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1.
Opt Lett ; 49(13): 3556-3559, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38950208

RESUMO

Optical image encryption has long been an important concept in the fields of photonic network processing and communication. Here, we propose a convolution-like operation-based optical image encryption algorithm exploiting a silicon photonic multiplexing architecture to achieve content security. Particularly, the encryption process is completed in a 3 × 3 cross-shaped photonic micro-ring resonator (MRR) array on chip. For the first time, to the best of our knowledge, this algorithm encodes information in an integrated intensity modulation, effectively reducing the encoding difficulty. Moreover, the high reliability and scalability of optical encryption are ensured using both linear and nonlinear operations on photonic chips according to characteristics of MRRs. As the encryption and decryption experiments show, the image restoration accuracy of our optical encryption algorithm exceeds 99% under real system noise at the pixel level, indicating its noise-robust property. Meanwhile, the peak signal-to-noise ratios of the restored and encrypted images are >60 and <15 dB, respectively, revealing both the high accuracy of the restored image and the small correlation between the encrypted and original images. This work adds to the rapidly expanding field of optical image encryption on photonic chips.

2.
Light Sci Appl ; 13(1): 142, 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38914544

RESUMO

Terahertz modulators play a critical role in high-speed wireless communication, non-destructive imaging, and so on, which have attracted a large amount of research interest. Nevertheless, all-optical terahertz modulation, an ultrafast dynamical control approach, remains to be limited in terms of encoding and multifunction. Here we experimentally demonstrated an optical-programmed terahertz switching realized by combining optical metasurfaces with the terahertz metasurface, resulting in 2-bit dual-channel terahertz encoding. The terahertz metasurface, made up of semiconductor islands and artificial microstructures, enables effective all-optical programming by providing multiple frequency channels with ultrafast modulation at the nanosecond level. Meanwhile, optical metasurfaces covered in terahertz metasurface alter the spatial light field distribution to obtain color code. According to the time-domain coupled mode theory analysis, the energy dissipation modes in terahertz metasurface can be independently controlled by color excitation, which explains the principle of 2-bit encoding well. This work establishes a platform for all-optical programmed terahertz metadevices and may further advance the application of composite metasurface in terahertz manipulation.

3.
J Inorg Biochem ; 257: 112612, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38761579

RESUMO

Considerable attention has been devoted to the exploration of organometallic iridium(III) (IrIII) complexes for their potential as metallic anticancer drugs. In this study, twelve half-sandwich IrIII imidazole-phenanthroline/phenanthrene complexes were prepared and characterized. Complexes exhibited promising in-vitro anti-proliferative activity, and some are obviously superior to cisplatin towards A549 cells. These complexes possessed suitable fluorescence, and a non-energy-dependent uptake pathway was identified, subsequently leading to their accumulation in the lysosome and the lysosomal damage. Additionally, complexes could inhibit the cell cycle (G1-phase) and catalyze intracellular NADH oxidation, thus substantiating the elevation of intracellular reactive oxygen species (ROS) level, which confirming the oxidative mechanism. Western blotting further confirmed that complexes could induce A549 cell apoptosis through the lysosomal-mitochondrial anticancer pathway, which was inconsistent with cisplatin. In summary, these complexes offer fresh concepts for the development of organometallic non­platinum anticancer drugs.


Assuntos
Antineoplásicos , Apoptose , Complexos de Coordenação , Imidazóis , Irídio , Fenantrolinas , Humanos , Irídio/química , Irídio/farmacologia , Antineoplásicos/farmacologia , Antineoplásicos/química , Fenantrolinas/química , Fenantrolinas/farmacologia , Imidazóis/química , Imidazóis/farmacologia , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Apoptose/efeitos dos fármacos , Células A549 , Espécies Reativas de Oxigênio/metabolismo , Fenantrenos/química , Fenantrenos/farmacologia , Proliferação de Células/efeitos dos fármacos , Lisossomos/metabolismo , Lisossomos/efeitos dos fármacos
4.
Adv Sci (Weinh) ; : e2402615, 2024 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-38757557

