Catalyst Halogenation Enables Rapid and Efficient Polymerizations with Visible to Near-Infrared Light

Author(s):  
Alex Stafford ◽  
Dowon Ahn ◽  
Emily Raulerson ◽  
Kun-You Chung ◽  
Kaihong Sun ◽  
...  

Driving rapid polymerizations with visible to near-infrared (NIR) light will enable nascent technologies in the emerging fields of bio- and composite-printing. However, current photopolymerization strategies are limited by long reaction times, high light intensities, and/or large catalyst loadings. Improving efficiency remains elusive without a comprehensive, mechanistic evaluation of photocatalysis to better understand how composition relates to polymerization metrics. With this objective in mind, a series of methine- and aza-bridged boron dipyrromethene (BODIPY) derivatives were synthesized and systematically characterized to elucidate key structure-property relationships that facilitate efficient photopolymerization driven by visible to NIR light. For both BODIPY scaffolds, halogenation was shown as a general method to increase polymerization rate, quantitatively characterized using a custom real-time infrared spectroscopy setup. Furthermore, a combination of steady-state emission quenching experiments, electronic structure calculations, and ultrafast transient absorption revealed that efficient intersystem crossing to the lowest excited triplet state upon halogenation was a key mechanistic step to achieving rapid photopolymerization reactions. Unprecedented polymerization rates were achieved with extremely low light intensities (< 1 mW/cm<sup>2</sup>) and catalyst loadings (< 50 μM), exemplified by reaction completion within 60 seconds of irradiation using green, red, and NIR light-emitting diodes.

2020 ◽  
Author(s):  
Alex Stafford ◽  
Dowon Ahn ◽  
Emily Raulerson ◽  
Kun-You Chung ◽  
Kaihong Sun ◽  
...  

Driving rapid polymerizations with visible to near-infrared (NIR) light will enable nascent technologies in the emerging fields of bio- and composite-printing. However, current photopolymerization strategies are limited by long reaction times, high light intensities, and/or large catalyst loadings. Improving efficiency remains elusive without a comprehensive, mechanistic evaluation of photocatalysis to better understand how composition relates to polymerization metrics. With this objective in mind, a series of methine- and aza-bridged boron dipyrromethene (BODIPY) derivatives were synthesized and systematically characterized to elucidate key structure-property relationships that facilitate efficient photopolymerization driven by visible to NIR light. For both BODIPY scaffolds, halogenation was shown as a general method to increase polymerization rate, quantitatively characterized using a custom real-time infrared spectroscopy setup. Furthermore, a combination of steady-state emission quenching experiments, electronic structure calculations, and ultrafast transient absorption revealed that efficient intersystem crossing to the lowest excited triplet state upon halogenation was a key mechanistic step to achieving rapid photopolymerization reactions. Unprecedented polymerization rates were achieved with extremely low light intensities (< 1 mW/cm<sup>2</sup>) and catalyst loadings (< 50 μM), exemplified by reaction completion within 60 seconds of irradiation using green, red, and NIR light-emitting diodes.


Micromachines ◽  
2019 ◽  
Vol 10 (2) ◽  
pp. 81
Author(s):  
Shunko Inada ◽  
Hayao Nakanishi ◽  
Masahiro Oda ◽  
Kensaku Mori ◽  
Akihiro Ito ◽  
...  

Laparoscopic surgery is now a standard treatment for gastric cancer. Currently, the location of the gastric cancer is identified during laparoscopic surgery via the preoperative endoscopic injection of charcoal ink around the primary tumor; however, the wide spread of injected charcoal ink can make it difficult to accurately visualize the specific site of the tumor. To precisely identify the locations of gastric tumors, we developed a fluorescent detection system comprising clips with glass phosphor (Yb3+, Nd3+ doped to Bi2O3-B2O3-based glasses, size: 2 mm × 1 mm × 3 mm) fixed in the stomach and a laparoscopic fluorescent detection system for clip-derived near-infrared (NIR) light (976 nm). We conducted two ex vivo experiments to evaluate the performance of this fluorescent detection system in an extirpated pig stomach and a freshly resected human stomach and were able to successfully detect NIR fluorescence emitted from the clip in the stomach through the stomach wall by the irradiation of excitation light (λ: 808 nm). These results suggest that the proposed combined NIR light-emitting clip and laparoscopic fluorescent detection system could be very useful in clinical practice for accurately identifying the location of a primary gastric tumor during laparoscopic surgery.


2020 ◽  
Vol 8 (41) ◽  
pp. 14378-14385
Author(s):  
You-Xuan Liu ◽  
Rong-Huei Yi ◽  
Chien-Hsiang Lin ◽  
Zu-Po Yang ◽  
Chin-Wei Lu ◽  
...  

Near-infrared (NIR) light-emitting devices with organic semiconductors have great potential for applications in bio-imaging, telecommunication, night-vision displays, and chemical sensing.


Nanophotonics ◽  
2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Yiyue Zhang ◽  
Masoumeh Keshavarz ◽  
Elke Debroye ◽  
Eduard Fron ◽  
Miriam Candelaria Rodríguez González ◽  
...  

