mitragyna africanus (WILLD.) collected in Nigeria, along with known seven Corynanthe-type oxindole alkaloids, two secoiridoids, three lignans, and a quinovic acid derivative. Their structures were elucidated by spectroscopic analyses.     

In situ organogelation at room temperature: direct synthesis of gelators in organic solvents

Organogels are formed through a conventional organogelation involving a heating process and an in situ organogelation at room temperature. The conventional organogelation is carried out by dissolution of gelators by heating, while the in situ organogelation is performed by mixing of highly reactive methyl 2,6-diisocyanatohexanoate (LDI) or 2-isocyanatoethyl 2,6-diisocyanatohexanoate (LTI) and alkylamines. The in situ organogelation produced the organogels within several seconds after mixing. The organogels prepared by the in situ organogelation showed quite similar FT-IR spectra and SEM photographs to those formed by conventional organogelation. Moreover, the in situ organogelation using LTI and octylamine as well as dodecylamine produced organogels of acetone, ethyl acetate, and acetonitrile that gelators 5 and 6 cannot gel through conventional organogelation.     

In vivo quantification of the metabolites in normal brain and brain tumors by proton MR spectroscopy using water as an internal standard

Metabolite concentrations in normal adult brains and in gliomas were quantitatively analyzed by in vivo proton magnetic resonance spectroscopy (MRS) using the fully relaxed water signal as an internal standard. Between January 1998 and October 2001, 28 healthy volunteers and 18 patients with gliomas were examined by in vivo proton MRS. Single-voxel spectra were acquired using the point-resolved spectroscopic (PRESS) pulse sequence with a 1.5 T scanner (TR/TE/Ave = 3000 ms/30 ms/64). The calculated concentrations of N-acetyl-aspartate (NAA), creatine (Cre), choline (Cho), and water(H(2)O) in the normal hemispheric white matter were 23.59 +/- 2.62 mM (mean +/- SD), 13.06 +/- 1.8 mM, 4.28 +/- 0.8 mM, and 47280.96 +/- 5414.85 mM, respectively. The metabolite concentrations were not necessarily uniform in different parts of the brain. The concentrations of NAA and Cre decreased in all gliomas (p < 0.001). The NAA/Cho and NAA/H(2)O ratios can distinguish the normal brain from gliomas and low-grade from high-grade astrocytoma (p < 0.001). The concentration of taurine (Tau) in medulloblastomas was 29.64 +/- 5.76 mM. This is the first quantitative analysis of Tau in medulloblastoma in vivo and confirms earlier in vitro findings.