RESUMO

Non-Hermitian degeneracies, also known as exceptional points (EPs), have presented remarkable singular characteristics such as the degeneracy of eigenvalues and eigenstates and enable limitless opportunities for achieving fascinating phenomena in EP photonic systems. Here, the general theoretical framework and experimental verification of a non-Hermitian metasurface that holds a pair of anti-chiral EPs are proposed as a novel approach for efficient terahertz (THz) switching. First, based on the Pancharatnam-Berry (PB) phase and unitary transformation, it is discovered that the coupling variation of ±1 spin eigenstates will lead to asymmetric modulation in two orthogonal linear polarizations (LP). Through loss-induced merging of a pair of anti-chiral EPs, the decoupling of ±1 spin eigenstates are then successfully realized in a non-Hermitian metasurface. Final, the efficient THz modulation is experimentally demonstrated, which exhibits modulation depth exceeding 70% and Off-On-Off switching cycle less than 9 ps in one LP while remains unaffected in another one. Compared with conventional THz modulation devices, the metadevice shows several figures of merits, such as a single frequency operation, high modulation depth, and ultrafast switching speed. The proposed theory and loss-induced non-Hermitian device are general and can be extended to numerous photonic systems varying from microwave, THz, infrared, to visible light.

5.
J Inorg Biochem ; 257: 112586, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38728860

RESUMO

Ferrocene, ruthenium(II) and iridium(III) organometallic complexes, potential substitutes for platinum-based drugs, have shown good application prospects in the field of cancer therapy. Therefore, in this paper, six ferrocene-modified half-sandwich ruthenium(II) and iridium(III) propionylhydrazone complexes were prepared, and the anticancer potential was evaluated and compared with cisplatin. These complexes showed potential in-vitro anti-proliferative activity against A549 cancer cells, especially for Ir-based complexes, and showing favorable synergistic anticancer effect. Meanwhile, these complexes showed little cytotoxicity and effective anti-migration activity. Ir3, the most active complex (ferrocene-appended iridium(III) complex), could accumulate in the intracellular mitochondria, disturb the cell cycle (S-phase), induce the accumulation of reactive oxygen species, and eventually cause the apoptosis of A549 cells. Then, the design of these complexes provides a good structural basis for the multi-active non­platinum organometallic anticancer complexes.


Assuntos
Antineoplásicos , Apoptose , Complexos de Coordenação , Compostos Ferrosos , Hidrazonas , Irídio , Metalocenos , Rutênio , Humanos , Compostos Ferrosos/química , Compostos Ferrosos/farmacologia , Irídio/química , Irídio/farmacologia , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Metalocenos/química , Metalocenos/farmacologia , Rutênio/química , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Hidrazonas/química , Hidrazonas/farmacologia , Hidrazonas/síntese química , Células A549 , Apoptose/efeitos dos fármacos , Espécies Reativas de Oxigênio/metabolismo , Proliferação de Células/efeitos dos fármacos
6.
Opt Lett ; 49(4): 838-841, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38359195

RESUMO

We experimentally establish a 3 × 3 cross-shaped micro-ring resonator (MRR) array-based photonic multiplexing architecture relying on silicon photonics to achieve parallel edge extraction operations in images for photonic convolution neural networks. The main mathematical operations involved are convolution. Precisely, a faster convolutional calculation speed of up to four times is achieved by extracting four feature maps simultaneously with the same photonic hardware's structure and power consumption, where a maximum computility of 0.742 TOPS at an energy cost of 48.6 mW and a convolution accuracy of 95.1% is achieved in an MRR array chip. In particular, our experimental results reveal that this system using parallel edge extraction operators instead of universal operators can improve the imaging recognition accuracy for CIFAR-10 dataset by 6.2% within the same computing time, reaching a maximum of 78.7%. This work presents high scalability and efficiency of parallel edge extraction chips, furnishing a novel, to the best of our knowledge, approach to boost photonic computing speed.