Abstract Lead halide perovskites have attracted tremendous attention in photovoltaics due to their impressive optoelectronic properties. However, the poor stability of perovskite-based devices remains a bottleneck for further commercial development. Two-dimensional perovskites have great potential in optoelectronic devices, as they are much more stable than their three-dimensional counterparts and rapidly catching up in performance. Herein, we demonstrate high-quality two-dimensional novel perovskite thin films with alternating cations in the interlayer space. This innovative perovskite provides highly stable semiconductor thin films for efficient near-infrared light-emitting diodes (LEDs). Highly efficient LEDs with tunable emission wavelengths from 680 to 770 nm along with excellent operational stability are demonstrated by varying the thickness of the interlayer spacer cation. Furthermore, the best-performing device exhibits an external quantum efficiency of 3.4% at a high current density (J) of 249 mA/cm2 and remains above 2.5% for a J up to 720 mA cm−2, leading to a high radiance of 77.5 W/Sr m2 when driven at 6 V. The same device also shows impressive operational stability, retaining almost 80% of its initial performance after operating at 20 mA/cm2 for 350 min. This work provides fundamental evidence that this novel alternating interlayer cation 2D perovskite can be a promising and stable photonic emitter.


2021 ◽  
pp. 103879
Author(s):  
Hyung-Joo Lee ◽  
Gwang-Hoon Park ◽  
Jin-Su So ◽  
Choong-Hun Lee ◽  
Jae-Hoon Kim ◽  
...  

2011 ◽  
Vol 20 (7) ◽  
pp. 1405-1415 ◽  
Author(s):  
Brian D. Hodgson ◽  
David M. Margolis ◽  
Donna E. Salzman ◽  
Dan Eastwood ◽  
Sergey Tarima ◽  
...  

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Mary K. Popp ◽  
Imane Oubou ◽  
Colin Shepherd ◽  
Zachary Nager ◽  
Courtney Anderson ◽  
...  

Photothermal therapy (PTT) treatments have shown strong potential in treating tumors through their ability to target destructive heat preferentially to tumor regions. In this paper we demonstrate that PTT in a murine melanoma model using gold nanorods (GNRs) and near-infrared (NIR) light decreases tumor volume and increases animal survival to an extent that is comparable to the current generation of melanoma drugs. GNRs, in particular, have shown a strong ability to reach ablative temperatures quickly in tumors when exposed to NIR light. The current research tests the efficacy of GNRs PTT in a difficult and fast growing murine melanoma model using a NIR light-emitting diode (LED) light source. LED light sources in the NIR spectrum could provide a safer and more practical approach to photothermal therapy than lasers. We also show that the LED light source can effectively and quickly heatin vitroandin vivomodels to ablative temperatures when combined with GNRs. We anticipate that this approach could have significant implications for human cancer therapy.


Vascular ◽  
2021 ◽  
pp. 170853812110514
Author(s):  
Nail Kahraman ◽  
Gündüz Yümün ◽  
Deniz Demir ◽  
Kadir K Özsin ◽  
Sadık A Sünbül ◽  
...  

Objectives Varicose veins that cannot be seen with the naked eye can be easily detected with Near Infrared (NIR) light. With a minimally invasive procedure performed with NIR light guided, the need for reoperation is reduced, while optimal treatment of venous insufficiency and symptoms is provided. In this study, the detection of residual varicose veins after varicose vein surgery using NIR light and the results of treatment of sclerotherapy were investigated. Methods In this retrospective study, treatment and clinical outcomes of patients’ who underwent NIR light-guided foam sclerotherapy for Clinical-Etiology-Anatomy-Pathophysiology (CEAP) (C1, C2) stage residual varicose veins after surgical varicose treatment between 2014 and 2017 were examined. Data of patients who underwent foam sclerotherapy with NIR light were collected and analyzed. Results A total of 151 patients and 171 lower extremity varicose veins were treated with surgery. 55 (35.7%) of the patients were male, and 96 (62.3%) were female. Their age ranges from 20 to 64, with an average age of 45.38. 4 (2.6%) of the patients had phlebectomy. 137 of patients (90.7%) had ligation of perforated veins, phlebectomy, and great saphenous vein (GSV) stripping, 10 of patients (6.6%) had GSV stripping, perforating vein ligation, phlebectomy, and small saphenous vein (SSV) surgery. No residual leakage was observed in the controls of GSV, SSV, and perforating veins by duplex ultrasonography (DUS). In the first month after varicose surgery, an average of 1.64 ± 1.05 sessions of sclerotherapy was applied to patients with CEAP C1, C2 stage residual varicose veins. 70 patients had one session of sclerotherapy, 37 patients had two sessions of sclerotherapy, 20 patients had three sessions of sclerotherapy, and 11 patients had four sessions of sclerotherapy administrated. The need for complementary therapy was required for all female patients; 13 of the male patients did not require complementary sclerotherapy. While single-session sclerotherapy was applied to most male patients (32 (58.18%), 10 (18.18%) patients received two sclerotherapy sessions. After completing sclerotherapy, 7 (4.63%) patients had superficial venous thrombosis, and 13 (8.60%) patients had hyperpigmentation. Conclusion Surgical treatment is a safe and effective technique in venous insufficiency. Nevertheless, residual varicose veins may remain, and these can be detected noninvasively with NIR light. Foam sclerotherapy with NIR light is a minimally invasive and safe treatment method for small residual varicose veins after the operation. We think that sclerotherapy with NIR light as a complementary treatment is a practical, reliable, and demanding treatment for clinical improvement, especially in female patients.


2016 ◽  
Vol 18 (6) ◽  
pp. 5034-5039 ◽  
Author(s):  
Jia-Hong Hsu ◽  
Hai-Ching Su

NIR EL can be achieved by adjusting the device thickness of non-doped saturated red LECs.


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