Jul 26, 2015

Hexahedron Prism-Anchored Octahedronal CeO2: Crystal Facet-Based Homojunction Promoting Efficient Solar Fuel Synthesis

Key Laboratory of Modern Acoustics (MOE), Institute of Acoustics, Department of Physics, National Laboratory of Solid State Microstructures, School of Physics, §Eco-Materials and Renewable Energy Research Center (ERERC), Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China
Faculty of Materials Science and Engineering, Key Laboratory of Advanced Materials of Yunnan Province, Kunming University of Science and Technology, Kunming 650093, China
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.5b05926
Publication Date (Web): July 20, 2015
Copyright © 2015 American Chemical Society


Abstract Image
An unprecedented, crystal facet-based CeO2 homojunction consisting of hexahedron prism-anchored octahedron with exposed prism surface of {100} facets and octahedron surface of {111} facets was fabricated through solution-based crystallographic-oriented epitaxial growth. The photocatalysis experiment reveals that growth of the prism arm on octahedron allows to activate inert CeO2 octahedron for an increase in phototocatalytic reduction of CO2 into methane. The pronounced photocatalytic performance is attributed to a synergistic effect of the following three factors: (1) band alignment of the {100} and {111} drives electrons and holes to octahedron and prism surfaces, respectively, aiming to reach the most stable energy configuration and leading to a spatial charge separation for long duration; (2) crystallographic-oriented epitaxial growth of the CeO2 hexahedron prism arm on the octahedron verified by the interfacial lattice fringe provides convenient and fast channels for the photogenerated carrier transportation between two units of homojuntion; (3) different effective mass of electrons and holes on {100} and {111} faces leads to high charge carrier mobility, more facilitating the charge separation. The proposed facet-based homojunction in this work may provide a new concept for the efficient separation and fast transfer of photoinduced charge carriers and enhancement of the photocatalytic performance.

Stepwise Motion in a Multivalent [2](3)Catenane

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
§ University of Chinese Academy of Sciences, Beijing 100049, China
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.5b05758
Publication Date (Web): July 17, 2015
Copyright © 2015 American Chemical Society


Abstract Image
The motions of biomolecular machines are usually multistep processes, and are involved in a series of conformational changes. In this paper, a novel triply interlocked [2](3)catenane composed of a tris(crown ether) host eTC and a circular ditopic guest with three dibenzyl ammonium (DBA) sites and three N-methyltriazolium (MTA) sites was reported. Due to the multivalency nature of the catenane, the acid–base triggered motion was performed by a stepwise manner. The coconformations of the four related stable states have been directly identified and quantified which confirmed the multistep process. In order to quantify the dynamics with environmental acidity changes, the values of the three levels of dissociation constant pKa have been determined. The special interlocked topology of the [2](3)catenane also endows the motion of each crown ether ring in the host with unexpected selectivity for the MTA sites. This study provides clues to comprehend the underlying motion mechanism of intricate biological molecular machines, and further design artificial molecular machine with excellent mechanochemistry properties.

Jul 13, 2015

Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts

  • Gulen Yesilbag Tonga,
  • Youngdo Jeong,
  • Bradley Duncan,
  • Tsukasa Mizuhara,
  • Rubul Mout,
  • Riddha Das,
  • Sung Tae Kim,
  • Yi-Cheun Yeh,
  • Bo Yan,
  • Singyuk Hou, and
  •  Vincent M. Rotello
    Nature Chemistry
    Published online


Bioorthogonal catalysis broadens the functional possibilities of intracellular chemistry. Effective delivery and regulation of synthetic catalytic systems in cells are challenging due to the complex intracellular environment and catalyst instability. Here, we report the fabrication of protein-sized bioorthogonal nanozymes through the encapsulation of hydrophobic transition metal catalysts into the monolayer of water-soluble gold nanoparticles. The activity of these catalysts can be reversibly controlled by binding a supramolecular cucurbit[7]uril ‘gate-keeper’ onto the monolayer surface, providing a biomimetic control mechanism that mimics the allosteric regulation of enzymes. The potential of this gated nanozyme for use in imaging and therapeutic applications was demonstrated through triggered cleavage of allylcarbamates for pro-fluorophore activation and propargyl groups for prodrug activation inside living cells.

