Enhanced hydrolysis rates for the cleavage of bis(4-nitrophenyl)phosphate (BNPP), a model phosphodiester, may be achieved by using appropriately designed ditopic receptors containing the known phosphate-binding nucleus, sapphyrin, attached covalently to suitably oriented polyhydroxyl subunits. Evidence for the interaction between sapphyrin and BNPP comes from solid-state X-ray diffraction analysis of a diprotonated dihydroxylated sapphyrin-BNPP complex and from solution-phase (31)P NMR spectroscopic binding studies. The sapphyrins described in this paper may have a role to play as oligonucleotide cleavage agents.
- MeSH
- difrakce rentgenového záření MeSH
- hydrolýza MeSH
- hydroxylace MeSH
- katalýza MeSH
- kinetika MeSH
- molekulární struktura MeSH
- nitrofenoly chemie MeSH
- porfyriny chemie MeSH
- vodíková vazba MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- bis(4-nitrophenyl)phosphate MeSH Prohlížeč
- nitrofenoly MeSH
- porfyriny MeSH
- sapphyrin MeSH Prohlížeč
A new, stepwise synthesis of calix[4]phyrins is described. It relies on the condensation of a ketone with pyrrole to form a dipyrromethane containing a quaternary carbon center that is subsequently condensed with an aromatic aldehyde. This methodology, in contrast to the previous rational approach described by this group (involving formation of a trisubstituted dipyrromethane via the condensation of an aldehyde with pyrrole, followed by condensation of this dipyrromethane with acetone), allows for a variety of bulky, ketone-derived substituents to be incorporated into the meso-like positions. The resulting systems, while all containing the same central macrocyclic core, display conformational properties that reflect the nature of these meso-like substituents; these conformational features were independently assessed by X-ray diffraction analysis, NMR spectroscopy, and quantum chemical calculations.
- MeSH
- difrakce rentgenového záření MeSH
- kalixareny chemická syntéza chemie MeSH
- magnetická rezonanční spektroskopie MeSH
- molekulární konformace MeSH
- molekulární modely MeSH
- porfyriny chemická syntéza chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Research Support, U.S. Gov't, P.H.S. MeSH
- Názvy látek
- kalixareny MeSH
- porfyriny MeSH
The use of near-infrared (NIR)-excited Fourier-transform (FT) Raman spectroscopy as a technique for evaluating the extent of photosensitizer localization in tumor (human pancreatic adenocarcinomas)-bearing mice has been tested using lutetium(III) texaphyrin analogue Lu-T2B2Tex. The complex was injected subcutaneously in the form of three injections given during the course of 3 days. The kinetics of biodistribution were then followed over a time scale of 1-6 days. The NIR-FT-Raman spectra of tissue samples obtained from the xenographic tumor, muscle, heart, brain, liver, spleen, kidney and blood were recorded and used to identify the presence of Lu-T2B2Tex in these tissues. Five Raman sensitizer markers were used to estimate the relative content of Lu-T2B2Tex in tumor at various postinjection times. UV-Visible (Vis) absorption spectroscopic detection of this sensitizer in tissue extracts was applied as a conventional method. Both spectroscopic methods were in good agreement with each other and confirm that Lu-T2B2Tex localizes well in tumor tissue. Maximal drug content was observed 3 days after the final injection. This time delay seems to be optimal for tumor irradiation in photodynamic therapy.
