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| Open AccessSelective CO2 reduction to CH3OH over atomic dual-metal sites embedded in a metal-organic framework with high-energy radiation
Most approaches for CH3OH production focus on thermochemical, electrolytic, and photolytic processes. Here the authors report a radiolytic route to produce CH3OH from CO2 and water by atomic Cu-Ni dual sites embedded in a metal-organic framework.
- Changjiang Hu
- , Zhiwen Jiang
- & Jun Ma
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Article
| Open AccessVisible-light-driven reversible shuttle vicinal dihalogenation using lead halide perovskite quantum dot catalysts
The dihalogenation of alkenes is a significant chemical reaction, but its reaction conditions are demanding. Here, the authors show a photocatalytically assisted shuttle strategy using perovskite quantum dot catalysts for reversible vicinal dihalogenation under visible light illumination.
- Yonglong Li
- , Yangxuan Gao
- & Wei Xie
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Article
| Open AccessUnlocking full and fast conversion in photocatalytic carbon dioxide reduction for applications in radio-carbonylation
While the reduction of CO2 to CO is a very active research topic, use of the reduced CO in organic synthesis is not yet mature. Herein, the authors report a photocatalytic process that unlocks full CO2-to-CO conversion, opening opportunities for access to 11C- and 14C-labeled pharmaceuticals.
- Serena Monticelli
- , Alex Talbot
- & Davide Audisio
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Article
| Open AccessDeconvolution volumetric additive manufacturing
Volumetric additive manufacturing generally suffers from systematic undercuring of fine features, which limits its application range. Here, authors develop a model to predict print time variation with feature size and propose a deconvolution method, enabling precise fabrication of intricate structures.
- Antony Orth
- , Daniel Webber
- & Chantal Paquet
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Article
| Open AccessDiaryl-hemiindigos as visible light, pH, and heat responsive four-state switches and application in photochromic transparent polymers
Hemiindigo derivatives can act as photoswitches, but their applicability is limited by synthetic challenges. Here, the authors report the synthesis of modified photoswitches and demonstrate four-state switching, chemical fueling, and reversible inscription into transparent polymers.
- Maximilian Sacherer
- , Frank Hampel
- & Henry Dube
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Article
| Open AccessLong-term durability of metastable β-Fe2O3 photoanodes in highly corrosive seawater
Achieving long-term stable photoelectrochemical water decomposition in highly corrosive seawater remains a challenge. Here, the authors report a strategy for enhancing metal-oxygen interaction to achieve high stability of metastable β-Fe2O3 photoelectrochemical seawater splitting.
- Changhao Liu
- , Ningsi Zhang
- & Zhigang Zou
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Article
| Open AccessAggregation-regulated room-temperature phosphorescence materials with multi-mode emission, adjustable excitation-dependence and visible-light excitation
Room temperature phosphorescent materials have potential in a range of applications, but it is challenging to achieve multiple emission and excitation modes. Here, the authors report the development of RTP materials with different emission modes by regulating the aggregation state.
- Jingxuan You
- , Xin Zhang
- & Jun Zhang
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Article
| Open AccessAccessing parity-forbidden d-d transitions for photocatalytic CO2 reduction driven by infrared light
This study demonstrates the effectiveness and generality of utilizing ultrathin Cu-based hydrotalcite-like hydroxy salts as catalysts for infrared light-driven CO2 reduction based on their d-d orbital transition mechanism.
- Xiaodong Li
- , Li Li
- & Xinliang Feng
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Article
| Open AccessSub-picosecond collapse of molecular polaritons to pure molecular transition in plasmonic photoswitch-nanoantennas
Pump-probe spectroscopy is a versatile technique to explore ultrafast dynamics on the femtosecond timescale. Here the authors report a pump-probe experiment and quantum modeling combined study revealing dynamics of collective polaritonic states that are formed between a molecular photoswitch and plasmonic nanoantennas.
- Joel Kuttruff
- , Marco Romanelli
- & Nicolò Maccaferri
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Article
| Open AccessChalcogen-bridged coordination polymer for the photocatalytic activation of aryl halides
Chalcogen-bridged naphthalene diimide coordination polymers are designed and synthesised as potent excited state reductants for the activation of inert bonds in a series of aryl halides.
