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| Open AccessProtein control of photochemistry and transient intermediates in phytochromes
Phytochromes are photoreceptors responsible for sensing light in plants, fungi and bacteria. Here the authors use computational simulations to reveal the molecular mechanism of photoactivation and characterize the involved reaction intermediates.
- Giacomo Salvadori
- , Veronica Macaluso
- & Benedetta Mennucci
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Article
| Open AccessTowards the engineering of a photon-only two-stroke rotary molecular motor
Improving the efficiency of light-driven molecular rotary motors is a challenging task. Here, the authors combine theoretical modeling, synthesis and spectroscopy to prepare a prototype molecular motor capable of avoiding inefficient thermally activated motion; thus offering prospects to implement a 2-stroke photon-only molecular motor.
- Michael Filatov(Gulak)
- , Marco Paolino
- & Massimo Olivucci
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Article
| Open AccessLight activation of Orange Carotenoid Protein reveals bicycle-pedal single-bond isomerization
Orange Carotenoid protein (OCP) is the only photoreceptor with a carotenoid for sensing. Here, the authors report crystal structures of the early OCP photoproduct, suggesting that photo-sensing involves single bond isomerization.
- Volha U. Chukhutsina
- , James M. Baxter
- & Jasper J. van Thor
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Article
| Open AccessOn the fluorescence enhancement of arch neuronal optogenetic reporters
Arch-3 rhodopsin variants are common fluorescent reporters of neuronal activity. Here, the authors show with quantum chemical modelling that a set of these proteins reveals a direct proportionality between their observed fluorescence intensity and the stability of an exotic excited-state diradical intermediate.
- Leonardo Barneschi
- , Emanuele Marsili
- & Massimo Olivucci
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Article
| Open AccessSupramolecular photodynamic agents for simultaneous oxidation of NADH and generation of superoxide radical
Tumour hypoxia is a major issue for conventional photodynamic therapies, Here, the authors report on the supramolecular assembly of electron acceptors with photosensitizers which have improved reactive oxygen species production and are able to directly oxidise NHDH and demonstrate application against hypoxic tumours.
- Kun-Xu Teng
- , Li-Ya Niu
- & Qing-Zheng Yang
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Article
| Open AccessHemipiperazines as peptide-derived molecular photoswitches with low-nanomolar cytotoxicity
The development of photochromic systems is an important and growing area of research, in particular for bioactive molecular photoswitches. Here, the authors report on photopharmacological antimitotic agents, operational under visible light, based on a peptide-derived hemipiperazine photochrome.
- Susanne Kirchner
- , Anna-Lena Leistner
- & Zbigniew Pianowski
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Article
| Open AccessCoemissive luminescent nanoparticles combining aggregation-induced emission and quenching dyes prepared in continuous flow
Developing efficient light harvesting systems at low cost is a challenge. Here, the authors synthesized coemissive dyes in a continuous flow microreactor featuring a controlled cascade FRET process combining aggregation-induced emission and quenching.
- Chong Li
- , Qi Liu
- & Shengyang Tao
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Article
| Open AccessPhotoredox-catalyzed C–C bond cleavage of cyclopropanes for the formation of C(sp3)–heteroatom bonds
The development of new methodologies for the construction of C(sp3)–heteroatom bonds under mild conditions is desirable. Here the authors report the formation of C(sp3)–heteroatom bonds via ring opening of arylcyclopropanes enabled by photoredox catalysis.
- Liang Ge
- , Chi Zhang
- & Chao Feng
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Article
| Open AccessPhotoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes
Three-component carboacylation of simple alkenes often requires directing groups and strained substrates. Here, the authors report a photoredox N-heteroyclic carbene/Pd-catalysed alkylacylation of alkenes with aldehydes and unactivated alkyl halides; exogenous photosensitizer or external reductant are not required.
- You-Feng Han
- , Ying Huang
- & Song Ye
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Article
| Open AccessSynergistic interplay between photoisomerization and photoluminescence in a light-driven rotary molecular motor
Combining photofunctionalities in a single molecule is challenging due to inherent detrimental interactions. Here, the authors construct a molecular motor that exhibits photoinduced rotary motion together with bright photoluminescence.
- Ryojun Toyoda
- , Nong V. Hoang
- & Ben L. Feringa
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Article
| Open AccessMicrobial biofilms as living photoconductors due to ultrafast electron transfer in cytochrome OmcS nanowires
Despite enormous potential of solar-driven biocatalysis, most living systems lack photoactive proteins and require toxic and expensive synthetic materials limiting the performance. Here, a class of natural photoconductors is demonstrated through sub-picosecond heme-to-heme electron transfer in bacteria-produced protein nanowires.
