One- and Two-Photon Uncaging of Carbon Monoxide (CO) with Real-Time Monitoring: On-Demand Carbazole-Based Dual CO-Releasing Platform to Test over Single and Combinatorial Approaches for the Efficient Regression of Orthotopic Murine Melanoma In Vivo.

Herein, we report three new metal-free, photochemically active single, dual, and combinatorial CORMs (photoCORMs) based on a carbazole-fused 1,3-dioxol-2-one moiety which released one equivalent of CO, two equivalent of CO, and a combination of one equivalent of each CO and anticancer drug upon one- and two-photon excitation, respectively. The photoCORMs exhibited good cellular uptake and real-time monitoring ability of CO uncaging by a color change approach in cancerous B16F10 cells. Interestingly, the cytotoxicity assay on B16F10 cells indicated that the dual photoCORM has increased anticancer activity over the single and combinatorial photoCORMs upon irradiation. Our results also showed that CO could accelerate the effectiveness of the well-known anticancer drug (chlorambucil). Finally, the in vivo evaluation of the dual photoCORM on an established murine melanoma tumor (C57BL/6J mouse model) manifested a significant regression of tumor volume and led to significant improvement (>50%) in the overall survivability.

Indirect photodegradation of fludioxonil by hydroxyl radical and singlet oxygen in aquatic environment: Mechanism, photoproducts formation and eco-toxicity assessment.

Fludioxonil has been proven valuable as a broad-spectrum fungicide. However, there are concerns about its risk posed to non-target organisms in aquatic environments. In this paper, the mechanism, photoproducts transformation and eco-toxicity of fludioxonil during •OH/1O2-initiated process were systematically studied using quantum chemistry and computational toxicology. The results indicate that the two favorable pathways of •OH/1O2-initiated reactions are both occurred in pyrrole ring. It can conclude that the rate constants of •OH and 1O2 are 1.23 × 1010 and 3.69 × 107 M-1 s-1 at 298K, respectively, which results in half-lives of <2 days in surface waters under sunlit near-surface conditions. Based on toxicity assessments, these photoproducts showed a decreased aquatic toxicity but the majority products are still toxic. This study gives more insight into the chemical transformation mechanism of fludioxonil in aquatic environments.

Structural elucidation and estimation of the acute toxicity of the major UV-visible photoproduct of fludioxonil - detection in both skin and flesh samples of grape.

Ultraviolet (UV)-visible irradiation of fludioxonil was investigated with two photoreactors using either a mercury or xenon vapor lamp. In both cases, it led to the formation of only one photoproduct in significant amount: 2-(2,2-difluorobenzo[d][1,3]dioxol-4-yl)-2-(nitrosomethylene)-4-oxobutanenitrile, which has been characterized using Liquid Chromatography - High Resolution - Tandem Mass Spectrometry (LC-HR-MS/MS) coupling. A photolysis pathway has been proposed to rationalize its formation in degassed water. In vitro bioassays on Vibrio fischeri bacteria showed that UV-vis irradiation of an aqueous solution of fludioxonil significantly increases its toxicity. Because no other by-product was detected in significant amount, the photoproduct mentioned above may be considered mainly responsible for this increase in toxicity. Grape berries treated with a 50 ppm aqueous solution of fludioxonil were submitted to UV-visible irradiation under laboratory conditions. The fungicide and photoproduct were detected in both skin and flesh of berries, even after they have been rinsed with water. The ability of the photoproduct to pass through the fruit skin is comparable with that of fludioxonil. These results are of concern for consumers because they mean that water tap rinsing does not lead to efficient removing of both compounds.

Sesamin as a co-initiator for unfilled dental restorations.

A natural component, sesamin (SA), was used to replace conventional amine as co-initiator for dental composite. A combination of camphorquinone (CQ) and SA was employed to initiate the photopolymerization of 2-2-bis[4-(2-hydroxy-3-methacryloxyprop-1-oxy)phenyl] propane/triethylene glycol dimethacrylate (70/30wt.%). The kinetics was recorded by real-time Fourier transform infrared spectroscopy. The mechanical properties were measured by dynamic mechanical analysis, the cell toxicity was investigated by MTT assay and a mixture of CQ and ethyl 4-N,N-dimethylaminobenzoate (EDMAB) was used as control in the same photocuring condition. The results indicated that the addition of SA as co-initiator greatly improved the rate of polymerization and final double-bond conversion (DC) when compared with the system initiated by CQ alone. Compared with EDMAB, the final DC of the CQ/SA system (71%) was slightly lower than that of CQ/EDMAB (76%); SA resulted in approximately the same storage modulus at around 37 degrees C, but a slightly higher glass transition temperature. SA produced lower yellowing effect and good in vitro biocompatibility. The water sorption and solubility for two mixtures were very close and within the range of the ISO 4049 specification. These results suggest that SA is an effective alternative co-initiator to conventional amine. The natural compound characteristics of SA make it more promising than amine in dental resin formulations.

A natural component as coinitiator for unfilled dental resin composites.

A natural component, 1,3-benzodioxole (BDO), was used for the purpose of replacing the conventional amine for dental composite. Camphorquinone (CQ)/BDO was used to initiate the photopolymerization of urethane dimethacrylate (UDMA)/triethylene glycol dimethacrylate (TEGDMA) (70/30 wt %). The kinetics was recorded by real-time Fourier transformation infrared spectroscopy (FTIR). The mechanical properties were measured by dynamic mechanical analyzer (DMA), and CQ/ethyl 4-N,N-dimethylaminobenzoate (EDMAB) mixture was used as control in the same photocuring condition. The results indicated that, the addition of BDO as coinitiator greatly improved the rate of polymerization and final double bond conversion (DC), when compared with the system initiated by CQ alone. BDO and EDMAB were found to reach almost the same final DC (75%), though the kinetics of two systems was different. Comparing with EDMAB, BDO brought approximately the same glass transition temperature (Tg), but slightly higher storage modulus around 37 degrees C. The water sorption and solubility for two mixtures were almost the same and within the range of the ISO 4049's standards. These results suggested that BDO was an effective alternative to conventional amine for coinitiator. And the human diet characteristics of BDO made it more promising than amine in the dental resin formulations.