7.
Dalton Trans ; 53(2): 552-563, 2024 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-38054240

RESUMO

Ferrocenyl derivatives and organometallic iridium(III) complexes have been prospective substitutes for platinum-based anticancer drugs. Eight half-sandwich iridium(III) ferrocene-thiosemicarbazide (Fc-TSC) Schiff base anticancer complexes were prepared in this study. These complexes displayed a dimeric structure and exhibited a particular fluorescence due to the "enol" orientation of the TSC pro-ligand. An energy-dependent pathway of the uptake mechanism was ascertained, which ended in the lysosome and led to lysosome damage and apoptosis. Flow cytometry confirmed that the complexes could block the cell cycle (G1 phase) and improve the levels of intracellular reactive oxygen species, indicating an anticancer mechanism of oxidation. Then, a lysosomal-mitochondrial anticancer pathway was verified through western blotting. In vivo toxicity assays confirmed that these complexes showed better anti-migration ability and less toxicity in comparison to cisplatin. Thus, these complexes provide a new strategy for the design of non-platinum organometallic anticancer drugs.


Assuntos
Antineoplásicos , Complexos de Coordenação , Irídio/farmacologia , Irídio/química , Bases de Schiff/farmacologia , Metalocenos/farmacologia , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Estudos Prospectivos , Antineoplásicos/farmacologia , Antineoplásicos/química , Apoptose , Espécies Reativas de Oxigênio/metabolismo , Proliferação de Células , Linhagem Celular Tumoral
8.
Adv Sci (Weinh) ; 10(36): e2304972, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37897321

RESUMO

Non-Hermitian degeneracies, also known as exceptional points (EPs), have attracted considerable attention due to their unique physical properties. In particular, metasurfaces related to EPs can open the way to unprecedented devices with functionalities such as unidirectional transmission and ultra-sensitive sensing. Herein, an active non-Hermitian metasurface with a loss-induced parity-time symmetry phase transition for ultrafast terahertz metadevices is demonstrated. Specifically, the eigenvalues of the non-Hermitian transmission matrix undergo a phase transition under optical excitation and are degenerate at EPs in parameter space, which is accompanied by the collapse of chiral transmission. Ultrafast EP modulation on a picosecond time scale can be realized through variations in the transient loss at a non-Hermitian metasurface pumped by pulsed excitation. Furthermore, by exploiting the physical characteristics of chiral transmission EPs, a switchable quarter-wave plate based on the photoactive metasurface is designed and experimentally verified and realized the corresponding function of polarization manipulation. This work opens promising possibilities for designing functional terahertz metadevices and fuses EP physics with active metasurfaces.

9.
J Inorg Biochem ; 249: 112393, 2023 12.
Artigo em Inglês | MEDLINE | ID: mdl-37806004

RESUMO

Half-sandwich iridium(III) (IrIII) complexes and ferrocenyl (Fc) derivatives are becoming the research hotspot in the field of anticancer because of their good bioactivity and unique anticancer mechanism different from platinum-based drugs. Then, a series of half-sandwich IrIII-Fc pyridine complexes have been prepared through the structural regulation in this study. The incorporation of half-sandwich IrIII complex with Fc unit successfully improves their anticancer activity, and the optimal performance (IrFc5) is almost 3-fold higher than that of cisplatin against A549 cells, meanwhile, which also shows better anti-proliferative activity against A549/DDP cells. Complexes can aggregate in the intracellular lysosome of A549 cells and induce lysosomal damage, disrupt the cell cycle, increase the level of intracellular reactive oxygen species, and eventually lead to cell apoptosis. Half-sandwich IrIII-Fc heteronuclear metal complexes possess a different anticancer mechanism from cisplatin, which can serve as a potential alternative to platinum-based drugs and show a good application prospect.


Assuntos
Antineoplásicos , Complexos de Coordenação , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Cisplatino/farmacologia , Irídio/farmacologia , Irídio/química , Metalocenos/farmacologia , Antineoplásicos/farmacologia , Antineoplásicos/química , Apoptose , Linhagem Celular Tumoral
10.
Ying Yong Sheng Tai Xue Bao ; 34(9): 2527-2535, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37899120