- Jens Neu
- , Catharine C. Shipps
- & Nikhil S. Malvankar
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Article
| Open AccessFluorescence-based monitoring of the pressure-induced aggregation microenvironment evolution for an AIEgen under multiple excitation channels
The develop of organic functional materials requires the exploration of the pressure dependent emissive mechanisms of molecular structures, conformations and stacking modes. Here, Tong et al propose a strategy for monitoring the pressure-induced fluorescence under multiple excitation channels.
- Shuang Tong
- , Jianhong Dai
- & Xinggui Gu
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Article
| Open AccessDe novo protein design of photochemical reaction centers
De novo development of a simplified photosynthetic reaction center protein can clarify practical engineering principles needed to build enzymes for efficient energy conversion. Here, the authors develop an artificial photosynthetic reaction center that functions without the need for sacrificial electron donors or acceptors.
- Nathan M. Ennist
- , Zhenyu Zhao
- & Christopher C. Moser
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Article
| Open AccessN-Heterocyclic carbene-based C-centered Au(I)-Ag(I) clusters with intense phosphorescence and organelle-selective translocation in cells
Photoluminescent gold clusters have unique chemical and physical properties based on their perturbed electronic structures. Here, the authors report the synthesis of carbon-centered Au(I)-Ag(I) clusters with high phosphorescence quantum yields using N-heterocyclic carbene ligands.
- Zhen Lei
- , Mizuki Endo
- & Mitsuhiko Shionoya
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Article
| Open AccessSelective skeletal editing of polycyclic arenes using organophotoredox dearomative functionalization
The synthesis of polycyclic structures bearing partially saturated (hetero)arenes is important as many of these structures have biological relevance. Here the authors develop a one-step method for selective dearomative functionalization of feedstock (hetero)arenes via organophotocatalysis.
- Peng Ji
- , Cassondra C. Davies
- & Wei Wang
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Article
| Open AccessVisible-light mediated catalytic asymmetric radical deuteration at non-benzylic positions
Catalytic asymmetric deuterations rely largely on two-electron reaction manifolds and are mostly limited to benzylic positions. Here, a metal-free platform using peptide- or sugar-derived chiral thiols and deuterium oxide allows for asymmetric open-shell deuteration at non-benzylic positions under visible-light irradiation.
- Qinglong Shi
- , Meichen Xu
- & Juntao Ye
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Article
| Open AccessPhotochemical and thermochemical pathways to S2 and polysulfur formation in the atmosphere of Venus
Polysulfur compounds have been ascribed as the unknown near-UV absorbers in Venusian atmosphere and play a key role in the sulfur chemical cycle of this planet. Here, authors establish their production from (SO)2 on the grounds of quantifications of photochemical and thermal pathways involved in the sulfur chemical cycle of the planet.
- Antonio Francés-Monerris
- , Javier Carmona-García
- & Daniel Roca-Sanjuán
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Article
| Open AccessHighly selective single and multiple deuteration of unactivated C(sp3)-H bonds
Deuteration of unactivated C(sp3)̵̵̵̵̵̵̵̵–H bonds is a simple route to deuterated compounds, of use in pharmaceutical chemistry, material science, and synthetic chemistry. Here, the authors describe a hydrogen/deuterium (H/D) exchange of remote unactivated C(sp3)̵̵̵̵̵̵̵̵–H bonds via photocatalysis, proceeding through hydrogen atom transfer.
- Nian Li
- , Jinhang Li
- & Jin Xie
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Article
| Open AccessBipolar charge collecting structure enables overall water splitting on ferroelectric photocatalysts
While ferroelectric materials are promising candidates for solar water splitting, most examples show poor activities. Here, authors prepare charge-collecting nanostructures on the positive and negative domains of BaTiO3 and demonstrate photocatalytic overall water splitting.
- Yong Liu
- , Mingjian Zhang
- & Fengtao Fan
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Article
| Open AccessA dynamic assembly-induced emissive system for advanced information encryption with time-dependent security
The development of advanced materials for information encryption is desirable. Here, the authors report materials that enable orthogonal and temporal encryption of information via dynamic assembly-induced multicolor pyrene-based supramolecular systems.
- Qian Wang
- , Biyan Lin
- & Da-Hui Qu
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Article
| Open AccessBreaking photoswitch activation depth limit using ionising radiation stimuli adapted to clinical application
Triggered therapeutics are of interest but currently suffer from limited penetration depth of light sources. Here, the authors report on the development of a system, called radioswitch, that uses ionising irradiation to switch an azobenzene modified drug to an active form for deep tissue triggered therapeutic application.
