Featured
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Article
| Open AccessRapid room-temperature phosphorescence chiral recognition of natural amino acids
Chiral recognition of amino acids with luminescence, despite its advantages, is usually slow and lacks generality. Here, the authors demonstrate that L-phenylalanine derived benzamide can manifest the structural difference between the natural, left-handed amino acid and its right-handed counterpart via the difference in room-temperature phosphorescence, irrespective of the specific chemical structure.
- Xiaoyu Chen
- , Renlong Zhu
- & Guoqing Zhang
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Article
| Open AccessEmbedding biocatalysts in a redox polymer enhances the performance of dye-sensitized photocathodes in bias-free photoelectrochemical water splitting
A robust and efficient dye-sensitized NiO bio-hybrid photocathode based on a redox polymer and [FeFe]- hydrogenase has been developed to couple with a BiVO4 photoanode for water splitting without applied bias.
- Fangwen Cheng
- , Olha Pavliuk
- & Haining Tian
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Article
| Open AccessEnhancing photocatalytic H2O2 production with Au co-catalysts through electronic structure modification
Photocatalytic H2O2 production using Au is hindered by its inherently weak O2 adsorption. Herein, the authors modify the electronic structure of Au with MoSx to form electron deficient Au sites to promote O2 adsorption and H2O2 production.
- Xidong Zhang
- , Duoduo Gao
- & Huogen Yu
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Article
| Open AccessQuantum phase synchronization via exciton-vibrational energy dissipation sustains long-lived coherence in photosynthetic antennas
Photosynthesis in biological systems occurs in a noisy environment that reduces the lifetime of coherences in the excitation energy transfer. Here the author demonstrate that long-lasting coherences are protected by quantum phase synchronization, realized in dimers by exciton-vibrational coupling where energy dissipation occurs predominantly in resonant anti-symmetric collective modes.
- Ruidan Zhu
- , Wenjun Li
- & Yuxiang Weng
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Article
| Open AccessAnomalous anti-Kasha excited-state luminescence from symmetry-breaking heterogeneous carbon bisnanohoops
It is a long-standing scientific controversy to achieve anti-Kasha emissions by tuning structures at a molecular level. Herein, the authors constructed two symmetry-breaking heterogeneous carbon bisnanohoops with unusual anti-Kasha characteristics.
- Xinyu Zhang
- , Cheng Chen
- & Pingwu Du
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Article
| Open AccessKeto-anthraquinone covalent organic framework for H2O2 photosynthesis with oxygen and alkaline water
Hydrogen peroxide photosynthesis is an important reaction that suffers from poor activity due to the high energy barrier of hydrogen extraction in water. Here, we report a keto-form anthraquinone framework that shows promising performance in alkaline conditions.
- Xiangcheng Zhang
- , Silian Cheng
- & Lizhi Zhang
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Article
| Open AccessUltra-photostable small-molecule dyes facilitate near-infrared biophotonics
Near-infrared small molecule dyes are attractive in biophotonics, but generally rely on expanded aromatic structures to achieve this redshift. Here the authors report the use of a ground state antiaromatic strategy for 14 aminofluorene dyes, and their use in imaging kidney injury.
- Kui Yan
- , Zhubin Hu
- & Fan Zhang
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Article
| Open AccessMolecular near-infrared triplet-triplet annihilation upconversion with eigen oxygen immunity
Molecular triplet-triplet upconversion is useful in a wide range of applications, but is limited by significant oxygen quenching. Here the authors report the combination of sensitiser and annihilator that is stable in aerated environments, and suitable for in vivo sensing.
- Xinyu Wang
- , Fangwei Ding
- & Guanying Chen
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Article
| Open AccessRetinal photoisomerization versus counterion protonation in light and dark-adapted bacteriorhodopsin and its primary photoproduct
Malakar et al. investigate the photochemical dynamics in the isomerization of bacteriorhodopsin light and dark-adapted forms and in the first photocycle intermediate, K. The results prompt a reevaluation of the counter ion model, revealing that a different protonation then that shown in the classic quadrupole so far considered must be employed to account for the experimental data.
- Partha Malakar
- , Samira Gholami
- & Sanford Ruhman
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Article
| Open AccessAqueous pyruvate partly dissociates under deep ultraviolet irradiation but is resilient to near ultraviolet excitation
The photochemistry of the pyruvate anion plays an important role in the Earth’s atmosphere and aqueous environments. Here, the authors show that excitation of aqueous pyruvate by 200 nm light leads to decarboxylation with a quantum efficiency of 20%, while excitation by 340 nm light does not cause a reaction.
