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51.
Rene Hornung Mathias K. Fehr Jill Monti-Frayne Tatiana B. Krasieva Bruce J. Tromberg Michael W. Berns Yona Tadir 《Photochemistry and photobiology》1999,70(4):624-629
Photodynamic therapy (PDT) uses light to activate a photosensitizer that has been absorbed or retained preferentially by cancer cells after systemic administration. The first pegylated photosensitizer, tetrakis-(m-methoxypolyethylene glycol) derivative of 7,8-dihydro-5,10,15,20-tetrakis(3-hydroxyphenyl)-21,23-[H]-porphyrin (PEG-m-THPC), was evaluated to target selectively unresectable pelvic ovarian cancer bulks. Our goals were two-fold: (1) to establish an ovarian cancer model suitable for the development of debulking techniques and (2) to characterize the pharmacokinetics and tumor selectivity of PEG-m-THPC by fluorescence microscopy. NuTu-19 ovarian cancer cells were injected into the caudal part of the right psoas muscle of Fisher rats. Five weeks later, 30 mg/kg body weight of PEG-m-THPC was injected intravenously. Necropsy was performed between 4 and 10 days following drug application, and fluorescence of the tumor and various abdominal organs was measured. All rats developed bulky pelvic tumors with an average diameter of 2.6 cm (+/- 0.6 SD). Tumor masses were encompassing and infiltrating pelvic organs in a similar manner to ovarian cancers in humans. Fluorescence of cancer tissue was maximal 8-10 days following drug application. At 8 days, the tumor-to-tissue ratio was 40:1 (+/- 12 SE) for most abdominal organs. We conclude that this tumor model may be used for the study of new pelvic debulking techniques, and that the tumor selectivity of PEG-m-THPC is exceptionally high 8 days after drug application. Based on these data, we are currently developing a PDT-based minimally invasive debulking technique for advanced ovarian cancer. 相似文献
52.
Jill K. Wolken Viet Q. Nguyen František Tureček 《Journal of mass spectrometry : JMS》1997,32(11):1162-1169
Hypervalent organic ammonium radicals were generated by collisional neutralization with dimethyl disulfide of protonated 1,4-diazabicyclo[2.2.2]octane (1H+), N,N′-dimethylpiperazine (2H+) and N-methylpiperazine (3H+). The radicals dissociated completely on the 5.1 μs time-scale. Radical 1H• underwent competitive N−H and N−C bond dissociations producing 1,4-diazabicyclo[2.2.2]octane and small ring fragments. Dissociations of radical 2H• proceeded by N−H bond dissociation and ring cleavage, whereas N−CH3 bond cleavage was less frequent. Radical 3H• underwent N−H, N−CH3 and N−Cring bond cleavages followed by post-reionization dissociations of the formed cations. The pattern of bond dissociations in the hypervalent ammonium radicals derived from six-membered nitrogen heterocycles is similar to those of aliphatic ammonium radicals. © 1997 John Wiley & Sons, Ltd. 相似文献
53.
This paper describes the use of ultrasonic guided waves for identifying the mass loading due to underwater limpet mines on ship hulls. The Dynamic Wavelet Fingerprint Technique (DFWT) is used to render the guided wave mode information in two-dimensional binary images because the waveform features of interest are too subtle to identify in time domain. The use of wavelets allows both time and scale features from the original signals to be retained, and image processing can be used to automatically extract features that correspond to the arrival times of the guided wave modes. For further understanding of how the guided wave modes propagate through the real structures, a parallel processing, 3D elastic wave simulation is developed using the finite integration technique (EFIT). This full field, technique models situations that are too complex for analytical solutions, such as built up 3D structures. The simulations have produced informative visualizations of the guided wave modes in the structures as well as mimicking directly the output from sensors placed in the simulation space for direct comparison to experiments. Results from both drydock and in-water experiments with dummy mines are also shown. 相似文献
54.
Oh BK Park S Millstone JE Lee SW Lee KB Mirkin CA 《Journal of the American Chemical Society》2006,128(36):11825-11829
Two-component triblock magnetic nanorods with gold end blocks and nickel interior blocks have been synthesized and used as affinity templates for the simultaneous and efficient separation of a three-component protein mixture. The gold blocks were selectively functionalized with 11-amino-1-undecanethiol, and then glutaraldehyde was used to covalently attach nitrostreptavidin to them. His-tagged proteins bind to the nickel block and biotin-tagged proteins bind to the functionalized gold ends, allowing one to separate a mixture of three proteins with a single material. Each surface-bound protein can be released selectively using imidazole for the His-tagged protein and biotin for the biotinylated protein. 相似文献
55.
Microwave reaction of RuCl3 with 2,2'-bipyridinyl-4,4'-dicarboxylic acid diethyl ester (debpy) in ethylene glycol generated Ru(bpy)3(2+) instead of the expected Ru(debpy)3(2+). Gas chromatography-mass spectrometry analysis of the headspace revealed CO2, and Ru(bpy)3(2+) was recovered from the filtrate. Further experiments suggest that RuCl3 decarboxylates debpy during microwave synthesis. 相似文献
56.
