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101.
Emily Oakley David Bellnier Alan Hutson Hannah Cooper Michael Habitzruther Sandra Sexton Leslie Curtin Lawrence Tworek Matthew Mallory Barbara Henderson Gal Shafirstein 《Photochemistry and photobiology》2020,96(2):397-404
The objective of the present study was to develop a predictive model for Photofrin®-mediated interstitial photodynamic therapy (I-PDT) of locally advanced tumors. Our finite element method was used to simulate 630-nm intratumoral irradiance and fluence for C3H mice and New Zealand White rabbits bearing large squamous cell carcinomas. Animals were treated with light only or I-PDT using the same light settings. I-PDT was administered with Photofrin® at 5.0 or 6.6 mg kg−1, 24 h drug-light interval. The simulated threshold fluence was fixed at 45 J cm−2 while the simulated threshold irradiance varied, intratumorally. No cures were obtained in the mice treated with a threshold irradiance of 5.4 mW cm−2. However, 20–90% of the mice were cured when the threshold irradiances were ≥8.6 mW cm−2. In the rabbits treated with I-PDT, 13 of the 14 VX2 tumors showed either local control or were cured when threshold irradiances were ≥15.3 mW cm−2 and fluence was 45 J cm−2. No tumor growth delay was observed in VX2 treated with light only (n = 3). In the mouse studies, there was a high probability (92.7%) of predicting cure when the initial tumor volume was below the median (493.9 mm3) and I-PDT was administered with a threshold intratumoral irradiance ≥8.6 mW cm−2. 相似文献
102.
Hannah E. Hackney Dr. Marco Paladino Hao Fu Prof. Dr. Dennis G. Hall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(63):14324-14329
This study describes the synthesis, structure, and photophysical properties of a new luminescent polyaromatic boronic acid scaffold, diazaboryl-naphthyl-ketones (DNKs). These stable compounds display extremely bright fluorescence, aggregation-induced emission, positive solvatochromism, and solid-state fluorescence. DFT calculations and X-ray crystallographic study revealed notable electronic and structural differences between these compounds and the parent diaminonaphthalene (DAN) adducts. Acylation of the DAN system causes a localization of both HOMO and LUMO onto the DNK unit, which validates the negligible influence of the B-aryl substituent. The LUMO energy is lowered, and its shape significantly altered. Photophysical data in solution and the solid state revealed blue-shifted, narrowed, and intense emissions for DNKs (up to 89 % quantum yield). The potential utility of the fluorogenic DNK system was demonstrated with a proof-of-concept for the determination of trace boronic acid contaminants in solid samples, down to one-ppm level, using HPLC with fluorescence detection. This method could be useful in pharmaceutical development for the quantitation of difficult-to-detect and potentially mutagenic residual boronic acid from late cross-coupling reactions in drug syntheses. 相似文献
103.
Dr. Zhong Wang Hannah R. Felstead Robert I. Troup Prof. Bruno Linclau Dr. Philip T. F. Williamson 《Angewandte Chemie (International ed. in English)》2023,62(21):e202301077
Bioactive compounds generally need to cross membranes to arrive at their site of action. The octanol-water partition coefficient (lipophilicity, logPOW) has proven to be an excellent proxy for membrane permeability. In modern drug discovery, logPOW and bioactivity are optimized simultaneously, for which fluorination is one of the relevant strategies. The question arises as to which extent the often subtle logP modifications resulting from different aliphatic fluorine-motif introductions also lead to concomitant membrane permeability changes, given the difference in molecular environment between octanol and (anisotropic) membranes. It was found that for a given compound class, there is excellent correlation between logPOW values with the corresponding membrane molar partitioning coefficients (logKp); a study enabled by novel solid-state 19F NMR MAS methodology using lipid vesicles. Our results show that the factors that cause modulation of octanol-water partition coefficients similarly affect membrane permeability. 相似文献
104.