- Jan Thøgersen
- , Fani Madzharova
- & Frank Jensen
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Article
| Open AccessDioxygen compatible electron donor-acceptor catalytic system and its enabled aerobic oxygenation
The photochemical properties of Electron Donor-Acceptor (EDA) complexes present exciting opportunities, but often require an inert atmosphere to maintain high efficiency. Here, the authors develop a photocatalytic system through rational design, which overcomes the oxygen-sensitive limitation of traditional EDA photocatalytic systems.
- Jialiang Wei
- , Junhong Meng
- & Ning Jiao
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Article
| Open AccessTuning light-driven oxidation of styrene inside water-soluble nanocages
Selective functionalization of C(sp2)–H bonds under ambient conditions is a persistent synthetic challenge in organic chemistry. Here the authors combine host-guest charge-transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration.
- Souvik Ghosal
- , Ankita Das
- & Jyotishman Dasgupta
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Article
| Open AccessChemoenzymatic indican for light-driven denim dyeing
Conventional blue denim dyeing has both environmental and health-related consequences. Here, Bidart et al. use enzyme engineering to develop a viable method for the bulk production of indican and demonstrate dying processes which could significantly reduce the negative consequences of this billion-dollar industry.
- Gonzalo Nahuel Bidart
- , David Teze
- & Ditte Hededam Welner
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Article
| Open AccessAnomalously bright single-molecule upconversion electroluminescence
The efficiency of upconversion electroluminescence remains very low for single-molecule emitters. Here, the authors report over one order of magnitude improvement in the emission efficiency via engineering energy-level alignments for triplet relayed upconversion involving only carrier injection.
- Yang Luo
- , Fan-Fang Kong
- & Zhen-Chao Dong
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Article
| Open AccessMetal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes
Enhancing the sp3-hybridized character of molecular structures in drug discovery is paramount. Here, the authors introduce a deoxygenative cross-electrophile coupling technique that pairs easily accessible carboxylic acid-derived redox-active esters with aldehyde sulfonyl hydrazones, employing Eosin Y as an organophotocatalyst under visible light irradiation.
- Stefano Bonciolini
- , Antonio Pulcinella
- & Timothy Noël
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Article
| Open AccessElucidation of the role of metals in the adsorption and photodegradation of herbicides by metal-organic frameworks
In this study, the authors explored the correlation between the structure and optoelectronic properties of metal organic frameworks for the removal of a harmful herbicide from water.
- Nan Chieh Chiu
- , Jacob M. Lessard
- & Kyriakos C. Stylianou
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Article
| Open AccessCharacterization of A π–π stacking cocrystal of 4-nitrophthalonitrile directed toward application in photocatalysis
Photoexcitation of the electron-donor-acceptor (EDA) complexes are an effective approach to achieve radicals by triggering electron transfer but the catalytic version of EDA complex photoactivation remains underdeveloped. Here, the authors introduce 4-nitrophthalonitrile as an electron acceptor to facilitate π-stacking with electron-rich aromatics to form EDA complexes.
- Ting Xue
- , Cheng Ma
- & Rong Zeng
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Article
| Open AccessAg3PO4 enables the generation of long-lived radical cations for visible light-driven [2 + 2] and [4 + 2] pericyclic reactions
Photoredox catalysis is an important approach for synthesizing fine chemicals from olefins, but the limited lifetime of radical cation intermediates severely restricts the efficiency. Here, the authors report that Ag3PO4 can efficiently catalyze intramolecular and intermolecular [2 + 2] and Diels–Alder cycloadditions under visible-light irradiation.
- Lirong Guo
- , Rongchen Chu
- & Yifeng Wang
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Article
| Open AccessWhy flying insects gather at artificial light
It is unclear why flying insects congregate around artificial light sources. Here, the authors use high-speed videography and motion-capture, finding that insects fly perpendicular to light sources due to a disruption of the dorsal light response.
- Samuel T. Fabian
- , Yash Sondhi
- & Huai-Ti Lin
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Article
| Open AccessBioinspired polymeric supramolecular columns as efficient yet controllable artificial light-harvesting platform
The formation of artificial light-harvesting systems with high donor/acceptor ratios for efficient energy transfer remains challenging. Here, the authors describe a polymeric supramolecular column-based light-harvesting system by modular columnar assembly of donor/acceptor chromophores, enabling superior light-harvesting efficiency and dynamic full-color tunable emission.
