Featured
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| Open AccessStatic charge is an ionic molecular fragment
What is static charge? Analysis of molecularly well-defined surfaces shows that static charge is an ionic molecular fragment. Contact electrification causes the heterolytic cleavage of covalent bonds, generating these fragments.
- Yan Fang
- , Chi Kit Ao
- & Siowling Soh
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Article
| Open AccessA programmable hybrid digital chemical information processor based on the Belousov-Zhabotinsky reaction
Computing platforms based on chemical processes can be an alternative to digital computers in some scenarios but have limited programmability. Here the authors demonstrate a hybrid computing platform combining digital electronics and an oscillatory chemical reaction and demonstrate its computational capabilities.
- Abhishek Sharma
- , Marcus Tze-Kiat Ng
- & Leroy Cronin
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Article
| Open AccessExtensive photochemical restructuring of molecule-metal surfaces under room light
The nature of the molecule-metal interface is crucial for many technological applications. Here, the authors show that the photostability of the material can be sensitive to room light when coated with a single molecular layer, with implications for devices and processes.
- Chenyang Guo
- , Philip Benzie
- & Jeremy J. Baumberg
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Article
| Open AccessElectrofreezing of liquid water at ambient conditions
By performing long ab initio molecular dynamics simulations of water under external electric fields, for up to 500 picoseconds, the authors identify a transition to a ferroelectric amorphous phase at ambient conditions.
- Giuseppe Cassone
- & Fausto Martelli
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Article
| Open AccessDisentangling the multiorbital contributions of excitons by photoemission exciton tomography
Understanding excitonic optical excitations is integral to improving optoelectronic and photovoltaic semiconductor devices. Here, Bennecke et al. use photoemission exciton tomography to unravel the multiorbital electron and hole contributions of entangled excitonic states in the prototypical organic semiconductor C60.
- Wiebke Bennecke
- , Andreas Windischbacher
- & Stefan Mathias
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Article
| Open AccessObservation of geometric phase effect through backward angular oscillations in the H + HD → H2 + D reaction
In a combined experimental and theoretical study of the H + HD → H2 + D reaction at low collision energy (1.72 eV), the authors obtain detailed information on the quantum reaction dynamics surrounding a conical intersection.
- Shihao Li
- , Jiayu Huang
- & Xueming Yang
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Article
| Open AccessTransient chemical and structural changes in graphene oxide during ripening
Graphene oxide is in demand for various applications - however, this is complicated by changing physicochemical properties over time. Here, the authors show the intrinsic, metastable, and transient states of graphene oxide colloids upon ripening.
- Hayato Otsuka
- , Koki Urita
- & Katsumi Kaneko
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Article
| Open AccessDirect in-situ insights into the asymmetric surface reconstruction of rutile TiO2 (110)
The reconstruction of rutile TiO2 (110) impacts its surface chemistry and catalytic properties. Here, the authors offer a detailed understanding of the asymmetric surface reconstruction of TiO2 (110)-(1×2) through a combination of STEM and DFT calculations.
- Wentao Yuan
- , Bingwei Chen
- & Yong Wang
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Article
| Open AccessLarge dynamics of a phase separating arginine-glycine-rich domain revealed via nuclear and electron spins
The authors show the RNA-induced droplet formation by a component of Cajal bodies and reveal the large nanoseconds mobility of glycine residues inside droplets as a molecular factor potentially contributing to the large dynamics of Cajal bodies.
- Giuseppe Sicoli
- , Daniel Sieme
- & Nasrollah Rezaei-Ghaleh
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Article
| Open AccessPhotooxidation driven formation of Fe-Au linked ferrocene-based single-molecule junctions
Metal-metal interfaces hold promise as contacting moieties for single-molecule devices with tunable functionality, yet the direct bonding has remained a challenge. Here, Lee et al. report the formation of Fe-Au bond without chemical ligand support in ferrocene-based molecular junctions.
- Woojung Lee
- , Liang Li
- & Latha Venkataraman
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Article
| Open AccessUnified picture of vibrational relaxation of OH stretch at the air/water interface
Using femtosecond time-resolved heterodyne-detected vibrational sum-frequency generation spectroscopy the authors determine the vibrational relaxation (T1) time of the O-H stretch at the air/water interface by observing the decay of excited-state OH signals, providing a comprehensive picture of the interfacial vibrational relaxation process of water.
- Woongmo Sung
- , Ken-ichi Inoue
- & Tahei Tahara
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Article
| Open AccessTwofold rigidity activates ultralong organic high-temperature phosphorescence
Obtaining high-temperature phosphorescence in organic materials can potentially lead to broader applications, but can be challenging to achieve. Here, the authors report the use of rigid molecules as both host and guest to give temperature resistance and therefore high-temperature phosphorescence.