- Le Zeng
- , Tiexin Zhang
- & Chunying Duan
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Article
| Open AccessPhotoredox-catalyzed diastereoselective dearomative prenylation and reverse-prenylation of electron-deficient indole derivatives
Prenylated and reverse-prenylated indoline alkaloids are widely present in nature. Here, the authors demonstrate a tandem photoredox radical dearomatization/Claisen rearrangement of electron-deficient indoles for the rapid assembly of these privileged scaffolds.
- Xuexue Chang
- , Fangqing Zhang
- & Yangbin Liu
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Article
| Open AccessIntegrated halide perovskite photoelectrochemical cells with solar-driven water-splitting efficiency of 20.8%
High-efficiency photoelectrodes, which integrate light absorption with catalysis, have been limited to costly materials. Here, the authors develop an anticorrosion barrier that enables low-cost semiconductors for integrated solar fuel devices with 20.8% solar-to-hydrogen energy conversion efficiency.
- Austin M. K. Fehr
- , Ayush Agrawal
- & Aditya D. Mohite
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Article
| Open AccessArylcarboxylation of unactivated alkenes with CO2 via visible-light photoredox catalysis
Despite the importance of polycyclic carboxylic acids and derivatives in various fields, general methods for the arylcarboxylation of alkenes with CO2 remain elusive. Here, the authors transform unactivated alkenes into high value-added polycyclic carboxylic acids and derivatives via visible-light photoredox-catalysis, using CO2 as the one-carbon feedstock.
- Wei Zhang
- , Zhen Chen
- & Da-Gang Yu
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Article
| Open AccessSolution-processable polymers of intrinsic microporosity for gas-phase carbon dioxide photoreduction
This works presents a series of solution processable, conjugated polymers of intrinsic microporosity, which are used as photocatalysts for carbon dioxide reduction to carbon monoxide in the presence of hydrogen.
- Floriana Moruzzi
- , Weimin Zhang
- & Iain McCulloch
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Article
| Open AccessUncovering the chiral bias of meteoritic isovaline through asymmetric photochemistry
Excess of l-amino acids in meteorites suggests an extraterrestrial origin of biomolecular homochirality, which may stem from chiral light-matter interactions. Here the authors support this hypothesis with asymmetric photolysis experiments on racemic isovaline films, showing that circularly polarized starlight can produce l-enantiomeric excesses that can be amplified during parent bodies’ alteration.
- Jana Bocková
- , Nykola C. Jones
- & Cornelia Meinert
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Article
| Open AccessNearly 100% selective and visible-light-driven methane conversion to formaldehyde via. single-atom Cu and Wδ+
Direct solar-driven methane (CH4) reforming is highly desirable but challenging. Here, the synergy of atomic Cu species and partially reduced tungsten (Wδ+), stabilized over an oxygen-vacancy-rich WO3, enables exceptional CH4 conversion to formaldehyde (HCHO) under visible light.
- Lei Luo
- , Xiaoyu Han
- & Junwang Tang
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Article
| Open AccessSingle-atomic-site platinum steers photogenerated charge carrier lifetime of hematite nanoflakes for photoelectrochemical water splitting
The achievable photocurrent of hematite, α-Fe2O3, is typically limited far below its theoretical limit. Here, the authors engineer single Pt atomic sites with surface oxygen vacancies into hematite photoanodes, which leads to enhanced photoelectrochemical water splitting.
- Rui-Ting Gao
- , Jiangwei Zhang
- & Limin Wu
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Article
| Open AccessFerricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy
Reliably identifying transient intermediates is crucial to elucidate chemical reaction mechanisms. Here, the authors use femtosecond Fe Kβ main line and valence-to-core x-ray emission spectroscopy to characterize a short-lived intermediate of the aqueous ferricyanide photo-aquation reaction.
- Marco Reinhard
- , Alessandro Gallo
- & Dimosthenis Sokaras
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Article
| Open AccessDesigning reliable and accurate isotope-tracer experiments for CO2 photoreduction
Current verification of CO2 photoreduction products using isotope-tracer methods is insufficient and can provide false-positive results. Here, rigorous protocols and case studies are presented to avoid pitfalls in isotope-tracer experiments.