- Alban Guesdon-Vennerie
- , Patrick Couvreur
- & Guillaume Bort
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Article
| Open AccessA visible-light activated secondary phosphine oxide ligand enabling Pd-catalyzed radical cross-couplings
Ligand design is key for improving the performance in light-enabled catalytic processes. Here, the authors report the synthesis of a visible-light–activated secondary phosphine oxide ligand and apply it to Pd-catalyzed radical cross-coupling reactions.
- Takahito Kuribara
- , Masaya Nakajima
- & Tetsuhiro Nemoto
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Article
| Open AccessRu(II) photocages enable precise control over enzyme activity with red light
The cytochrome P450 enzyme CYP1B1 is overexpressed in a variety of tumors, and is correlated with poor treatment outcomes; thus, it is desirable to develop CYP1B1 inhibitors to restore chemotherapy efficacy. Here the authors describe the creation of light-triggered CYP1B1 inhibitors as “prodrugs”, and achieve >6000-fold improvement in potency upon activation with low-energy (660 nm) light.
- Dmytro Havrylyuk
- , Austin C. Hachey
- & Edith C. Glazer
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Article
| Open AccessPorphyrin as a versatile visible-light-activatable organic/metal hybrid photoremovable protecting group
Photoremovable protecting groups (PPGs) represent one of the main contemporary implementations of photochemistry. Here, the authors show that meso-methylporphyrin unites traditionally exclusive features of organic and metal-complex PPGs within a single entity.
- Adiki Raja Sekhar
- , Youhei Chitose
- & Roy Weinstain
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Article
| Open AccessA practical fluorosulfonylating platform via photocatalytic imidazolium-based SO2F radical reagent
Sulfonyl fluorides have potential application in chemical biology, materials science, and drug discovery, but their preparation remains challenging. Here, the authors report an air-stable fluorosulfonylating reagent that enables the radical fluorosulfonylation, hydrofluorosulfonylation and migratory SO2F-difunctionalization of unsaturated hydrocarbons to construct a variety of sulfonyl fluoride compounds.
- Weigang Zhang
- , Heyin Li
- & Yi Wang
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Article
| Open AccessSecondary through-space interactions facilitated single-molecule white-light emission from clusteroluminogens
Although mature and systematic theories of molecular photophysics have been developed, it is still challenging to endow clusteroluminogens (CLgens) with designed photophysical properties by manipulating through-space interactions. Here, the authors design three CLgens that show multiple emissions and white-light emission in the crystalline state, and emphasize the important role of secondary through-space interactions between the acceptor and non-conjugated donor units.
- Jianyu Zhang
- , Parvej Alam
- & Ben Zhong Tang
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Article
| Open AccessGeneration and direct observation of a triplet arylnitrenium ion
Nitrenium ions are highly electrophilic reactive intermediates of formula R−N−R+, nitrogen analogue of carbenes. Here the authors report the detection of a triplet nitrenium ion using time-resolved spectroscopic methods and ab initio computations, allowing a glimpse at the properties and behavior of this important class of intermediates.
- Lili Du
- , Juanjuan Wang
- & Arthur H. Winter
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Article
| Open AccessDirect observation of ultrafast exciton localization in an organic semiconductor with soft X-ray transient absorption spectroscopy
A detailed understanding of ultrafast exciton dynamics is crucial for improving the efficiency of organic light-harvesting-devices. Here, the authors track exciton localization on a sub-50 fs timescale in an organic semiconductor using time resolved soft x-ray absorption spectroscopy.
- D. Garratt
- , L. Misiekis
- & J. P. Marangos
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Article
| Open AccessHigh-resolution two-dimensional electronic spectroscopy reveals the homogeneous line profile of chromophores solvated in nanoclusters
Understanding the interaction of single chromophores with nanoparticles remains a challenging task in nanoscience. Here the authors provide insight into the interaction between isolated base-free phthalocyanine molecules and He and Ne nanoclusters in the gas phase using high-resolution two-dimensional spectroscopy.
- Ulrich Bangert
- , Frank Stienkemeier
- & Lukas Bruder
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Article
| Open AccessUltrasensitive detection of local acoustic vibrations at room temperature by plasmon-enhanced single-molecule fluorescence
.Sensitive detection of weak acoustic signals at nanometer scale is challenging. Here, the authors present an acoustic detection system based on a single molecule as a probe, where frequency and amplitude of acoustic vibrations can be extracted from its minute variations in distance to the surface of a plasmonic gold nanorod.