- Kaijun Chen
- , Yongfeng Zhang
- & Xiang Ma
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Article
| Open AccessVisualization-enhanced under-oil open microfluidic system for in situ characterization of multi-phase chemical reactions
Under-oil open microfluidic systems have potential for studying multi-phase chemical reactions but have so far demonstrated largely only for biological applications. Here, the authors report the development of a system for in situ characterization of gas-liquid reactions by Raman spectroscopy.
- Qiyuan Chen
- , Hang Zhai
- & Bu Wang
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Article
| Open AccessMulticompartmental coacervate-based protocell by spontaneous droplet evaporation
Coacervate-based compartments are attractive as potential protocells, but formation and control of the compartments can be challenging. Here, the authors report the spontaneous formation of core-shell, cell-sized coacervate compartments driven by droplet evaporation.
- Cheng Qi
- , Xudong Ma
- & Zhou Liu
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Article
| Open AccessImaging the state-to-state charge-transfer dynamics between the spin-orbit excited Ar+(2P1/2) ion and N2
The charge-transfer reaction Ar++N2 → Ar+N2+ has been largely studied as a model gas-phase reaction but many aspects remain to be understood. Here, differential cross sections of the reaction are measured and calculated with Ar+ prepared in 2P1/2 state, showing that the charge-transfer dynamics differs significantly for Ar+(2P1/2) compared to Ar+(2P3/2) when colliding with N2.
- Guodong Zhang
- , Dandan Lu
- & Hong Gao
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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 AccessObserving growth and interfacial dynamics of nanocrystalline ice in thin amorphous ice films
In-situ cryo-electron microscopy in thin amorphous ice films and ice-dynamics simulations reveal polymorph-dependent growth kinetics of nanoscale ice crystals. Hetero-crystalline ice exhibits anisotropic growth: fast-growing facets are associated with low-density interfaces, driving tetrahedral ordering of interfacial H2O molecules and accelerating ice growth.
- Minyoung Lee
- , Sang Yup Lee
- & Dong June Ahn
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Article
| Open AccessAnisotropic carrier dynamics and laser-fabricated luminescent patterns on oriented single-crystal perovskite wafers
Based on differently-oriented MAPbBr3 single-crystal wafers, the authors revealed anisotropic carrier dynamics by using angle-resolved pump-probe technique, and the microstructural mechanism of the femtosecond laser-induced emission enhancement
- Chao Ge
- , Yachao Li
- & Yang Liu
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Article
| Open AccessBioinspired light-driven chloride pump with helical porphyrin channels
Artificial ion channels have potential in a range of applications, but achieving performance comparable to biological channels has been challenging. Here, the authors report an artificial, light-driven chloride pump, inspired by halorhodopsin, with a helical porphyrin channel array.
- Chao Li
- , Yi Zhai
- & Lei Jiang
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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 AccessSite-specific metal-support interaction to switch the activity of Ir single atoms for oxygen evolution reaction
Common methods for regulating metal-support interactions for single-atom catalysts usually suffer from interference of the variation of supports or sacrificing the stability of catalysts. Here, the authors report a facile electrochemical deposition strategy to design highly active oxygen evolution catalysts with site-specific metal-support interactions via selective anchoring of single atoms.
- Jie Wei
- , Hua Tang
- & Jie Zeng
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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 AccessHydrogen evolution with hot electrons on a plasmonic-molecular catalyst hybrid system
Direct participation of plasmon-induced hot electrons in the photoelectrocatalytic synthesis of hydrogen. This report solves a long-lasting contentious issue surrounding plasmonic materials on catalytic applications.
- Ananta Dey
- , Amal Mendalz
- & Jacinto Sá
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Article
| Open AccessRydberg electron stabilizes the charge localized state of the diamine cation
Previous theoretical interpretations of the Rydberg spectra of dimethylpiperazine (DMP) debated the existence of a localized minimum on the surface of the DMP+ cation. Here, the authors show a substantial influence of the Rydberg electron on the molecular structure, restoring the localized minimum.
- Marc Reimann
- , Christoph Kirsch
- & Martin Kaupp
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Article
| Open AccessSpin relaxation of electron and hole polarons in ambipolar conjugated polymers
Spin and charge dynamics are inevitably linked, the study of the one often illuminating the other. Here, the authors study spin relaxation in ambipolar polymers and, backed by simulations, show how charge dynamics and wavefunction localization together set relaxation times up to room temperature.
- Remington L. Carey
- , Samuele Giannini
- & Henning Sirringhaus
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Article
| Open AccessSpectroscopy and dynamics of the hydrated electron at the water/air interface
Hydrated electrons at the water/air interface participate in natural and synthetic processes, but investigation of their properties remains challenging. Here the authors show that most of their electron density is solvated below the dividing surface and solvates into the bulk in around 10 picoseconds, leaving its phenoxyl radical source at the interface.