To achieve spatial resolution of a multi-component gel, a double diffusion approach is used which enables the precise programming of self-assembled patterned domains with well-defined shapes and sizes. The low-molecular-weight gelators (LMWGs) used in this study are pH-responsive DBS-CO2H and thermally-responsive DBS-CONHNH2 (both based on 1,3:2,4-dibenzylidenesorbitol, DBS). A DBS-CONHNH2 gel was initially assembled in a tray, and then loaded at carefully-selected positions with either basified DBS-CO2H (i.e. DBS-carboxylate) or an acid. These soluble components subsequently diffuse through the pre-formed gel matrix, and in the domains when/where they mix, protonation of the DBS-carboxylate induces self-assembly of the DBS-CO2H network, leading to a patterned gel-in-gel object with well-defined shape and dimensions. Using a strong acid achieves fast gelation kinetics, creating smaller, better-defined macroscale objects but with less nanoscale order. Using a weak acid source with slow kinetics, gives slightly larger objects, but on the nanoscale the DBS-CO2H network formation is better controlled, giving more homogeneous nanoscale structures and stiffer objects. The patterned objects can be further reinforced by the presence of agarose polymer gelator. The shape of the patterning is programmed by both the shape of the central reservoir and the starting geometry in which the reservoirs are organised, with the balance between factors depending on assembly kinetics, as dictated by the choice of acid. This simple methodology therefore enables programming of patterned gels with spatiotemporal control and emergent patterning characteristics.To achieve spatial resolution of a multi-component gel, a double diffusion approach is used which enables the precise programming of emergent self-assembled patterned domains with well-defined shapes and sizes. 相似文献
105.
We examine the rhetorical methods of Leonardo of Pisa in his exposition of single false position in Liber Abbaci. For example, Leonardo makes extensive use of formulaic phrases in his solutions. Some of these formulas also seem to indicate whether a particular solution needs further justification. Although he prefers proofs in terms of the pseudo-Euclidean canon of al-Khwārizmī, sometimes such proof eludes Leonardo and he resorts instead to justification by experiment. We also look at the extent to which using symbolic representations might distort our view of Leonardo's thinking. 相似文献
106.
There is great demand for inferring causal effect heterogeneity and for open-source statistical software, which is readily available for practitioners. The mcf package is an open-source Python package that implements Modified Causal Forest (mcf), a causal machine learner. We replicate three well-known studies in the fields of epidemiology, medicine, and labor economics to demonstrate that our mcf package produces aggregate treatment effects, which align with previous results, and in addition, provides novel insights on causal effect heterogeneity. For all resolutions of treatment effects estimation, which can be identified, the mcf package provides inference. We conclude that the mcf constitutes a practical and extensive tool for a modern causal heterogeneous effects analysis. 相似文献
107.
108.
Marsden DM Nicholson RL Skindersoe ME Galloway WR Sore HF Givskov M Salmond GP Ladlow M Welch M Spring DR 《Organic & biomolecular chemistry》2010,8(23):5313-5323
The screening of large arrays of drug-like small-molecules was traditionally a time consuming and resource intensive task. New methodology developed within our laboratories provides an attractive low cost, 3D microarray-assisted screening platform that could be used to rapidly assay thousands of compounds. As a proof-of-principle the platform was exploited to screen a number of quorum sensing analogs. Quorum sensing is used by bacterium to initiate and spread infection; in this context its modulation may have significant clinical value. 3D microarray slides were probed with fluorescently labeled ligand-binding domains of the LuxR homolog CarR from Erwinia carotovora subsp. carotovora. The 3D microarray platform was used to discover the biologically active chloro-pyridine pharmacophore, which was validated using a fluorometric ligand binding assay and ITC. Analogs containing the chloro-pyridine pharmacophore were found to be potent inhibitors of N-acyl-homoserine-lactone (AHL) mediated quorum sensing phenotypes in Serratia (IC(50) = ~5 μM) and Pseudomonas aeruginosa (IC(50) = 10-20 μM). 相似文献
109.
Hannah G. Steeds Dr. Jonathan P. Knowles Dr. Wai L. Yu Dr. Jeffery Richardson Dr. Katie G. Cooper Prof. Kevin I. Booker-Milburn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(63):14330-14334
A three-step synthesis of the 2-azabicyclo[3.3.1]nonane ring system from simple pyrroles, employing a combined photochemical/palladium-catalysed approach is reported. Substrate scope is broad, allowing the incorporation of a wide range of functionality relevant to medicinal chemistry. Mechanistic studies demonstrate that the process occurs by acid-assisted C−N bond cleavage followed by β-hydride elimination to form a reactive diene, demonstrating that efficient control of what might be considered off-cycle reactions can result in productive tandem catalytic processes. This represents a short and versatile route to the biologically important morphan scaffold. 相似文献
110.