Jul 8, 2015


Graphical abstract: Self-organisation of dodeca-dendronized fullerene into supramolecular discs and helical columns containing a nanowire-like core

Self-organisation of dodeca-dendronized fullerene into supramolecular discs and helical columns containing a nanowire-like core

Chem. Sci., 2015,6, 3393-3401

DOI: 10.1039/C5SC00449G

Brønsted Acidity in Metal–Organic Frameworks

Department of Chemistry, University of California—Berkeley, Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720, United States
§ King Fahd University of Petroleum and Minerals, Dhahran 34464, Saudi Arabia
Chem. Rev., Article ASAP
DOI: 10.1021/acs.chemrev.5b00221
Publication Date (Web): June 19, 2015
Table of Contents:
  • 1. Introduction
  • 2. Preparation Methods
    • 2.1. Encapsulated Brønsted Acid Molecules
    • 2.2. Ligated Brønsted Acid Groups
    • 2.3. Covalently Bound Brønsted Acid Functional Groups of Organic Linking Units
  • 3. Characterization Methods
    • 3.1. Indicators and Titration Methods
    • 3.2. Test Reactions
    • 3.3. Gas Sorption Techniques
    • 3.4. Vibrational Spectroscopy Methods
    • 3.5. Solid-State Nuclear Magnetic Resonance (NMR) Methods
    • 3.6. Diffraction Techniques
  • 4. Applications
    • 4.1. Ammonia Capture
    • 4.2. Proton-Conducting Materials
    • 4.3. Catalysis
  • 5. Summary and Outlook

Catalytic C–C Bond Activations via Oxidative Addition to Transition Metals

Laboratory of Asymmetric Catalysis and Synthesis, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne 1015, Switzerland
Chem. Rev., Article ASAP
DOI: 10.1021/acs.chemrev.5b00138
Publication Date (Web): June 5, 2015


Table of Contents
  • 1. Introduction
  • 2. Strain-Driven C–C Bond Activations
    • 2.1. C–C Bond Activations of Three-Membered Rings
      • 2.1.1. C–C Bond Activations of Cyclopropanes
      • 2.1.2. C–C Bond Activations of Alkylidenecyclopropanes
      • 2.1.3. C–C Bond Activations of Vinylcyclopropanes
      • 2.1.4. C–C Bond Activation of Cyclopropenes
    • 2.2. C–C Bond Activations of Four-Membered Rings
      • 2.2.1. C–C Bond Activations of Biphenylenes
      • 2.2.2. C–C Bond Activations of Cyclobutenediones and Benzocyclobutenediones
      • 2.2.3. C–C Bond Activations of Cyclobutenones and Benzocyclobutenones
      • 2.2.4. C–C Bond Activations of Cyclobutanones
  • 3. C–C Bond Activations of Unstrained Substrates
    • 3.1. C–C Bond Activations Assisted by Chelation
      • 3.1.1. Permanent Directing Groups
      • 3.1.2. Temporary Directing Groups
    • 3.2. Decarbonylation
    • 3.3. C–CN Bond Activation
      • 3.3.1. Carbocyanation of Alkynes
      • 3.3.2. Carbocyanation of Alkenes
      • 3.3.3. Coupling Reactions via C–CN Bond Activations
  • 4. Summary and Outlook

Biological Applications of Supramolecular Assemblies Designed for Excitation Energy Transfer

Hui-Qing Peng , Li-Ya Niu , Yu-Zhe Chen , Li-Zhu Wu , Chen-Ho Tung *§, and Qing-Zheng Yang *
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Key Laboratory of Radiopharmaceuticals, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, People’s Republic of China
§ Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Shandong Normal University, Jinan 250014, People’s Republic of China
Chem. Rev., Article ASAP
DOI: 10.1021/cr5007057
Publication Date (Web): June 4, 2015

Table of Contents:
  • 1. Introduction
    • 1.1. Energy Transfer Processes and Their Mechanisms
      • 1.1.1. Fluorescence Resonance Energy Transfer
      • 1.1.2. Electron Exchange
    • 1.2. Self-Assemblies for Energy Transfer
  • 2. Artificial Light-Harvesting Systems
    • 2.1. Multiporphyrin Arrays for Light Harvesting
    • 2.2. Low Molecular Weight Gels for Light Harvesting
    • 2.3. Biomaterials for Light Harvesting
      • 2.3.1. Proteins for Light Harvesting
      • 2.3.2. DNA as a Scaffold
    • 2.4. Organic–Inorganic Hybrid Materials for Light Harvesting
    • 2.5. Other Scaffolds for Light Harvesting
  • 3. Bioimaging
    • 3.1. Multicolor Imaging
    • 3.2. NIR Imaging
    • 3.3. Stimuli-Responsive Bioimaging
      • 3.3.1. Photoresponsive Imaging
      • 3.3.2. pH-Responsive Imaging
    • 3.4. Upconversion Luminescence Bioimaging
  • 4. Biosensor
    • 4.1. Ratiometric Biosensing
    • 4.2. Upconversion Luminescence Biosensing
    • 4.3. Biosensing by Signal Amplification
  • 5. Photodynamic Therapy
    • 5.1. Photodynamic Therapy Based on Single-Photon Excitation
    • 5.2. Photodynamic Therapy Based on Multiphoton Excitation
      • 5.2.1. Photodynamic Therapy Based on Two-Photon Excitation
      • 5.2.2. Photodynamic Therapy Based on Upconversion Nanoparticles
  • 6. Conclusion