- Caleb J. C. Jordan
- , Marc P. Coons
- & Jan R. R. Verlet
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Article
| Open AccessProbing the critical nucleus size in tetrahydrofuran clathrate hydrate formation using surface-anchored nanoparticles
The critical nucleus, which considered a key step in the formation of clathrate hydrates, has not yet been empirically confirmed. Here, the authors probe the critical nucleus size in clathrate formation of tetrahydrofuran and thus provide mechanistic insights.
- Han Xue
- , Linhai Li
- & Jianjun Wang
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Article
| Open AccessInitial-site characterization of hydrogen migration following strong-field double-ionization of ethanol
Excitation of hydrogen-rich molecules often causes hydrogen migration, but characterisation of the individual sites is challenging. Here, the authors show that measurements of several isotopologues of ethanol can identify each hydrogen site’s contribution to the final products.
- Travis Severt
- , Eleanor Weckwerth
- & Itzik Ben-Itzhak
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Article
| Open AccessGiant adiabatic temperature change and its direct measurement of a barocaloric effect in a charge-transfer solid
Cyano-RbMnFeCo shows a large barocaloric effect with reversible adiabatic temperature changes of 74 K (340 MPa) and 85 K (560 MPa). Here, the authors observe temperature change of +44 K (440 MPa), stable after repeating over 100 times.
- Shin-ichi Ohkoshi
- , Kosuke Nakagawa
- & Ryu Hatano
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Article
| Open AccessSelective amide bond formation in redox-active coacervate protocells
Coacervate droplets are promising protocells that sequester nutrients, but how new peptides could be synthesized inside coacervates remains a mystery. Here, the authors develop redox-active coacervates that facilitate the formation of new peptide bonds.
- Jiahua Wang
- , Manzar Abbas
- & Evan Spruijt
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Article
| Open AccessDirecting polymorph specific calcium carbonate formation with de novo protein templates
Most proteins mediating biomineralization in nature are not well structured, and the structures of the relevant protein-mineral interfaces regulating mineralization are elusive. Here, the authors computationally design proteins that modulate calcium carbonate mineralization to generate hybrid materials and elucidate the roles of designed proteins in controlling mineralization.
- Fatima A. Davila-Hernandez
- , Biao Jin
- & David Baker
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Article
| Open AccessHot luminescence from single-molecule chromophores electrically and mechanically self-decoupled by tripodal scaffolds
A fundamental challenge for molecular electronics is the change in photophysical properties of molecules upon direct electrical contact. Here, the authors observe hot luminescence emitted by single-molecule chromophores that are electrically and mechanically self-decoupled by a tripodal scaffold.
- Vibhuti Rai
- , Nico Balzer
- & Michal Valášek
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Article
| Open AccessAnti-Kasha triplet energy transfer and excitation wavelength dependent persistent luminescence from host-guest doping systems
Anti-Kasha processes have potential in organic luminogens, but design of materials with these characteristics is challenging. Here, the authors report the development of a host-guest system with anti-Kasha behaviour and triplet energy transfer.
- Weiwei Xie
- , Wenbin Huang
- & Ben Zhong Tang
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Article
| Open AccessMulti-step nucleation pathway of C-S-H during cement hydration from atomistic simulations
The nucleation of calcium silicate hydrate is a crucial step in cement hydration, but is still a poorly understood process. Here the authors use atomistic simulations to study primary particles and their aggregation, revealing a potential C-S-H “basic building block”.
- Xabier M. Aretxabaleta
- , Jon López-Zorrilla
- & Hegoi Manzano
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Article
| Open AccessSharp zero-phonon lines of single organic molecules on a hexagonal boron-nitride surface
Low-temperature spectroscopy of single fluorescent molecules can be of use to study dynamics in the nano-environment around them. Here, Smit et al. show that the fluorescence wavelength of molecules on the surface of hexagonal boron-nitride is particularly sensitive to how clean this surface is.
- Robert Smit
- , Arash Tebyani
- & Michel Orrit
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Article
| Open AccessThe role of halogens in Au–S bond cleavage for energy-differentiated catalysis at the single-bond limit
Investigation of the reaction process at the single-bond interface is key to understanding the catalytic reaction mechanism. Here, the authors develop a STM-BJ method to monitor the catalytic process from the perspective of single-bond energy.
- Peihui Li
- , Songjun Hou
- & Xuefeng Guo
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| Open AccessExtent of carbon nitride photocharging controls energetics of hydrogen transfer in photochemical cascade processes
Savateev et al. investigate proton-coupled electron transfer from persistent graphitic carbon nitride radical to oxygen and imines. The results of their study find application in cascade photocatalysis – selective tetramerization of benzylic amines.
