Surface IR (infrared) modes of crystalline and fumed (amorphous) silica particles, calcined at temperatures up to 1095 degrees C, have been studied by Fourier transform infrared spectroscopy. The ability of these same particles to lyse cells has been measured by a hemolysis protocol. The untreated crystalline and amorphous materials differ by a factor of 40 in specific surface area, and the intensity per unit mass of the sharp surface silanol band near 3745 cm-1 in the amorphous material is an order of magnitude larger than in the crystalline material. A similar difference is observed in the lysing potential of the two materials. The intensity of the silanol band increases after calcination for both materials, reaching peak values near 500 degrees C, followed by a dramatic drop at higher calcination temperatures, and reaching negligible values for materials calcined near 1100 degrees C. The lysing potential data follow essentially the same pattern for both crystalline and fumed silica. These results are consistent with the hypothesis that the surface silanol groups are involved in cell lysis. Further experiments are suggested to evaluate the relationship between the surface structure of silica particles and their potential cytotoxicity.ImagesFIGURE 2. AFIGURE 2. BFIGURE 2. CFIGURE 2. D
Surface IR (infrared) modes of crystalline and fumed (amorphous) silica particles, calcined at temperatures up to 1095°C, have been studied by Fourier transform infrared spectroscopy. The ability of these same particles to lyse cells has been measured by a hemolysis protocol. The untreated crystalline and amorphous materials differ by a factor of 40 in specific surface area, and the intensity per unit mass ofthe sharp surface silanol band near 3745 cm-' in the amorphous material is an order of magnitude larger than in the crystalline material. A similar difference is observed in the lysing potential of the two materials. The intensity of the silanol band increases after calcination for both materials, reaching peak values near 500°C, followed by a dramatic drop at higher calcination temperatures, and reaching negligible values for materials calcined near 1100C. The lysing potential data follow essentially the same pattern for both crystalline and fumed silica. These results are consistent with the hypothesis that the surface silanol groups are involved in cell lysis. Further experiments are suggested to evaluate the relationship between the surface structure of silica particles and their potential cytotoxicity.
Systematic functionalization of perfluoroaryl azides with chelating agents capable of complexing
transition metals produces a new class of bifunctional photolabile chelating agents (BFPCAs). The
strategy to shield the azide functionality from the electronic and steric influence of the electron-rich metal Pd through ester and amide bridges raised CH insertion efficiency to unprecedented
levels (>92%) in a model solvent (cyclohexane). In contrast, perfluoroaryl azides attached to
chelating agents via hydrazones show no significant CH insertion in cyclohexane upon photolysis.
Measurements of the lifetimes of the singlet nitrenes derived from these agents by flash photolysis
techniques correlate well with the efficiency of CH insertion by demonstrating longer lifetimes
(10−50 times) for singlet nitrenes derived from azidotetrafluorinated esters and amides compared
with the related hydrazones, which failed to yield significant CH insertion. A representative BFPCA
12 is chelated to diagnostic radionuclide 99mTc and covalently attached to human serum albumin
via photochemical activation extending the favorable bimolecular insertion characteristics of BFPCA
to tracer level concentrations in buffer conditions. Flash photolysis experiments correlate singlet
nitrene lifetimes with the efficiency of intermolecular insertion reactions. This work provides new
photo-cross-linking technology, useful in radiodiagnostics and radiotherapy in nuclear medicine.
Functionalization of perfluoro aryl azides by bifunctional chelating agents (BFCAs) capable of forming high specific activity complexes with (99m)Tc (for gamma-imaging) and (188)Re (for radiotherapy) is described. The synthesis of multidonor BFCAs containing N(2)S(2), N(4), and N(3)S donor groups containing imidazole, pyridine, and pyrazine functionalities that may be important for tuning the pharmacokinetic parameters is also described. Functionalization of perfluoro aryl azides at various sites on BFCAs yields novel bifunctional photolabile chelating agents (BFPCAs) that are useful for covalent attachment to biomolecules. A representative Re-BFPCA 8a in a model solvent, diethylamine, proceeded to give a high yield of intermolecular NH insertion product without the decomplexation of the metal ion from 8a. All products originated from the photolysis of 8a in diethylamine are characterized by analytical techniques, and a plausible mechanism of formation of different photolytic products is suggested. The high yield of intermolecular NH insertion of Re-BFPCA 8a is extended to labeling of human serum albumin (HSA) and Fab fragments under aqueous conditions. The photolabeling technology developed here offers a new way to attach diagnostically and therapeutically useful radiotracers (e.g., (99m)Tc, (188)Re) to Fab fragments for potential noninvasive imaging and therapy of cancer.
The efficiency of photolabeling of HSA and IgG with [14C]methyl 4-azido-2,3,5,6-tetrafluorobenzoate has been studied using size exclusion chromatography in conjunction with liquid scintillation counting. Labeling efficiencies of 78% for HSA and 82% for IgG have been determined. The extent of bond insertion into proteins exceeds the C-H insertion efficiency in cyclohexane with less wastage into anilinium and azo side products. These results suggest that the photoprobe accesses hydrophobic regions of both proteins prior to photolysis.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.