- Bin Mu
- , Xiangnan Hao
- & Wei Tian
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Article
| Open AccessPt-doped Ru nanoparticles loaded on ‘black gold’ plasmonic nanoreactors as air stable reduction catalysts
An air-stable plasmonic catalyst using Pt-Ru on black gold achieves 90% selectivity in acetylene semi-hydrogenation using plasmonic photochemistry. Mechanistic experiments highlight the role of non-thermal and thermal effects for this reaction.
- Gunjan Sharma
- , Rishi Verma
- & Vivek Polshettiwar
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Article
| Open AccessElectrophotocatalytic hydrogenation of imines and reductive functionalization of aryl halides
Open-shell catalytically active species are widely used in energy-consuming redox reactions, but their excited-state lifetimes are usually short. Here, the authors report a closed-shell thioxanthone-hydrogen anion species generated under electrochemical conditions, which can be photochemically converted to a potent and long-lived reductant.
- Wen-Jie Kang
- , Yanbin Zhang
- & Hao Guo
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Article
| Open AccessOrigin of the multi-phasic quenching dynamics in the BLUF domains across the species
Here the authors combine 19 F NMR and femtosecond transient absorption to characterise the structural origin of the multiphasic quenching dynamics in various species of BLUF domains, highlighting the importance of the heterogeneous active-site H-bond network.
- Yalin Zhou
- , Siwei Tang
- & Dongping Zhong
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Article
| Open AccessPhotocatalytic aerobic oxidation of C(sp3)-H bonds
The authors report a family of photocatalysts containing Ce active sites and perylene diimide ligands for the aerobic oxidation of substituted toluene, ethylbenzene, benzyl alcohol, thioanisole, and benzylamine in acetonitrile.
- Lei Zhang
- , Run-Han Li
- & Ya-Qian Lan
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Article
| Open AccessElucidating protonation pathways in CO2 photoreduction using the kinetic isotope effect
Yin et al. reveal a protonation pathway in CO2 photoreduction on TiO2, challenging electron activation theories and diversifying photocatalyst design, distinct from Fischer-Tropsch and Sabatier processes.
- Shikang Yin
- , Yiying Zhou
- & Pengwei Huo
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Article
| Open AccessPhotogenerated outer electric field induced electrophoresis of organic nanocrystals for effective solid-solid photocatalysis
Charge accumulation in organic photocatalysts leads to an overlooked macroscopic particle migration, crucial for heterogeneous photocatalytic kinetics. Authors demonstrate self-driven electrophoresis of organic nanocrystals via rationally designed photogenerated outer electric field (OEF).
- Yan Guo
- , Bowen Zhu
- & Yongfa Zhu
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Comment
| Open AccessImproving reproducibility of photocatalytic reactions—how to facilitate broad application of new methods
Photocatalysis, as a powerful tool for synthetic transformations, has the potential to impact industrial applications. In this commentary, we discuss the challenges and requirements with respect to reproducing published photocatalytic reactions in the (life science) industry.
- Santiago Cañellas
- , Manuel Nuño
- & Elisabeth Speckmeier
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Article
| Open AccessMetallopolymer strategy to explore hypoxic active narrow-bandgap photosensitizers for effective cancer photodynamic therapy
Iridium-based photosensitizers exhibit good photocatalytic performance, but the in vivo applications are hindered by conventional O2-dependent Type-II photochemistry and poor absorption. Here, the authors report a general metallopolymerization strategy for engineering iridium complexes exhibiting Type-I photochemistry and enhancing absorption intensity in the blue to near-infrared region.
- Zhao Zhang
- , Zixiang Wei
- & Xuanjun Zhang
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Article
| Open AccessPhotoinduced copper-catalyzed C–N coupling with trifluoromethylated arenes
Selective defluorinative functionalization is a synthetic route to pharmaceutically important fluorine-containing compounds but activation of inert C–F bonds remains challenging. Here the authors report activation of di-or trifluoromethylated arenes for radical C–N coupling with carbazoles and aromatic amines using photoexcited copper catalysis.
- Jun Huang
- , Qi Gao
- & Jin Xie
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Article
| Open AccessHighly scalable photoinduced synthesis of silanols via untraversed pathway for chlorine radical (Cl•) generation
Contrary to photocatalysis, the use of photochemical energy solely to initiate reactions is underexplored. Here, the authors demonstrate light initiated synthesis of functionalized organosilanols, silanediols, and polymeric siloxanol under ambient reaction conditions.