Colloidal Quantum Dot Solar Cells

Department of Electrical and Computer Engineering, University of Toronto, 10 King’s College Road, Toronto, Ontario M5S 3G4, Canada
Division of Physical Sciences and Engineering, Solar & Photovoltaics Engineering Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
§ School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, China
Department of Electrical and Computer Engineering, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, United States
Chem. Rev., Article ASAP
DOI: 10.1021/acs.chemrev.5b00063
Publication Date (Web): June 24, 2015

Table of Contents

  • 1. Introduction
  • 2. Quantum Dot Synthesis
    • 2.1. Nucleation, Growth, and Stabilization
    • 2.2. Synthetic Methods
    • 2.3. Control of Quantum Dot Physical Properties
      • 2.3.1. Quantum Dot Size
      • 2.3.2. Quantum Dot Shape
    • 2.4. Control of Quantum Dot Chemical Properties
      • 2.4.1. Solution-Phase Ligand Exchange
      • 2.4.2. Alloying and Doping
      • 2.4.3. Core/Shell Quantum Dots
  • 3. Materials Processing
    • 3.1. Physical Processing
    • 3.2. Chemical Processing
      • 3.2.1. Ligand Exchange
      • 3.2.2. Processing Conditions
      • 3.2.3. Impurity Management
  • 4. Optoelectronic Properties of Colloidal Quantum Dots
    • 4.1. Carrier Mobility
    • 4.2. Trap Density
    • 4.3. Carrier Lifetime and Diffusion Length
    • 4.4. Doping Density
  • 5. Device Physics and Performance
    • 5.1. Schottky CQD Solar Cells
    • 5.2. Heterojunction CQD Solar Cells
    • 5.3. Bulk Heterojunction CQD Solar Cells
    • 5.4. Quantum Junction and Nanoheterojunction CQD Solar Cells
    • 5.5. Quantum Funnels
    • 5.6. Graded Doping Architectures
    • 5.7. Electrical Contact Development
      • 5.7.1. Strategies To Improve Hole Collection
      • 5.7.2. Strategies To Improve Electron Collection
    • 5.8. Optical Engineering of CQD Solar Cells
      • 5.8.1. Geometric and Nanophotonic Light Trapping
      • 5.8.2. Plasmonic Enhancement of CQD Solar Cells
    • 5.9. CQD Solar Cell Concepts beyond the Single-Junction Limit
      • 5.9.1. Multiple-Junction CQD Solar Cells
      • 5.9.2. Hot Carrier Effects in CQD Solar Cells
  • 6. Conclusion

Molecular Catalysts for Water Oxidation

Department of Chemistry and Energy Sciences Institute, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, United States
Chem. Rev., Article ASAP
DOI: 10.1021/acs.chemrev.5b00122
Publication Date (Web): July 7, 2015


Table of Contents
  • 1. Introduction
    • 1.1. Role of Water Oxidation in Energy Storage
    • 1.2. Natural Photosynthetic Water Oxidation(7)
    • 1.3. Water Electrolysis
    • 1.4. Heterogeneous Oxide-Based Catalysts
  • 2. Molecular Catalysts for Water Oxidation
    • 2.1. Manganese Catalysts
    • 2.2. Ruthenium Catalysts
    • 2.3. Iridium Catalysts
    • 2.4. Iron Catalysts
    • 2.5. Cobalt Catalysts
    • 2.6. Other Catalysts
  • 3. Outlook and Conclusions

Light-Driven and Phonon-Assisted Dynamics in Organic and Semiconductor Nanostructures