RESUMO

The measurement and evaluation of carbon budget of marine industry is the basis for promoting green and efficient development of marine economy under the goal of carbon neutrality. We constructed a carbon accounting system for the marine industry in Jiangsu Province, and assessed carbon efficiency and neutrality. The results showed that from 2016 to 2020, the total amount of marine carbon sinks in Jiangsu Province were 894.8 to 2773.2 thousand tons, while carbon emissions of major marine industries were 3538.4 to 4350.6 thousand tons. The net emissions of marine industries ranged from 1478.7 to 2906.1 thousand tons. Both of carbon sinks and emissions were significantly increased in this period. In terms of carbon sinks, the offshore wind power accounted for the largest contribution, followed by ecosystem carbon sequestration, and mariculture carbon sequestration was the smallest. In terms of carbon emissions, the marine transportation industry played a dominant role, followed by coastal tourism and marine fisheries, while the marine engineering and construction industry and marine shipping industry accounted for a small proportion. In general, the carbon neutral status showed that marine industry in Jiangsu Province was in carbon deficit from 2016-2020, but the net emissions were decreasing year by year. The net carbon sink efficiency of mariculture in Jiangsu Province was lower than the national level, and carbon efficiency of offshore wind power was stable.


Assuntos
Carbono , Ecossistema , Carbono/análise , Indústrias , China , Sequestro de Carbono , Dióxido de Carbono/análise , Desenvolvimento Econômico
11.
Transl Pediatr ; 12(4): 695-708, 2023 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-37181033

RESUMO

Background: To determine the prevalence of refractive error and ocular biometric data (corneal curvature, axial length, and central corneal thickness) in 6 to 15 years old children of Li and Han ethnicities of China. Methods: This study was a cross-sectional study. A cluster sampling method was used to select 2 nine-year consistent schools in the Ledong and Wanning areas of Hainan Province, with a total of 4,197 students, 3,969 valid data. Eyesight test, slit lamp, autorefraction after cycloplegia, and ocular biometric assessment were performed. The chi-square test and logistic regression analysis was taken as the comparative method. Results: Myopia, hyperopia, and astigmatism are defined as: myopia: SE ≤-0.50 D; hyperopia: 0.50 D

12.
Inorg Chem ; 62(8): 3395-3408, 2023 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-36763897

RESUMO

Half-sandwich iridium(III) complexes show potential value in the anticancer field. However, complexes with favorable luminescence performance are rare, which limits further investigation of the anticancer mechanism. In this paper, 10 triphenylamine-modified fluorescent half-sandwich iridium(III) pyridine complexes {[(η5-Cpx)Ir(L)Cl2]} (Ir1-Ir10) were prepared and showed potential antiproliferative activity, effectively inhibiting the migration of A549 cells. Ir6, showing the best activity among these complexes, exhibited excellent fluorescence performance (absolute fluorescence quantum yield of 15.17%) in solution. Laser confocal detection showed that Ir6 followed an energy-dependent cellular uptake mechanism, specifically accumulating in mitochondria (Pearson co-localization coefficient of 0.95). A Western blot assay further confirmed the existence of a mitochondrial apoptotic channel. Additionally, Ir6 could arrest the cell cycle at the G2/M phase, catalyze NADH oxidation, reduce the mitochondrial membrane potential, induce an increase in the level of intracellular reactive oxygen species, and exhibit a mechanism of oxidation. An in vivo antitumor assay confirmed that Ir6 can effectively inhibit tumor growth and is safer than cisplatin.


Assuntos
Antineoplásicos , Complexos de Coordenação , Complexos de Coordenação/farmacologia , Antineoplásicos/farmacologia , Irídio/farmacologia , Cisplatino/farmacologia , Piridinas/farmacologia , Apoptose , Proliferação de Células , Linhagem Celular Tumoral , Espécies Reativas de Oxigênio/metabolismo
13.
J Environ Manage ; 328: 116986, 2023 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-36527802

RESUMO

Carbon compensation is an effective way of reducing carbon emissions. However, previous studies in this field have been limited and have not examined high-precision scientific carbon compensation under regional inequity. The present study examined initial carbon compensation in the grid and developed a new equitable carbon compensation model. Additionally, it modified the carbon compensation value for each province and analysed how land-use change affected carbon compensation. The results show that, after the modification, the entire carbon deficit reached 17.34 × 108 t C in 2015, representing a decrease of 14% compared with the initial carbon deficit. The area with negative carbon deficit values accounted for 36% of the whole area, concentrated mainly in the south, southwest and northwest. Without modification, the initial carbon compensation reached 537 × 108 USD, and only Yunnan, Sichuan and Hainan provinces being eligible to receive compensation. The final modified carbon compensation was approximately 20% of the initial values, and 11 provinces were eligible to obtain compensation. The other provinces responsible for paying the carbon compensation costs were typically concentrated in Central and Eastern China. Land-use changes in 2015 led to increases in the initial carbon compensation and modified carbon compensation of 3.74 × 108 and 0.13 × 108 USD, respectively. The per-unit land-use change caused greater increases in carbon emissions in China's big cities and the provinces in Central and East China. Some policies, such as macro-control by the central government, diversified forms and patterns of compensation, and auxiliary measures should be formulated/proposed.


