To evaluate the performance of a 3D T1-weighted gradient-echo (3D T1GRE) computed tomography (CT)-like magnetic resonance imaging (MRI) sequence for detecting and assessing wrist and hand fractures compared to conventional CT. Subjects with acute wrist or hand fracture in CT underwent additional 3 T MRI including a CT-like 3D T1GRE sequence and were compared to patients without fractures. Two radiologists assessed fracture morphology on both modalities according to the Arbeitsgemeinschaft Osteosynthese (AO) and graded image quality and diagnostic confidence on a 5-point Likert scale. Besides diagnostic test evaluation, differences in image quality and diagnostic confidence between CT-like MRI and CT were calculated using the Wilcoxon test. Agreement of AO classification between modalities and readers was assessed using Cohen’s Kappa. Twenty-eight patients with 43 fractures and 43 controls were included. Image quality (3D T1GRE 1.19 ± 0.37 vs. CT 1.22 ± 0.42; p = 0.65) and diagnostic confidence (3D T1GRE 1.28 ± 0.53 vs. CT 1.28 ± 0.55; p = 1.00) were rated excellent for both modalities. Regarding the AO classification, intra- (rater 1 and rater 2, κ = 0.89; 95
The method for laser and light assisted hair removal is based on the theory of selective photothermolysis. Selective absorption of hair chromophores from lasers and broad band light sources results in destruction of hair follicles while leaving the skin undamaged. A discussion of the basic principles of selective photothermolysis as it applies to hair removal by lasers and light sources is presented, followed by a comparative review of three melanin target based systems: Ruby laser, Alexandrite laser, and a broad band intense pulsed light. These systems are efficient and safe with proper patient selection. Multiple treatments are necessary due to the nature of the hair growth cycle.
Aluminium phthalocyanines sulfonated to a different degree ( AlPcS n ) and consisting of various isomeric species were studied by spectroscopic techniques to determine their tendencies to form dimers and aggregates. These characteristics were compared with the cell-penetrating properties of the species, using the Ehrlich ascites mouse tumor cell line, to arrive at structure-activity relationships. AlPcS n preparations consisting of the least number of isomeric species exhibited the highest tendency to form dimers and aggregates, whereas the more complex preparations, consisting of many isomeric products, showed more consistent monomeric features in aqueous environments. Uptake in cells was shown to correlate well with the overall hydrophobicity of the preparation and inversely with its degree of aggregation in the extracellular environment. Among the purified, single isomeric AlPcS n the amphiphilic disulfonated AlPcS 2a , enriched in positional isomers featuring sulfonate groups on adjacent phthalic subunits, showed the best membrane-penetrating properties. Even higher cell uptake was observed for the AlPcS 2mix reflecting a combination of optimal lipophilicity and a low degree of aggregation. Similarly, in the case of AlPcS 4 , the pure isomeric compound showed less cell uptake than the mixed isomeric preparation of similar hydrophobicity, reflecting the higher degree of aggregation invoked by its symmetrical structure. Our data indicate that mixed sulfonated phthalocyanine preparations may exert higher photodynamic efficacy in biological applications as compared to the pure isomeric constituents.
Photodynamic therapy (PDT) has been described in terms of cellular and vascular effects. The precise mechanisms of cellular and vascular damage are still unknown. In this study, the photodynamic inactivation of endothelial cells in vitro and damage to the microvasculature in vivo by naturally occurring porphyrins (uroporphyrin III (UP), coproporphyrin III (CP) and protoporphyrin IX (PP)) were investigated. The chick chorioallantoic membrane model (CAM model) was used, which is convenient for the study of damage to the microcirculation induced by PDT. The hydrophilic porphyrins UP and CP exhibited low cytotoxicity towards endothelial cells. Only small amounts of UP and CP were taken up, resulting in weak inactivation after irradiation. In contrast, the more lipophilic PP showed a marked cytotoxicity. Considerable amounts of PP were accumulated in the cells, leading to pronounced inactivation after light exposure. For the three porphyrins, damage to the microvasculature was observed. The damage caused by the hydrophilic porphyrins UP and CP was strongly dependent on the drug and light dose. For vascular injury, the efficacy was graded as UP < CP < PP.
