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1.
J Am Chem Soc ; 145(20): 11364-11374, 2023 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-37183414

RESUMO

Ru catalysts promoted with alkali and alkaline earth have shown superior ammonia (NH3) synthesis activities under mild conditions. Although these promoters play a vital role in enhancing catalytic activity, their function has not been clearly understood. Here, we synthesize a series of Ba-Ru/MgO catalysts with an optimal Ru particle size (∼2.3 nm) and tailored BaO-Ru interfacial structures. We discover that the promoting effect is created through the separate storage of H+/e- pairs at the BaO-Ru interface. Chemisorbed H atoms on Ru dissociate into H+/e- pairs at the BaO-Ru interface, where strongly basic, nonreducible BaO selectively captures H+ while leaving e- on Ru. The resulting electron accumulation in Ru facilitates N2 activation via enhanced π-backdonation and inhibits hydrogen poisoning during NH3 synthesis. Consequently, the formation of intimate BaO-Ru interface without an excessive loss of accessible Ru sites enables the synthesis of highly active catalysts for NH3 synthesis.

2.
Angew Chem Int Ed Engl ; 62(34): e202304244, 2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37366041

RESUMO

In many industrially important reactions, caustic mineral acid catalysts have been successfully replaced with green solid acids such as zeolites. In this context, extensive efforts have been devoted to replacing HCl to produce methylenedianiline (MDA), a key intermediate in polyurethane production. Unfortunately, limited success has been achieved thus far due to low activity, selectivity towards the desired 4,4'-MDA, and rapid catalyst deactivation. Here we report that meso-/microporous hierarchical LTL zeolite exhibits unprecedentedly high activity, selectivity, and stability. The one-dimensional cage-like micropores of LTL promote the bimolecular reaction between two para-aminobenzylaniline intermediates to selectively produce 4,4'-MDA and inhibit the formation of undesired isomers and heavy oligomers. Meanwhile, the secondary mesopores alleviate mass transfer limitations, resulting in a 7.8-fold higher MDA formation rate compared to solely microporous LTL zeolite. Due to suppressed oligomer formation and fast mass transfer, the catalyst exhibits inappreciable deactivation in an industrially relevant continuous flow reactor.

3.
Appl Opt ; 55(20): 5419-22, 2016 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-27409320

RESUMO

We demonstrate photoacoustic (PA) imaging using a compact gain-switched Ti:sapphire laser. Additionally, a simple laser configuration is provided. The Ti:sapphire laser is pumped using a frequency-doubled pulsed neodymium-doped yttrium aluminum garnet pulse laser operating at a repetition rate of 10 Hz, with a pump energy of 37 mJ. No water cooling is required for the Ti:sapphire crystal. The output pulse energy and pulse duration of the laser are 13.6 mJ and 11 ns, respectively. Thus, the power conversion efficiency is 36.7%. As the end mirror in a laser cavity is adjusted in a horizontal direction, the output wavelength can be tuned within a range of 725-880 nm with a spectral bandwidth of approximately 1 nm. The laser has a small footprint size of 50 cm×35 cm including even laser pumping. Because the near-infrared region has significant advantages in the context of absorption and scattering in biological tissues, our laser can be used for PA imaging. Apart from obtaining PA images of a tube filled with indocyanine green immersed in water and placed under chicken breast tissue, our laser system could also be used for the simultaneous PA and ultrasound (US) dual-modality imaging of blood vessels lying beneath the skin of a human middle finger. We used a commercially available US machine for the PA and US dual-modality imaging.

4.
Medicine (Baltimore) ; 101(45): e31684, 2022 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-36397414

RESUMO

BACKGROUND: Postoperative pain after open thoracotomy is known to be very severe and affects sleep quality. This study aimed to investigate the effects of a programmed intermittent epidural bolus injection versus continuous epidural injection for controlling nighttime pain and improving sleep quality after thoracotomy. METHODS: Seventy-six patients scheduled for open thoracotomy for lung cancer or other lung diseases were enrolled. The participants were divided into 2 groups. Group A was continuously injected with 0.2% levobupivacaine at 1.1 mL/h, and group B was injected intermittently with 3 mL 0.2% levobupivacaine at 3 hours intervals through a thoracic epidural catheter via a programmed infusion pump. Within 48 hours after surgery, the degree of pain control using visual analog scale and the patients' sleep conditions on postoperative day (POD) 0 and 1 were evaluated, and other adverse events were investigated. RESULTS: On POD 1 night, the visual analog scale in group B showed lower than group A (P = .009). Comparison of time to fall asleep showed no differences between 2 groups. Total sleep time was no difference on POD 0 but was longer in group B than that in group A on POD 1 (P = .042). Awakening from sleep on POD 0 was lower in group B than that in group A (P = .033), and satisfaction with sleep quality on POD 0 was superior in group B compared to group A (P = .005). Postoperative nausea and vomiting occurred more frequently in group B than in group A (P = .018). CONCLUSION: The programmed intermittent epidural bolus technique of patient-controlled epidural analgesia reduces postoperative nighttime pain and improves sleep quality in patients undergoing thoracotomy for lung cancer or other lung diseases.


Assuntos
Analgesia Epidural , Pneumopatias , Neoplasias Pulmonares , Humanos , Toracotomia/efeitos adversos , Levobupivacaína , Analgesia Epidural/métodos , Qualidade do Sono , Injeções Epidurais , Dor Pós-Operatória/tratamento farmacológico , Dor Pós-Operatória/prevenção & controle , Dor Pós-Operatória/etiologia , Neoplasias Pulmonares/etiologia , Pneumopatias/etiologia
5.
J Biomed Opt ; 22(9): 91513, 2017 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-28444151

RESUMO

We propose a compact and easy to use photoacoustic imaging (PAI) probe structure using a single strand of optical fiber and a beam combiner doubly reflecting acoustic waves for convenient detection of lymph nodes and cancers. Conventional PAI probes have difficulty detecting lymph nodes just beneath the skin or simultaneously investigating lymph nodes located in shallow as well as deep regions from skin without any supplementary material because the light and acoustic beams are intersecting obliquely in the probe. To overcome the limitations and improve their convenience, we propose a probe structure in which the illuminated light beam axis coincides with the axis of the ultrasound. The developed PAI probe was able to simultaneously achieve a wide range of images positioned from shallow to deep regions without the use of any supplementary material. Moreover, the proposed probe had low transmission losses for the light and acoustic beams. Therefore, the proposed PAI probe will be useful to easily detect lymph nodes and cancers in real clinical fields.


Assuntos
Linfonodos/diagnóstico por imagem , Neoplasias/diagnóstico por imagem , Técnicas Fotoacústicas , Acústica , Humanos , Ultrassonografia
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