Assuntos
Dióxido de Carbono , Carbono , China , Carbono/análise , Cidades , Dióxido de Carbono/análise , Desenvolvimento Econômico
14.
Adv Sci (Weinh) ; 10(2): e2204494, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36385743

RESUMO

Miniaturized ultrafast switchable optical components with high efficiency and broadband response are in high demand to the development of optical imaging, sensing, and high-speed communication. Sharp Fano-type resonance switched by active materials is one of the key concepts that underpins the control of light in metaoptics with high sensitivity. However, actuating such metasurfaces exhibits a long-standing trade-off between modulation depth and operational bandwidth. Here, the limitations are circumvented by theoretical analysis, numerical simulation, and experimental realization of an achromatic Fano metasurface so that a high contrast of tunability with ultrafast switching rate over a broad range of frequency is achieved. By developing the physics of inter-mode coupling, the Fano metasurface is designed according to a complete phase diagram derived from coupled mode theory. Unlike conventional Fano metasurfaces, the cross-polarized inter-metaatoms coupling is discovered as a superior ability of high-efficiency broadband achromatic polarization conversion. To prove the ultrasensitive nature, a metadevice is constructed by incorporating a thin amorphous Ge layer with a weak photoconductivity perturbation. Transmission modulation over broadband frequency range from 0.6 to 1.1 THz is thus successfully realized, featuring its merits of modulation depth over 90% and On-Off-On switching cycle less than 10 ps.

15.
Nanomaterials (Basel) ; 12(23)2022 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-36500756

RESUMO

Two-dimensional (2D) molybdenum telluride (MoTe2) is attracting increasing attention for its potential applications in electronic, optoelectronic, photonic and catalytic fields, owing to the unique band structures of both stable 2H phase and 1T' phase. However, the direct growth of high-quality atomically thin MoTe2 with the controllable proportion of 2H and 1T' phase seems hard due to easy phase transformation since the potential barrier between the two phases is extremely small. Herein, we report a strategy of the phase-controllable chemical vapor deposition (CVD) synthesis for few-layer (<3 layer) MoTe2. Besides, a new understanding of the phase-controllable growth mechanism is presented based on a combination of experimental results and DFT calculations. The lattice distortion caused by Te vacancies or structural strain might make 1T'-MoTe2 more stable. The conditions for 2H to 1T' phase conversion are determined to be the following: Te monovacancies exceeding 4% or Te divacancies exceeding 8%, or lattice strain beyond 6%. In contrast, sufficient Te supply and appropriate tellurization velocity are essential to obtaining the prevailing 2H-MoTe2. Our work provides a novel perspective on the preparation of 2D transition metal chalcogenides (TMDs) with the controllable proportion of 2H and 1T' phase and paves the way to their subsequent potential application of these hybrid phases.

16.
J Org Chem ; 87(19): 13102-13110, 2022 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-36103134

RESUMO

A mechanistic investigation of α-alkynylation and α-allenylation of aldehydes under the synergistic catalysis of AuCl/amine was performed using density functional theory (DFT) calculations. For such a reaction that delivers two products, this study reveals that the reaction undergoes such a mechanistic mode: reactants → alkynyl product → allenyl product, implying that the allenyl product cannot be obtained directly from reactants. The product ratio obtained experimentally was rationalized based on the computed results that both products can reversibly interconvert with AuCl as the catalyst and with N-containing Lewis bases as additives such as 4,5-diazafluorenone. For the relative stability of alkynyl versus allenyl compounds, unsaturated substituents are found to favor the allenyl compounds.