Porphyrins and porphine analogs have been shown to induce cytotoxic effects on cells and tissues after exposure to light, an effect which is currently being studied as a new modality for treatment of cancer, termed photodynamic therapy (PDT). One of the important factors in PDT is the preferential uptake of sensitizers by rapidly proliferating tissues. Previous studies showed that cytoskeletal structures are affected by porphyrin-induced PDT. In the present study we investigate the inhibitory efficiency of porphines on tubulin assembly in vitro. We analyze the efficiency of several sulfonated porphine isomers: tetraphenylporphine n-sulfonate (TPPSn) where n equals 4, 2a and 2o (a and o refer to adjacent and opposite substitution, respectively) and the structural isomers of tetra(o-,m-, and p-hydroxyphenyl)porphine (o-,m- ,p-THPP), in order to find a possible structure-activity relationship. The efficiency of the sensitizers was assayed by their capacity to inhibit microtubule assembly. Binding to monomeric tubulin is essential for effective inhibition of assembly, with or without exposure to light. Without exposure to light, TPPS2o was found to be the most potent inhibitor, followed by TPPS2a and to a much smaller extent by TPPS4. All THPP isomers have negligible inhibitory effect. Upon exposure to white light, microtubule assembly was inhibited in the same order:TPPS2o greater than TPPS2a greater than TPPS4 greater than THPP. All porphines were found to have high affinity to the same site on tubulin even those who had almost no dark effect on tubulin assembly (THPP). Addition of the porphines to assembled microtubules did not lead to their depolymerization even after prolonged irradiation. Since it was previously suggested that porphines may share the same binding site on tubulin as bis-ANS, a known tubulin assembly inhibitor, we performed competition studies with this inhibitor and the porphines. It was shown that bis-ANS does not share the same site on tubulin as the porphines and therefore their effects are additive.
In vivo uptake of the natural porphyrins, uroporphyrin III (UP), coproporphyrin III (CP) and protoporphyrin IX (PP), was monitored by fluorescence microscopy. Experiments were performed using the chick chorioallantoic membrane (CAM) model, which allowed video documentation of fluorescence both in real time and after integration over a chosen time interval (usually 2 s). Sensitizers at a concentration of 50 (mu) M (100 (mu) L) were injected into a medium-sized vein (diameter approximately 40 micrometer) using an ultra-fine 10 micrometer diameter needle. Fluorescence images were quantitated by subtracting the fluorescence intensity of surrounding CAM tissue (Fmatrix) from the intravascular fluorescence intensity (Fintravascular), after transformation of the video frames into digital form. The differential fluorescence intensity, Fintravascular - Fmatrix, is a measure of the biodistribution. Real time measurements clearly showed that CP and UP fluorescence is associated with moving erythrocytes and not with endothelial cells of the vessel wall. Fluorescence intensity was monitored, up to 60 minutes after injection, by averaging the fluorescence over time intervals of 2 s and recording the integrated images. The fluorescence intensity reached its maximum in about 20 - 30 min after injection, presumably after monomerization inside erythrocyte membranes. The results are interpreted in terms of physical-chemical characteristics (e.g. hydrophilicity) and correlated with the photodynamically induced hemostasis in CAM blood vessels.
The chick chorioallantoic membrane (CAM) is a convenient model for the study of photodynamic therapy (PDT). This membrane has a rich vasculature, which mimics the tumor neovasculature, and can also serve as a host for implanted tumors. The transparency of the CAM enables in-vivo monitoring of vascular changes during and post PDT, without the need to sacrifice test animals at each time point. Video documentation and analysis of events occurring during and after irradiation permit the quantification of changes in vessel morphology, blood perfusion and tumor development. The compounds tested in this study belong to a family of potential sensitizers -- the porphycenes. These are phorphyrin isomers based on a 16-membered macrocycle, in which the four methine moieties linking the pyrrole rings have been replaced by two direct bonds and two ethine bridges. Experiments were performed on blood vessels of the intact CAM and on recurrent human melanoma cells implanted on the CAM. Tumor selectivity was demonstrated by measuring drug uptake using fluorescence methods. A sensitizer injected systemically into the embryo yolk sac could be detected in the blood vessels 30 min after injection; 1 h later the sensitizer had preferentially accumulated in the tumor. Tumors were irradiated at the optimal uptake time (after 1 h) for 16 min with a 20 mW HeNe laser. Video image analysis showed that 96 h after irradiation tumors had decreased to 5% of their original size. In contrast, non-irradiated control tumors on the same CAM, continued to proliferate and grew to more than twice their original size. In addition, we observed a difference in the damage mechanism after systemic compared to topical administration. Topical application followed by irradiation caused fast necrosis of tumors, which might suggest direct damage to tumor cells, whereas after systemic administration, PDT damage was manifested by slower necrosis, presumably caused by vascular destruction.