- Mingcai Xie
- , Hanyu Liu
- & Yuxi Tian
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Article
| Open AccessControllable multiple-step configuration transformations in a thermal/photoinduced reaction
Solid-state photochemical reactions of olefinic compounds provide access to organic cyclic molecules with specific configurations but the precise control of the stereochemistry in these reactions remains challenging. Here, the authors demonstrate control of the regiospecific configurations of C=C groups and the intermediates by varying temperatures in multi-step thermal and photoinduced ring opening and closing reactions using a single-crystal coordination polymer platform.
- Meng-Fan Wang
- , Yan Mi
- & Jian-Ping Lang
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Article
| Open AccessHigh-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO2
Photocatalytic nonoxidative coupling of methane (NOCM) emerges as an appealing approach for the production of value-added C2 + hydrocarbons and hydrogen. Here the authors propose a heteroatom engineering strategy to prepare Pd single atoms loaded TiO2 for active and selective photocatalytic NOCM.
- Wenqing Zhang
- , Cenfeng Fu
- & Yujie Xiong
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Article
| Open AccessSignal transduction in light-oxygen-voltage receptors lacking the active-site glutamine
Light-oxygen-voltage (LOV) photoreceptors perceive blue light to elicit spatio-temporally defined cellular responses, and their signalling process has been extensively characterized. Here the authors report that the light signal is still transduced in the absence of a conserved Gln residue, thought to be key.
- Julia Dietler
- , Renate Gelfert
- & Andreas Möglich
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Article
| Open AccessPhotovoltage memory effect in a portable Faradaic junction solar rechargeable device
A Faradaic junction solar rechargeable device is one of the promising technologies to address the problem of solar energy storage but the working mechanism remains unclear. Here, the authors report a photovoltage memory effect in a portable Si/CoOx/KBi(aq)/MnOx Faradaic junction device.
- Pin Wang
- , Mengfan Xue
- & Zhigang Zou
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Article
| Open AccessOutpacing conventional nicotinamide hydrogenation catalysis by a strongly communicating heterodinuclear photocatalyst
Although multinuclear, supramolecular photocatalysts show promise in their ability to separate the processes required for lightdriven energy production into light absorption, charge separation and fuel production by individual parts of the molecule, mechanistic understanding of the performance limiting processes are lacking. Here the authors synthesize two new dinuclear catalysts and compare them to a benchmark through detailed spectroscopic studies, obtaining significant chemical insight.
- Linda Zedler
- , Pascal Wintergerst
- & Sven Rau
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Article
| Open AccessTriplet-driven chemical reactivity of β-carotene and its biological implications
The endoperoxides of β-carotene play a key role in signaling of photooxidative stress in plant cells and are regarded as the products of chemical deactivation of singlet oxygen. The authors show that these compounds are instead formed in a reaction between oxygen and β-carotene in their triplet states, revealing the importance of the triplet states in the photoprotection of photosynthetic apparatus.
- Mateusz Zbyradowski
- , Mariusz Duda
- & Leszek Fiedor
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Article
| Open AccessPhotoinduced ynamide structural reshuffling and functionalization
Although ynamides have emerged as a versatile class of compounds for organic synthesis, the radical chemistry of ynamides usually proceeds with the expected connectivity largely intact. Here the authors show a methodology by which the C(sp)–N bond undergoes scission, alkyne migration and functionalization under blue LED light in the absence of metals or additives.
- Mohana Reddy Mutra
- & Jeh‐Jeng Wang
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Article
| Open AccessTwo-photon-absorbing ruthenium complexes enable near infrared light-driven photocatalysis
The field of homogeneous metal- and photocatalysis typically uses one-photon-absorbing photosensitizers, which are highly functional, but require higher-energy light. Here the authors report a group of ruthenium polypyridyl complexes possessing two-photon-absorption capabilities, active with irradiation with lower-energy (740 nm) light.
- Guanqun Han
- , Guodong Li
- & Yujie Sun
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Article
| Open AccessThe initial charge separation step in oxygenic photosynthesis
The photosystem II reaction center (PSII-RC) is a model system to understand the initial steps of photosynthesis, but its excited state dynamics is difficult to disentangle with most spectroscopic methods. Here the authors perform a two-dimensional electronic-vibrational spectroscopic study of PSII-RC, providing detailed insight into such dynamics and into the mechanism of charge separation.