- Argha Saha
- , Wajid Ali
- & Debabrata Maiti
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Article
| Open AccessPotential window alignment regulating ion transfer in faradaic junctions for efficient photoelectrocatalysis
Band alignment theory has been widely used to design semiconductor heterojunctions for photo(electro)catalysis, but it cannot describe coupled electron and ion transfer process. Here, the authors propose potential window alignment theory to remarkably improve the performance of heterojunctions.
- Hongzheng Dong
- , Xiangyu Pan
- & Zhigang Zou
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Article
| Open AccessNickel/photoredox dual catalyzed arylalkylation of nonactivated alkenes
Dicarbofunctionalization of nonactivated alkenes is a simple way to rapidly build molecular complexity, but these transformations have not been extensively explore under metallaphotoredox conditions. Here, the authors develop a nickel/photoredox dual catalytic system for arylalkylation of alkenes.
- Yuxi Gao
- , Lijuan Gao
- & Chengfeng Xia
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Article
| Open AccessIn situ observation of a stepwise [2 + 2] photocycloaddition process using fluorescence spectroscopy
Using highly sensitive and selective in situ techniques to investigate the dynamics of intermediates formation is key to better understand reaction mechanisms but investigating the early stages of solid-state reactions or transformations is still challenging. Here the authors use in situ fluorescence spectroscopy to observe the evolution of intermediates during a two-step [2 + 2] photocycloaddition process in a coordination polymer.
- Meng-Fan Wang
- , Yun-Hu Deng
- & Jian-Ping Lang
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Article
| Open AccessSelf-activated superhydrophilic green ZnIn2S4 realizing solar-driven overall water splitting: close-to-unity stability for a full daytime
A superhydrophilic green hollow ZnIn2S4 was fabricated to realize unassisted photocatalytic overall water splitting. This work could provide an innovative aperture for efficient solar-driven green hydrogen production to achieve carbon neutrality.
- Wei-Kean Chong
- , Boon-Junn Ng
- & Siang-Piao Chai
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Article
| Open AccessStraightforward synthesis of functionalized γ-Lactams using impure CO2 stream as the carbon source
Direct utilization of CO2 is important in organic synthesis but purification of CO2 gas expensive and energy intensive. Here the authors described a straightforward synthetic route for the synthesis of γ-lactams, a pivotal core structure of bioactive molecules, by using impure CO2 stream as the carbon source.
- Yuman Qin
- , Robin Cauwenbergh
- & Shoubhik Das
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Article
| Open AccessThe carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter
Recent experimental evidence shows a new type of intrinsic fluorescence in biomolecules void of aromatic chemical compounds whose origin is unclear. Here, the authors use non-adiabatic AIMD simulations to show a potential carbonyl-lock mechanism originating this phenomenon.
- Gonzalo Díaz Mirón
- , Jonathan A. Semelak
- & Uriel N. Morzan
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Article
| Open AccessAnaerobic photoinduced Cu(0/I)-mediated Glaser coupling in a radical pathway
The reaction mechanism of the historic copper-catalyzed Glaser coupling has been debated to be based on redox cycles of Cu ions in specific oxidation states or on a radical mechanism based on Cu(0)/Cu(I). Here, the authors demonstrate two coexisting Glaser coupling pathways which can be differentiated by anaerobic/irradiation or aerobic reaction conditions
- Siqi Zhang
- & Liang Zhao
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Article
| Open AccessNanomechanical action opens endo-lysosomal compartments
Endo-lysosomal escape is a highly inefficient process. Here the authors present a lipid-based nanoscale molecular machine that achieves efficient cytosolic transport of biologics by destabilizing endo-lysosomal compartments through nanomechanical action upon light irradiation.
- Yu Zhao
- , Zhongfeng Ye
- & Qiaobing Xu
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Article
| Open AccessMulti-scale molecular dynamics simulations of enhanced energy transfer in organic molecules under strong coupling
Placing an organic material in an optical cavity can enhance exciton transport, but the mechanism is poorly understood. Here, using molecular dynamics simulations, the authors obtained atomistic insights into that mechanism.