Abstract— The antibacterial photodynamic effects of uncharged (o‐tetrahydroxyphenyl porphine [THPP], m‐THPP and p‐THPP), cationic (5,10,15,20‐tetra[4‐N‐methylpyridyllporphine [TMPyP]) and anionic (5,10,15,20‐tetra[4‐sulfonatophenyl porphine] [TPPS4]) porphines on Staphylococcus aureus and Escherichia coli bacteria inactivation were examined. The results show that uncharged porphines provoked antibacterial photodynamic activity on S. aureus, and also on E. coli in the presence of the membrane‐disorganizing peptide polymixin B nonapeptide (PMNP). The TMPyP compound was highly photoactive toward gram‐positive bacteria but only marginally effective on gram‐negative cells, whereas TPPS4 showed no activity on either gram‐positive or gram‐negative bacteria. The photoactivity of TMPyP is due to the electrostatic attraction between the positively charged sensitizer molecule and the negatively charged membrane of the gram‐positive target cells. For TPPS4, the inactivity toward gram‐positive bacteria is due to electrostatic repulsion between the charged sensitizer molecule and the cell membrane. For gram‐negative bacteria, the inactivity is conceivably due to preferential (electrostatic) binding to the positively charged PMNP, which is an adjuvant for membrane disorganization, but has no effect on cell viability. For hydrophobic sensitizers, the photoactivity depends on the state of aggregation. The extent of deaggregation of the different THPP isomers was determined by fluorescence measurements of bound sensitizers and could be positively correlated with their photoinactivation capacity. We conclude that the structure‐activity relationships of these porphines are affected by their net charge and by aggregation.
Photodynamic therapy (PDT) was performed in the chick embryo chorioallantoic membrane (CAM) for the purpose of quantitative evaluation of several porphycenes as potential photosensitizers. Porphycenes are structural isomers of porphine possessing lower symmetry of the macrocycle and are characterized by 10-fold higher absorption at the therapeutic wavelengths for PDT (lambda > 630 nm). PDT-induced damage to CAM blood vessels included vasoconstriction and blanching, as was monitored during irradiation and videotaped. Image analysis techniques enabled us to follow PDT-induced constriction of vessel diameter (to 50%), reduction of blood perfusion (to 40% lower optical density) and shrinkage of implanted tumours (to 10% of their original area). The observed PDT efficacy of functionalized porphycenes is positively correlated with the number of polar substituents.
Novel porphyrinoid photosensitizers are currently being considered for use in photodynamic therapy (PDT) of cancer. This class of sensitizers combines high absorption characteristics at the therapeutic wavelengths ((lambda) > 600 nm) and good tumor targeting properties. We have investigated the in-vivo uptake and photodynamic damage of several porphycenes. Our model system was the chick chorioallantoic membrane (CAM) which we have adapted for use in PDT studies. The CAM assay allows fast screening of novel drugs and obtaining statistically relevant results with minute quantities of the drug. Sensitizers were `trapped' in EPC (egg phosphatidylcholine) or in DPPC (dipalmitoyl phosphatidylcholine); their efficiencies were independent of the vehicle used for application of the sensitizer. The efficiencies of various porphycenes in PDT, as a function of drug and light dose, compare well with those of standard porphyrins and phthalocyanines.© (1994) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.