- Yusuke Yoneda
- , Eric A. Arsenault
- & Graham R. Fleming
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Article
| Open AccessAn osmium-peroxo complex for photoactive therapy of hypoxic tumors
Photodynamic therapy has been a promising technique for the treatment of tumours. In this manuscript, the authors report on the photoactivation of the osmium peroxo complex and its potential use for chemotherapy and photodynamic therapy under blue light irradiation against tumours in their hypoxic environment.
- Nong Lu
- , Zhihong Deng
- & Pingyu Zhang
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Article
| Open AccessAn unexpected strategy to alleviate hypoxia limitation of photodynamic therapy by biotinylation of photosensitizers
Type I photodynamic therapy (PDT) sensitizers show good hypoxia tolerance but only few strategies are available for the design of purely organic Type I photosensitizers (PS). Here, the authors use biotinylation as design strategy to obtain PS-Biotin sensitizers with high efficiency for the generation of superoxide anion radicals and singlet oxygen.
- Jing An
- , Shanliang Tang
- & Wen-Heng Zheng
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Article
| Open AccessControlling forward and backward rotary molecular motion on demand
Being able to control motion at the molecular level is vital for many future developments in the molecular sciences. Here, the authors report the controlled forward and backward rotation of a molecular motor guided by external stimuli.
- L. Pfeifer
- , S. Crespi
- & B. L. Feringa
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Article
| Open AccessLight-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage
The cleavage and formation of carbon−carbon bonds is an important strategy for structural modifications in organic syntheses. Herein, the authors present a photoinduced method to construct biaryl compounds through dual inert C−C bond cleavage.
- Dawei Cao
- , Mohamad Ataya
- & Chao-Jun Li
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Article
| Open AccessSynthesis of fluorescent organic nano-dots and their application as efficient color conversion layers
Compared to inorganic nanoparticles, organic nanoparticles aren’t as well understood. Here the authors explore the use of surfactants to prepare organic semiconductor nanoparticles with outstanding photophysical properties.
- Yeasin Khan
- , Soonjae Hwang
- & Jang Hyuk Kwon
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Article
| Open AccessPhoto-induced trifunctionalization of bromostyrenes via remote radical migration reactions of tetracoordinate boron species
Tetracoordinate boron species are common radical precursors in organic synthesis, but the boron species are discarded as by-products. Herein the authors report a strategy to incorporate both the alkyl moiety and boron species into the eventual products, yielding organoboron compounds.
- Chaokun Li
- , Shangteng Liao
- & Qiuling Song
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Article
| Open AccessEnantioselective functionalization at the C4 position of pyridinium salts through NHC catalysis
A catalytic method for the enantioselective and C4-selective functionalization of pyridine derivatives is yet to be developed. Here the authors report an efficient method for the asymmetric β-pyridylations of enals that involve N-heterocyclic carbene (NHC) catalysis with excellent control over enantioselectivity and pyridyl C4-selectivity.
- Hangyeol Choi
- , Gangadhar Rao Mathi
- & Sungwoo Hong
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Article
| Open AccessStereoselective intermolecular radical cascade reactions of tryptophans or ɤ-alkenyl-α-amino acids with acrylamides via photoredox catalysis
Photocatalytic radical cascade reactions enable the facile construction of diverse cyclic compounds, though they rely on templated precursors. In this paper, the authors report on stereoselective intermolecular radical cascade reaction between tryptophan or ɤ-alkenyl substituted amino acids and acrylamides to synthesise multi-substituted trans-fused hexahydrocarbazoles or 1,3,5-trisubstituted cyclohexanes.
- Jiang-Tao Li
- , Jian-Nan Luo
- & Chun-Xiang Zhuo
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Article
| Open AccessBinary dopant segregation enables hematite-based heterostructures for highly efficient solar H2O2 synthesis
Photoelectrochemical H2O2 production offers a renewable means for chemical synthesis, yet water oxidation to H2O2 remains a challenge. Here, authors prepare heterostructured, metal-doped hematite mesocrystals that show a high selectivity for photoelectrochemical H2O2 alongside H2 production.
- Zhujun Zhang
- , Takashi Tsuchimochi
- & Takashi Tachikawa
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Article
| Open AccessExtra kinetic dimensions for label discrimination
Label discrimination is challenging in fluorescence microscopy due to broad spectra and narrow lifetime distribution. Here, the authors introduce extra kinetic dimensions by illuminating reversibly photoswitchable fluorophores with different intensities, and discriminate 20 spectrally similar fluorophores.
- Raja Chouket
- , Agnès Pellissier-Tanon
- & Ludovic Jullien