- Ilia Sokolovskii
- , Ruth H. Tichauer
- & Gerrit Groenhof
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Article
| Open AccessKinetics of the xanthophyll cycle and its role in photoprotective memory and response
This study explores how the photosynthetic alga Nannochloropsis oceanica, rapidly adapts to changing light conditions, using a short-term “memory" system involving the xanthophyll cycle, which is widespread in photosynthetic organisms.
- Audrey Short
- , Thomas P. Fay
- & Graham R. Fleming
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Article
| Open AccessPhotoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons
Organoboron compounds are of high interest in organic synthesis due to the versatility of boryl substituents that allows access to further modifications. Here, the authors report on the development of an oxidative C(sp3)−H borylation reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy
- Ping-Fu Zhong
- , Jia-Lin Tu
- & Wujiong Xia
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Article
| Open AccessVisible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons
The direct and selective coupling between unactivated C(sp2)-H and C(sp3)-H bonds is widely recognized as one of the most challenging tasks in organic synthesis. Here, the authors present an iron halidepromoted photochemical aerobic oxidation strategy for achieving such transformations.
- Qian-Yu Li
- , Shiyan Cheng
- & Lei Gong
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Article
| Open AccessMetal-free photoinduced C(sp3)–H/C(sp3)–H cross-coupling to access α‑tertiary amino acid derivatives
The cross-dehydrogenative coupling (CDC) reaction is the most efficient method for constructing α-tertiary amino acids (ATAAs). Here, the authors present a mild, metal-free CDC reaction for the construction of ATAAs with good regioselectivity.
- Yujun Li
- , Shaopeng Guo
- & Ke Zheng
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Article
| Open AccessA metal-free photoactive nitrogen-doped carbon nanosolenoid with broad absorption in visible region for efficient photocatalysis
Carbon nanosolenoid materials with Riemann surfaces have unique structures and novel physical properties. Here, the authors report a nitrogen-doped carbon nanosolenoid heterojunction material with distinctive photocatalytic properties for light driven hydrogen production and organic transformations.
- Yu Zhou
- , Xinyu Zhang
- & Pingwu Du
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Article
| Open AccessDecarboxylation of β-boryl NHPI esters enables radical 1,2-boron shift for the assembly of versatile organoborons
The 1,2 migration reaction on tetracoordinate boron species have been well investigated but less work looked on 1,2-boryl radical shift for the construction of organoborons. Here, the authors demonstrate a visible-light-induced photoredox neutral decarboxylative radical cross-coupling reaction, which undergoes a radical 1,2-boron shift to give a translocated C-radical for further capture of versatile radical acceptors
- Yu Guo
- , Xiaosha Wang
- & Qiuling Song
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Article
| Open AccessLaser-induced nitrogen fixation
Emerged sustainable techniques for nitrogen fixation still lack ammonia yield rate to be practically relevant. Here, the authors demonstrate a laser–induced method to deliver a yield rate of 30.9 µmol s-1 cm−2 at ambient conditions, which is two orders of magnitude higher than other methods.
- Huize Wang
- , Ranga Rohit Seemakurthi
- & Markus Antonietti
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Article
| Open AccessTailored photoenzymatic systems for selective reduction of aliphatic and aromatic nitro compounds fueled by light
The selective enzymatic reduction of nitroaliphatic and nitroaromatic compounds is challenging. Here, the authors report selective (sun)light-driven photoenzymatic reduction of a wide variety of nitro compounds to aliphatic amines and amino-, azoxy- and azo-aromatics using flavin-dependent nitroreductases and chlorophyll as photocatalyst
- Alejandro Prats Luján
- , Mohammad Faizan Bhat
- & Gerrit J. Poelarends
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Article
| Open AccessOrganophotocatalysed synthesis of 2-piperidinones in one step via [1 + 2 + 3] strategy
The synthesis of 2-piperidinone derivatives remains challenging. Here, the authors develop an organophotocatalysed [1 + 2 + 3] strategy to enable the one-step access to diverse 2-piperidinones from ammonium salts, alkenes, and unsaturated carbonyl compounds.
- Yi-Dan Du
- , Shan Wang
- & Wei Shu
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Article
| Open AccessTricolor visible wavelength-selective photodegradable hydrogel biomaterials
Photodegradable gels are useful for regenerative medicine and tissue engineering, but typically respond to UV light. Here, the authors report a family of 3 photolabile linkers that cleave rapidly and with unique tricolor wavelength-selectivity to visible light.
- Teresa L. Rapp
- & Cole A. DeForest