- Shengyao Wang
- , Bo Jiang
- & Jinhua Ye
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Article
| Open AccessPhotocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes
Geminal and vicinal borosilanes are useful building blocks in synthetic chemistry. But in contrast to the well-established transition-metal catalyzed methods, radical approaches are rarely explored. Here, the authors report the synthesis of geminal borosilanes from α-selective hydrosilylation of alkenyl boronates via photoinduced hydrogen atom transfer (HAT) catalysis
- Degong Kong
- , Muliang Zhang
- & Jie Wu
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Article
| Open AccessPhotothermal-enabled single-atom catalysts for high-efficiency hydrogen peroxide photosynthesis from natural seawater
Photoproduction of solar fuels and important chemicals is of significant interest. Here, the authors construct a cobalt single atom-based photothermal-photocatalytic heterostructure that realizes efficient hydrogen peroxide photosynthesis from earth-abundant seawater.
- Wei Wang
- , Qun Song
- & Ning Wang
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Article
| Open AccessHigh-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling
To achieve efficient photocatalytic non-oxidative methane coupling, a strong polarization environment with abundant activation sites for C-H scissoring is needed. This can be created through the fabrication of high-density frustrated Lewis pairs on lamellar Nb2O5 using a thermal-reduction promoted phase-transition process.
- Ziyu Chen
- , Yutao Ye
- & Jinlong Zhang
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Article
| Open AccessAn electron-hole rich dual-site nickel catalyst for efficient photocatalytic overall water splitting
Vast majority of photocatalysts for hydrogen production relies on additional sacrificial agents and noble metal cocatalysts. It is of great importance yet challenging to achieve photocatalytic overall water splitting with decent performance. Here, the authors report Ni2P based photocatalyst assisted by H2O2-craking reaction for overall water splitting with H2 and O2 production of 1507 μmol h−1 g−1 H2 and 702 μmol h−1 g−1.
- Xiaoqing Yan
- , Mengyang Xia
- & Guidong Yang
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Article
| Open AccessStrong synergy between gold nanoparticles and cobalt porphyrin induces highly efficient photocatalytic hydrogen evolution
The reaction efficiency of reactants near plasmonic nanostructures can be enhanced under illumination. Here, the authors show that the activity of a Co porphyrin molecular catalyst bound to Au nanoparticles is enhanced by plasmonic effects, yielding a high photocatalytic hydrogen generation rate.
- Huixiang Sheng
- , Jin Wang
- & Gang Lu
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Article
| Open AccessPoly(heptazine imide) ligand exchange enables remarkable low catalyst loadings in heterogeneous metallaphotocatalysis
The development of heterogeneous metallaphotocatalysis is of great interest for sustainable organic synthesis. Herein, the authors demonstrate the incorporation of privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered and crystalline potassium poly(heptazine imide) (K-PHI).
- Liuzhuang Xing
- , Qian Yang
- & Yunfei Cai
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Article
| Open AccessUltrafast motion in a third generation photomolecular motor
Controlling molecular motion at nanoscale is important for the design of nanomachines. Here the authors use ultrafast vibrational and electronic spectroscopy to characterize the mechanism of motion of a light driven molecular motor designed to support translational movement.
- Palas Roy
- , Wesley R. Browne
- & Stephen R. Meech
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Article
| Open AccessSinglet fission as a polarized spin generator for dynamic nuclear polarization
Singlet fission (SF) can create spin-polarized quintet states in organic systems, but this effect and its potential applications have not been sufficiently explored. Here, authors demonstrate that SF in supramolecular assemblies of pentacene chromophores improves the sensitivity of magnetic resonance of water molecules through dynamic nuclear polarization in a water-glycerol glass.
- Yusuke Kawashima
- , Tomoyuki Hamachi
- & Nobuhiro Yanai
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Article
| Open AccessDesigning covalent organic frameworks with Co-O4 atomic sites for efficient CO2 photoreduction
A class of inexpensive aminoanthraquinone organic dyes are shown to facilitate visible-light-driven CO2 reduction. Overall reaction efficiencies were found to be optimal when both electron donating and accepting groups were on a single dye molecule.