17.
J Inorg Biochem ; 237: 112010, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36152469

RESUMO

Ferrocenyl derivatives and half-sandwich iridium(III) complexes have received extensive attention in the field of anticancer. In this paper, series of configuration-controlled ferrocene-modified half-sandwich iridium(III) pyridine complexes were prepared. The combination of half-sandwich iridium(III) complexes and ferrocenyl unit successfully improved the anticancer activity of these complexes, especially for trans-configurational one towards A549 cells, and the best-performing (FeIr5) was almost 3.5 times more potent than that of cisplatin. In addition, these complexes could inhibit the migration of A549 cells. Complexes can accumulate in intracellular lysosomes (PCC: >0.75), induce lysosomal damage, disturb the cell circle, decrease the mitochondrial membrane potential, improve the intracellular reactive oxygen species (ROS) levels, and eventually lead to apoptosis. Meanwhile, complexes could bind to serum protein following a static quenching mechanism and transport through it. Then, ferrocene-modified half-sandwich iridium(III) pyridine complexes hold the promise as potential organometallic anticancer agents for further investigation.


Assuntos
Antineoplásicos , Complexos de Coordenação , Irídio/farmacologia , Metalocenos/farmacologia , Complexos de Coordenação/farmacologia , Antineoplásicos/farmacologia , Apoptose , Piridinas/farmacologia , Espécies Reativas de Oxigênio/metabolismo , Linhagem Celular Tumoral , Proliferação de Células
18.
J Org Chem ; 87(17): 11681-11692, 2022 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-35984222

RESUMO

Density functional theory (DFT) calculations have been conducted to study the mechanisms, substituent effects, and the role of bases in Au- and Cu-catalyzed hydroacylation of terminal alkyne with glyoxal derivatives. The two reactions, despite being catalyzed by the same group of transition metals, follow distinctive reaction mechanisms. Through the detailed DFT calculations, insights into the mechanisms are obtained, and the substituent effects and the role of the bases are understood.

19.
Opt Lett ; 47(15): 3916-3919, 2022 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-35913347

RESUMO

Integrating metal halide perovskites onto plasmonic nanostructures has recently become a trending method of enabling superior emissive performance of perovskite nanophotonic devices. In this work, we present an in-depth study on the spontaneous emission properties of hybrid systems comprising CsPbBr3 nanocrystals and silver nanostructures. Specifically, a 5.7-fold increment of the photoluminescence (PL) intensity and a 1.65-fold enhancement of the PL relaxation rate is attained when the transition energy of CsPbBr3 is spectrally resonant with the oscillational frequency of Ag nanodisks (NDs), which is attributed to the intense exciton-plasmon coupling-induced Purcell effect. Furthermore, a 540-fs ultrafast energy transfer from the CsPbBr3 excitons to Ag plasmons is revealed by femtosecond pump-probe experiments, suggesting the key mechanism responsible for the Purcell-enhanced radiative emission. Our finding offers a unique understanding of the enhanced emissive behavior in the plasmon-coupled perovskite system and paves the way for further applications.

20.
J Am Chem Soc ; 144(24): 10958-10967, 2022 06 22.
Artigo em Inglês | MEDLINE | ID: mdl-35675512

RESUMO

While asymmetric synthesis has been established as a powerful synthetic tool for the construction of versatile enantioenriched molecules in the most efficient and practical manner, the resolution of racemates is still the most universal industrial approach to the synthesis of chiral compounds. However, the direct formation of enantiopure Z-isomers through the catalytic nonenzymatic kinetic resolution of racemic E-alkenes remains challenging. Herein, we disclose an unprecedented enantioselective E → Z isomerization mediated by a photoexcited chiral copper complex. This catalytic system enables kinetic resolution of 2-styrylpyrrolidines. This process is difficult to realize under thermal conditions. Mechanistic experiments and density functional theory (DFT) calculations revealed that different overall sensitization rates of the substrate-catalyst complex of the two enantiomers led to the observed excellent kinetic resolution efficiency. This photochemical transformation expands the potential of kinetic resolution beyond their established ground-state reactivity, furnishing a novel reaction mode for enantioselective catalysis at its excited state.


Assuntos
Alcenos , Cobre , Alcenos/química , Catálise , Cobre/química , Isomerismo , Estereoisomerismo
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