- Oleksandr Savateev
- , Karlo Nolkemper
- & Markus Antonietti
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Article
| Open AccessThe unusual quadruple bonding of nitrogen in ThN
Nitrogen can form a maximum of three shared electron-pair bonds to complete its octet, suggesting the maximum bond order of nitrogen is three. Here, the authors report a joint photoelectron spectroscopy and quantum chemical study, showing a quadruple bond between nitrogen and thorium in thorium nitride.
- Zejie Fei
- , Jia-Qi Wang
- & Jun Li
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Article
| Open AccessMicroscopic theory, analysis, and interpretation of conductance histograms in molecular junctions
Conductance histograms are common setups to study molecular junctions, but the dispersion of the signals makes it difficult to interpret at microscopic level. Here the authors develop a physical model of molecular junctions that connects this observable with molecular properties.
- Leopoldo Mejía
- , Pilar Cossio
- & Ignacio Franco
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Article
| Open AccessStructural characterization of tin in toothpaste by dynamic nuclear polarization enhanced 119Sn solid-state NMR spectroscopy
Stannous fluoride (SnF2) is a common fluoride source and antimicrobial agent used in commercial toothpaste products. Here, the authors show how dynamic nuclear polarization can be used to perform 119Sn nuclear magnetic resonance spectroscopy experiments that probe the molecular structure of tin ions in commercial toothpastes.
- Rick W. Dorn
- , Scott L. Carnahan
- & Aaron J. Rossini
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Article
| Open AccessGeneralised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks
The kinetics of guest-induced structural transition shown by flexible metal–organic frameworks (MOFs) remain poorly understood despite being crucial for process design. Here, three MOFs are studied to reveal the framework-dependent kinetic nature.
- Yuta Sakanaka
- , Shotaro Hiraide
- & Satoshi Watanabe
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Article
| Open AccessDirect time-resolved observation of surface-bound carbon dioxide radical anions on metallic nanocatalysts
Understanding the activity and selectivity of metal catalysts requires elucidating the dynamics of CO2•− radicals bound to the surface. Here, the authors use pulse radiolysis to directly observe the stabilization process of CO2•− radicals at nanoscale metallic sites from nanoseconds to seconds.
- Zhiwen Jiang
- , Carine Clavaguéra
- & Mehran Mostafavi
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Article
| Open AccessRevealing the role of double-layer microenvironments in pH-dependent oxygen reduction activity over metal-nitrogen-carbon catalysts
By combining theoretical simulations and spectroscopic measurements, Peng Li et al. demonstrated that distinct interfacial double-layer structures play a key role in the pH-dependent oxygen reduction kinetics over metal-nitrogen-carbon catalysts.
- Peng Li
- , Yuzhou Jiao
- & Shengli Chen
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Article
| Open AccessRedox signaling-driven modulation of microbial biosynthesis and biocatalysis
Microbial communication has significant implications for industrial applications, but constructing communication systems which support coordinated behaviors is challenging. Here, the authors report an electron transfer triggered redox communication network and demonstrate its ability to coordinate microbial metabolism.
- Na Chen
- , Na Du
- & Quan Yuan
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Article
| Open AccessDefying decomposition: the curious case of choline chloride
A rational design of deep eutectic solvents (DESs) is hindered because fundamental DES components, such as choline chloride (ChCl), decompose before melting. Here authors determine the melting properties of ChCl, unveiling ionic plastic crystals as a platform for DESs that meet modern sustainability, health, and safety requirements.
- Adriaan van den Bruinhorst
- , Jocasta Avila
- & Margarida Costa Gomes
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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 AccessLiquid spherical shells are a non-equilibrium steady state of active droplets
Dissipative structures are governed by non-equilibrium thermodynamics. Here, the authors describe a size-dependent transition from active droplets to active spherical shells—a dissipative structure that arises from reaction diffusion gradients.
- Alexander M. Bergmann
- , Jonathan Bauermann
- & Job Boekhoven
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Article
| Open AccessIntegrative solution structure of PTBP1-IRES complex reveals strong compaction and ordering with residual conformational flexibility
An integrated structural biology approach is utilized to elucidate the solution structure of the polypyrimidine-tract binding protein 1 (PTBP1/hnRNP I) complexed with an internal ribosome entry site (IRES) RNA fragment from encephalomyocarditis virus (EMCV).
- Georg Dorn
- , Christoph Gmeiner
- & Frédéric H.-T. Allain
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Article
| Open AccessTunable encapsulation of sessile droplets with solid and liquid shells
Encapsulated liquids are important for several microreactor applications, including (bio)chemistry in confined spaces. Here, the authors report on oil-infused particle shells that allow control of shell thickness, stability, and permeability for applications in crystal growth and cell cultivation.
- Rutvik Lathia
- , Satchit Nagpal
- & Prosenjit Sen