- Qian Zhang
- , Shuaiqi Gao
- & Jianji Wang
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Article
| Open AccessRoom-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2
A photocatalyst for CO2 reduction to C3H8 is prepared by implanting Cu single atoms on vacancy rich TiO2 single layers. Key reaction intermediates, *CHOCO and *CH2OCOCO, are stabilized on the catalyst which promotes C-C bond formation.
- Yan Shen
- , Chunjin Ren
- & Yong Zhou
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Article
| Open AccessRed light-driven electron sacrificial agents-free photoreduction of inert aryl halides via triplet-triplet annihilation
The functionalization of aryl halides via photocatalysis typically involves the use of blue light. Here, the authors report the photoreduction of aryl halides enabled by red light; the method does not require a sacrificial electron donor.
- Le Zeng
- , Ling Huang
- & Gang Han
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Article
| Open AccessPhotocatalytic CO2 reduction with aminoanthraquinone organic dyes
A class of inexpensive aminoanthraquinone organic dyes are shown to facilitate visible-light-driven CO2 reduction. Overall reaction efficiencies were found to be optimal when both electron donating and accepting groups were on a single dye molecule.
- Qinqin Lei
- , Huiqing Yuan
- & Zhiji Han
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Article
| Open AccessReal-time observation of the buildup of polaron in α-FAPbI3
Polaron formation is considered to play a crucial role to enhance photoelectric performance of hybrid halide perovskites. Here, the authors report the real-time observation of polaron formation process by terahertz emission spectroscopy and reveal two different polaron modes in FAPbI3 films.
- Xingyu Yue
- , Chunwei Wang
- & Juan Du
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Article
| Open AccessOne-stone-for-two-birds strategy to attain beyond 25% perovskite solar cells
Long-term stability and stable efficiency are essential for large-area fabrication of perovskite solar cells. Here, the authors achieve in situ anion-fixation and undercoordinated-Pb passivation using amidino-based ligand, realizing maximum power conversion efficiency of 25.3% with T95 over 500 h.
- Tinghuan Yang
- , Lili Gao
- & Kui Zhao
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Article
| Open AccessAn unexpected synthesis of azepinone derivatives through a metal-free photochemical cascade reaction
Photochemical nitrene transfer offers a green avenue for heterocyclic syntheses. Here, the authors developed a metal-free, visible light-mediated cascade reaction for the preparation of azepinone derivatives.
- Lina Song
- , Xianhai Tian
- & A. Stephen K. Hashmi
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Article
| Open AccessDearomative triple elementalization of quinolines driven by visible light
Organoboron and organosilicon compounds have potential applications in various fields including materials science and medicinal chemistry. Here the authors report a protocol that enables the dearomative carbo-sila-boration of quinolines.
- Shiho Ishigaki
- , Yuki Nagashima
- & Ken Tanaka
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Article
| Open AccessAtomically dispersed iridium catalysts on silicon photoanode for efficient photoelectrochemical water splitting
Single atom catalysts not only maximize the atomic efficiency of noble metal but also introduce unconventional geometric and electronic structures. Here, the authors demonstrate the decoration of iridium single atoms on silicon photoanodes to boost the photogenerated charge carrier kinetics.
- Sang Eon Jun
- , Youn-Hye Kim
- & Ho Won Jang
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Article
| Open AccessModulating stereoselectivity in allylic C(sp3)-H bond arylations via nickel and photoredox catalysis
The selective construction of C-C double bonds in alkenes, which can be one of two isomers, is a fundamental focus of organic chemistry. Here, the authors systematically investigated the stereoselectivity in allylic C(sp3)-H bond arylations and demonstrated a ligand switch could allow a stereodivergent synthesis of silyl enol ethers.
- Long Huang
- , Marcin Szewczyk
- & Magnus Rueping
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Article
| Open AccessSymmetry-breaking host–guest assembly in a hydrogen-bonded supramolecular system
Self-assembly processes usually yield symmetric compounds. Here, the authors report the distortion of a symmetric hydrogen-bonded resorcin[4]arene cage upon encapsulation of an iridium complex.
- Shinnosuke Horiuchi
- , Takumi Yamaguchi
- & Keisuke Umakoshi
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Article
| Open AccessEnhanced chiroptic properties of nanocomposites of achiral plasmonic nanoparticles decorated with chiral dye-loaded micelles
Circularly polarized luminescent materials with large dissymmetry and efficiency are in demand. Here, the authors investigate chirality-induced spin polarization in achiral gold nanorods decorated with chiral dye-loaded micelles to enhance chiroptic activity.