Lifetimes of TPPS4 (meso-tetraphenylporphine tetrasulfonate) triplet states were measured for liquid solutions of different acidity and viscosity and as a function of acceptor concentration for different acceptors (bovine serum albumin, tryptophan and furfuryl alcohol). Triplet lifetimes were estimated by monitoring the decay of TPPS4 delayed fluorescence of E-type. The lifetime of delayed fluorencence depends on the concentration of O2, since the latter is an effective quencher of the triplet state. The lifetime is shown to be influenced mainly by degree of aggregation state of TPPS4 and, therefore, by the pH of the solution, decreasing with pH and for each pH remaining constant over a wide range of acceptor concentrations. The monomeric species is found to have the longest triplet lifetime in aqueous phosphate-buffered saline solution at neutral pH, especially when bound to albumin, despite of the low viscosity and protonated nature of the medium.
The chick chorioallantoic membrane (CAM) model was used to study vascular effects of photodynamic therapy (PDT) and hyperthermia (HPT) and the synergism of these modalities. The CAM is a convenient medium for monitoring the modifications of the vasculature. It is possible to view the CAM and to examine structural changes of individual blood vessels in real tune. Moreover, the CAM is a closed system which lends itself to mathematical modeling of the temporal and spatial temperature profile and in which HPT can be performed quantitatively and to a selected depth, using different lasers. A porphyrin‐type photosensitizer solution was applied to areas of the CAM, defined by teflon O‐rings placed on the surface. Uptake dynamics of the sensitizer into the CAM was determined by analyzing its fluorescence in vivo. The CAM area was irradiated with a dual‐wavelength laser system composed of a dye laser at 644 nm (to induce PDT) and a CO 2 laser at 10.6 μm (to bring about HPT). Damage to the CAM vasculature, due to combined PDT + HPT, was compared to the outcome of the separate modalities, and a synergistic effect of about 40% was observed. © 1992 Wiley‐Liss, Inc.
Photodynamic therapy (PDT) has been described in terms of cellular and vascular effects. The precise mechanisms of cellular and vascular damage are still unknown. In this study, the photodynamic inactivation of endothelial cells in vitro and damage to the microvasculature in vivo by naturally occurring porphyrins (uroporphyrin III (UP), coproporphyrin III (CP) and protoporphyrin IX (PP)) were investigated. The chick chorioallantoic membrane model (CAM model) was used, which is convenient for the study of damage to the microcirculation induced by PDT. The hydrophilic porphyrins UP and CP exhibited low cytotoxicity towards endothelial cells. Only small amounts of UP and CP were taken up, resulting in weak inactivation after irradiation. In contrast, the more lipophilic PP showed a marked cytotoxicity. Considerable amounts of PP were accumulated in the cells, leading to pronounced inactivation after light exposure. For the three porphyrins, damage to the microvasculature was observed. The damage caused by the hydrophilic porphyrins UP and CP was strongly dependent on the drug and light dose. For vascular injury, the efficacy was graded as UP < CP < PP.
The singlet-oxygen-mediated reaction of meso-tetraphenylporphine tetrasulphonate (TPPS4) with different chemical acceptors in buffered aqueous solution was studied as a function of temperature. Imidazole, tryptophan, dimethyl p-nitrosoaniline, (RNO) and furfuryl alcohol served as acceptors. The measurements were performed in real time by spectroscopic or electrochemical monitoring of the consumption of the various reagents, acceptors or dissolved oxygen as a function of the absorbed energy. The results show the following increases in the reaction rate over the temperature range 15-45-degrees-C: tryptophan (86%), RNO (90%), furfuryl alcohol (150%) and imidazole (210%). The influence of temperature-correlated changes in the initial oxygen concentration and pH was investigated. Possible implications of the present results for the synergistic influence of hyperthermia and photodynamic therapy are discussed.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStructural characterization of the product of oxidation of a macrocyclic cobalt(II) complex in pyridine solutionEliana Sister, Varda Gottfried, Moshe Kapon, Menahem Kaftory, Zvi Dori, and Harry B. GrayCite this: Inorg. Chem. 1988, 27, 4, 600–604Publication Date (Print):February 1, 1988Publication History Published online1 May 2002Published inissue 1 February 1988https://pubs.acs.org/doi/10.1021/ic00277a007https://doi.org/10.1021/ic00277a007research-articleACS PublicationsRequest reuse permissionsArticle Views145Altmetric-Citations26LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts
AbstractThe title reaction gives the Co(III) complexes (II) isolated as their BF4 salts.