- MeSH
- adenokarcinom metabolismus MeSH
- blízká infračervená spektroskopie přístrojové vybavení metody MeSH
- dusičnany farmakokinetika MeSH
- fotosenzibilizující látky farmakokinetika MeSH
- inbrední kmeny myší MeSH
- lidé MeSH
- metaloporfyriny farmakokinetika MeSH
- modely u zvířat MeSH
- molekulární struktura MeSH
- myši nahé MeSH
- myši MeSH
- nádorové buněčné linie MeSH
- nádory slinivky břišní MeSH
- Ramanova spektroskopie přístrojové vybavení metody MeSH
- spektrofotometrie ultrafialová MeSH
- spektroskopie infračervená s Fourierovou transformací přístrojové vybavení metody MeSH
- tkáňová distribuce MeSH
- transplantace nádorů MeSH
- zvířata MeSH
- Check Tag
- lidé MeSH
- myši MeSH
- ženské pohlaví MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Research Support, U.S. Gov't, P.H.S. MeSH
- Názvy látek
- dusičnany MeSH
- fotosenzibilizující látky MeSH
- metaloporfyriny MeSH
- motexafin lutetium MeSH Prohlížeč
A new series of cytosine-substituted metalloporphyrin conjugates (containing Co(II) and Zn(II) as the coordinated metals) were designed and investigated as nucleotide receptors in PVC-membrane-based ion-selective electrodes under neutral conditions. The potentiometric results indicate that these systems, in particular the Co(II)-containing complex, may be potentially useful sensors for complementary nucleotide substrates in the presence of 10 mol% tridodecylmethylammonium chloride (K(Pot.)(5'-GMP/5'-AMP)= 0.045).
- MeSH
- biosenzitivní techniky * MeSH
- cytosin chemie MeSH
- elektrody MeSH
- ionty MeSH
- kvartérní amoniové sloučeniny chemie farmakologie MeSH
- metaloporfyriny chemie MeSH
- molekulární struktura MeSH
- nukleotidy metabolismus MeSH
- polyvinylchlorid chemie MeSH
- potenciometrie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Research Support, U.S. Gov't, P.H.S. MeSH
- Názvy látek
- cytosin MeSH
- ionty MeSH
- kvartérní amoniové sloučeniny MeSH
- metaloporfyriny MeSH
- nukleotidy MeSH
- polyvinylchlorid MeSH
- tridodecylmethylammonium MeSH Prohlížeč
Six water-soluble macrocyclic photosensitizers, the members of two groups of expanded porphyrins (metallotexaphyrins and free-base sapphyrins) containing hydrophilic substituents and meso-tetra(4-sulfonatophenyl)-porphyrin, were tested by UV-Vis absorption and resonance Raman spectroscopy in the in vitro binding experiments with intact mitochondria isolated from swine liver. Studied macrocycles showed markedly different affinity to mitochondria. The highest uptake was observed for sapphyrin-sugar conjugate and metallotexaphyrins. Sapphyrin-polyamine conjugates exhibit something less affinity to mitochondria, while the porphyrin of anionic character showed very low mitochondrial uptake. Obtained spectroscopic results confirm that the binding process altered the self-aggregation degree of expanded porphyrins.
- MeSH
- algoritmy MeSH
- fotochemoterapie MeSH
- fotosenzibilizující látky chemická syntéza chemie MeSH
- jaterní mitochondrie chemie MeSH
- molekulární struktura MeSH
- porfyriny chemická syntéza chemie MeSH
- prasata MeSH
- Ramanova spektroskopie MeSH
- spektrofotometrie MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- srovnávací studie MeSH
- Názvy látek
- fotosenzibilizující látky MeSH
- porfyriny MeSH
The synthesis, characterization, and biolocalization properties of new, fully water-soluble sapphyrins is reported. These systems, which display light absorbing features that make them of potential interest as photodynamic therapy (PDT) sensitizers, were found to localize selectively in pancreatic carcinoma tissue in a xenographic murine model. In this model, the concentration ratios for malignant tissue to surrounding muscle tissue were found to be as high as 280 in the most favorable case. The concentrations of the water-soluble sapphyrins reported here, as well as a porphyrin control system, were determined as a function of time and tissue type.
- MeSH
- myši nahé MeSH
- myši MeSH
- nádory slinivky břišní metabolismus MeSH
- porfyriny chemická syntéza chemie farmakokinetika MeSH
- rozpustnost MeSH
- spektrofotometrie ultrafialová MeSH
- tkáňová distribuce MeSH
- transplantace heterologní MeSH
- transplantace nádorů MeSH
- zvířata MeSH
- Check Tag
- myši MeSH
- ženské pohlaví MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Research Support, U.S. Gov't, P.H.S. MeSH
- Názvy látek
- porfyriny MeSH
- sapphyrin MeSH Prohlížeč