- Tonghan Zhao
- , Dejing Meng
- & Pengfei Duan
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Article
| Open AccessLigand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes
The stereoselective synthesis of 1,3-dienes represents a challenge in organic synthesis. Here, the authors report a ligand-controlled stereodivergent access to both Z- and E-sulfonyl-1,3-dienes via photoredox and nickel catalysis.
- Tianyu Long
- , Chen Zhu
- & Lingling Chu
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| Open AccessProspects and good experimental practices for photocatalytic ammonia synthesis
The development of photocatalysts is greatly hindered by false positives or non-reproducible data. Here, The authors describe the current known causes of non-reproducible results in the literature and present solutions to mitigate these false positive results.
- Po-Wei Huang
- & Marta C. Hatzell
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Article
| Open AccessPhotochemical diazidation of alkenes enabled by ligand-to-metal charge transfer and radical ligand transfer
The difunctionalization of alkenes allows for efficient construction of molecular complexity. Combining Ligand-to-Metal Charge transfer (LMCT) and Radical Ligand Transfer (RLT), the authors show a photochemical diazidation using iron salts, allowing rapid preparation of vicinal diamines and other privileged synthetic motifs.
- Kang-Jie Bian
- , Shih-Chieh Kao
- & Julian G. West
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Article
| Open AccessStructural mechanism of signal transduction in a phytochrome histidine kinase
In this study, authors have solved cryo-EM structures of a bacteriophytochrome in its dark-adapted and illuminated states. The structures reveal the structural mechanism for photoactivation of the phytochrome.
- Weixiao Yuan Wahlgren
- , Elin Claesson
- & Sebastian Westenhoff
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Article
| Open AccessPhotoinduced β-fragmentation of aliphatic alcohol derivatives for forging C–C bonds
Transformations of alcohols, which are ubiquitous in chemistry and are native functionalities in many natural products and bioactive molecules, are cornerstones of organic synthesis. Here the authors describe photocatalyzed cross-couplings of activated alcohols with α-amino acids, providing a direct approach for a variety of unnatural amino acids.
- Yiman Gao
- , Jie Liu
- & Lingchao Cai
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Article
| Open AccessA theory-driven synthesis of symmetric and unsymmetric 1,2-bis(diphenylphosphino)ethane analogues via radical difunctionalization of ethylene
DPPEs are fundamental bidentate ligands with a C2-alkyl-linker chain for many transition-metal-catalyzed reactions. Here, authors utilize the AFIR method to develop a practical synthetic method for both symmetric and unsymmetric DPPEs with ethylene.
- Hideaki Takano
- , Hitomi Katsuyama
- & Tsuyoshi Mita
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Article
| Open AccessPhotocatalytic direct borylation of carboxylic acids
Boronic acids are useful reagents in organic synthesis and thus methods to prepare these compounds under mild conditions are desirable. Here, the authors synthesize boronic acids via photocatalytic decarboxylation of benzoic acids followed by borylation; guanidine-type additives are used to assist the process.
- Qiang Wei
- , Yuhsuan Lee
- & Zhibo Liu
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Article
| Open AccessAccessing chiral sulfones bearing quaternary carbon stereocenters via photoinduced radical sulfur dioxide insertion and Truce–Smiles rearrangement
The preparation of chiral sulfones featuring quaternary carbon stereocenters remains challenging. Here the authors report the synthesis of such compounds via a multicomponent reaction involving a photoinduced radical sulfur dioxide insertion followed by an asymmetric Truce–Smiles rearrangement.
- Jiapian Huang
- , Fei Liu
- & Jie Wu
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Article
| Open AccessStereoisomeric engineering of aggregation-induced emission photosensitizers towards fungal killing
Fungal infections are often major causes of disease in immune compromised patients and photodynamic therapy offers and attractive treatment. Here, the authors develop stereoisomeric photosensitizers via supramolecular assembly and demonstrate aggregation-induced photodynamic action against fungi.
- Wenping Zhu
- , Ying Li
- & Ben Zhong Tang
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Article
| 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