Chen L Kim YM Kucera DJ Harrison KE Bahmanyar S Scott JM Yazbeck D 《The Journal of organic chemistry》2006,71(15):5468-5473
A Claisen rearrangement/iodolactamization sequence starting from commercially available trifluoroacetaldehyde methyl hemiacetal, followed by a classical chemical resolution, provided enantiomerically pure 4,4-difluoro-3,3-dimethylproline (S)-1. No hazardous fluorination reagents were used, and the overall yield over 12 steps was greater than 28%. 相似文献
57.
Relative stabilities of uracil tautomers and cations formed by gas-phase protonation were studied computationally with the B3LYP, MP2, QCISD, and QCISD(T) methods and with basis sets expanding from 6-31G(d,p) to 6-311+G(3df,2p). In accordance with a previous density functional theory study, the dioxo tautomer 1a was the most stable uracil isomer in the gas phase. Gibbs free energy calculations using effective QCISD(T)/6-311+G(3df,2p) energies suggested >99.9% of 1a at equilibrium at 523 K. The most stable ion isomer corresponded to N-1 protonated 2,4-dihydroxypyrimidine, which however is not formed by direct protonation of 1a. The topical proton affinities in 1a followed the order O-8 > O-7 > C-5 > N-3 > N-1. The thermodynamic proton affinity of 1a was calculated as 858 kJ mol−1 at 298 K. A revision is suggested for the current estimate included in the ion thermochemistry database. 相似文献
58.
Kris Korsak Nazanin F Dolatshad Ayona T Silva M Jill Saffrey 《Chemistry Central journal》2012,6(1):1-7
Background
??Dragon??s Blood?? (DB) has long been used as an ethnomedicine in China to invigorate blood circulation for the treatment of traumatic injuries, blood stasis and pain. To comprehensively assess the quality of DB medicine, a precise and accurate method that can rapidly separate, characterize and quantify multiple active components of DB is crucial.Results
An ultra performance liquid chromatography (UPLC) coupled with photodiode array detection (PAD) and electrospray ionization mass spectrometry (ESI-MS) method was developed for characterization and determination of six flavonoids in DB. A comprehensive validation of the developed method was conducted, and confirmed that the method presented good sensitivity, precision and accuracy. All linear regressions were acquired with R 2 > 0.99, and the limits of detection ranged from 0.06 to 0.83 ng. The relative standard deviation (RSD) values were found to be within the range 1.4?C3.8% for the method repeatability test. Recovery studies for the quantified compounds were found to be within the range 94.2?C102.8% with RSD less than 4.9%. DB samples collected from different geographical regions were analyzed by the present method, and the results demonstrated that the contents of the six flavonoids in DB samples varied significantly. Three major active components among the six flavonoids, namely dracorhodin, (2S)-5-methoxyflavan-7-ol and (2S)-5-methoxy-6-methylflavan-7-ol, are suggested as the index for DB quality evaluation.Conclusions
Overall, the present hyphenation method is highly efficient and reliable, and hence suitable for the characterization and determination of the flavonoids of DB ethnomedicine. 相似文献59.
Ambrus JI Halliday JI Kanizaj N Absalom N Harpsøe K Balle T Chebib M McLeod MD 《Chemical communications (Cambridge, England)》2012,48(53):6699-6701
The 3-methylmaleimide congeners of the natural product methyllycaconitine (MLA) and an analogue covalently attach to functional cysteine mutants of the α7 nicotinic acetylcholine receptor (nAChR). 相似文献
60.
Brückner C Ogikubo J McCarthy JR Akhigbe J Hyland MA Daddario P Worlinsky JL Zeller M Engle JT Ziegler CJ Ranaghan MJ Sandberg MN Birge RR 《The Journal of organic chemistry》2012,77(15):6480-6494
The rational syntheses of meso-tetraaryl-3-oxo-2-oxaporphyrins 5, known as porpholactones, via MnO(4)(-)-mediated oxidations of the corresponding meso-tetraaryl-2,3-dihydroxychlorins (7) is detailed. Since chlorin 7 is prepared from the parent porphyrin 1, this amounts to a 2-step replacement of a pyrrole moiety in 1 by an oxazolone moiety. The stepwise reduction of the porpholactone 5 results in the formation of chlorin analogues, meso-tetraaryl-3-hydroxy-2-oxachlorin (11) and meso-tetraaryl-2-oxachlorins (12). The reactivity of 11 with respect to nucleophilic substitution by O-, N-, and S-nucleophiles is described. The profound photophysical consequences of the formal replacement of a pyrrole with an oxazolone (porphyrin-like chromophore) or (substituted) oxazole moiety (chlorin-like chromophore with, for the parent oxazolochlorin 12, red-shifted Q(x) band with enhanced oscillator strengths) are detailed and rationalized on the basis of SAC-CI and MNDO-PSDCI molecular orbital theory calculations. The single crystal X-ray structures of the porpholactones point at a minor steric interaction between the carbonyl oxygen and the flanking phenyl group. The essentially planar structures of all chromophores in all oxidation states prove that the observed optical properties originate from the intrinsic electronic properties of the chromophores and are not subject to conformational modulation. 相似文献