Chemistry and Biochemistry Department, North Dakota State University, Fargo, North Dakota 5810, United States
Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, United States
§ Theoretical Division, Center for Nonlinear Studies (CNLS) and Center for Integrated Nanotechnologies (CINT), Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States
Chem. Rev., 2015, 115 (12), pp 5929–5978
DOI: 10.1021/acs.chemrev.5b00012
Publication Date (Web): May 20, 2015
Table of Contents:
  • 1. Introduction
    • 1.1. Confinement Effects in Carbon-Based and Inorganic Nanomaterials
    • 1.2. Sensitivity of Photophysics of Quantum Dots to Surface Chemistry
    • 1.3. Chemical Functionalization and Electronic Properties of Carbon Nanotubes
    • 1.4. Self-Assembly and Disorder in Conjugated Polymer Materials
    • 1.5. Role of Computational Modeling toward Establishing Structure–Property Relationships in Nanostructured Materials
  • 2. Geometry Optimization and Ground-State Electronic Structure
    • 2.1. Applicability of Force Field, Semiempirical, and DFT Methods
    • 2.2. An Interplay of σ- and π-Bonding in Carbon-Based Systems
      • 2.2.1. Conjugated Polymers and Oligomers
      • 2.2.2. Single-Wall Carbon Nanotubes
    • 2.3. Quantum Dots: Shapes, Bonds, and Ligand Binding
      • 2.3.1. Models of Magic Size Nanocrystals
      • 2.3.2. Simulations of Surface Capping
      • 2.3.3. Benchmarking DFT Methods for Quantum Dot Systems
  • 3. Calculations and Analysis of Electronic Excitations
    • 3.1. ΔSCF and Time-Dependent SCF Methods for Simulations of Electronic Excitations
    • 3.2. Single-Electron versus Many-Electron Approaches to Excitations in Quantum Dots
    • 3.3. Excitonic Effects in Conjugated Polymers and Carbon Nanotubes
  • 4. Impact of Conformational Disorders and Surface Chemistry on Electronic Properties
    • 4.1. Stoichiometry and Surface Ligands in Quantum Dots
    • 4.2. Inter- and Intramolecular Disorder in Conjugated Polymers
      • 4.2.1. Combined Force-Field/DFT Methods for Amorphous Structures
      • 4.2.2. Participation Ratio as a Measure of Localization of Electronic States
      • 4.2.3. Origins of Trap States: Electron versus Hole Traps
    • 4.3. Surface Functionalization and Chemical Defects in Carbon Nanotubes
      • 4.3.1. Brightening of Carbon Nanotubes via Covalent Functionalization
      • 4.3.2. Noncovalent Functionalization by Bio- and Conjugated Polymers
  • 5. Excited-State Potential Energy Surfaces and Electron–Vibrational Couplings
    • 5.1. Electron–Phonon Effects in Quantum Dots
    • 5.2. Huang–Rhys Factors and Excitation Self-Trapping in Conjugated Systems
    • 5.3. Electron–Vibrational Couplings and Polarons in Conjugated Polymers
  • 6. Nonadiabatic Dynamics and Nonradiative Relaxation
    • 6.1. Photoexcited Dynamics in Quantum Dots
    • 6.2. Charge Transfer in Functionalized Carbon Nanotubes
    • 6.3. Internal Conversion and Energy Transfer in Conjugated Macromolecules
  • 7. Conclusion, Outlook, and Perspectives

The Golden Age of Transfer Hydrogenation

ISM, Université de Bordeaux, 351 Cours de la Libération, 33405 Talence Cedex, France
Chem. Rev., 2015, 115 (13), pp 6621–6686
DOI: 10.1021/acs.chemrev.5b00203
Publication Date (Web): June 10, 2015


Table of Contents:
  • 1. Introduction
    • 1.1. History, Basic Concepts, and Seminal Studies of Transfer Hydrogenation
    • 1.2. Scope of the Review
  • 2. Recent Advances and Trends in TH Using Transition-Metal Catalysts
    • 2.1. Homogeneous or Quasi-Homogeneous Transition-Metal Catalysts
      • 2.1.1. Iron-Based Catalysts
      • 2.1.2. Ruthenium-Based Catalysts
      • 2.1.3. Osmium-Based Catalysts
      • 2.1.4. Cobalt-Based Catalysts
      • 2.1.5. Rhodium-Based Catalysts
      • 2.1.6. Iridium-Based Catalysts
      • 2.1.7. Nickel-Based Catalysts
      • 2.1.8. Palladium-Based Catalysts
      • 2.1.9. Gold-Based Catalysts
      • 2.1.10. Bimetallic and Multimetallic Catalysts
      • 2.1.11. Other Transition Metals Catalysts
    • 2.2. Heterogeneous Transition-Metal Catalysts
      • 2.2.1. Magnetic Nanoparticle-Immobilized Catalysts
      • 2.2.2. Polymer-Immobilized Catalysts
      • 2.2.3. Silica-Immobilized Catalysts
      • 2.2.4. Carbon Material-Immobilized Catalysts
      • 2.2.5. Titanium Dioxide-Immobilized Catalysts
      • 2.2.6. Aluminum-Immobilized Catalysts
      • 2.2.7. Zirconium-Immobilized Catalysts
      • 2.2.8. Other Material-Immobilized Catalysts
  • 3. Organocatalysts in TH
  • 4. Other Catalysts or Protocols for TH
  • 5. Conclusions and Perspectives

Gaseous O2, NO, and CO in Signal Transduction: Structure and Function Relationships of Heme-Based Gas Sensors and Heme-Redox Sensors

Department of Cell Biology and Genetics and Key Laboratory of Molecular Biology in High Cancer Incidence Coastal Chaoshan Area of Guangdong Higher Education Institutes, Shantou University Medical College, Shantou, Guangdong 515041, China
Department of Biochemistry, Faculty of Science, Charles University in Prague, Prague 2 128 43, Czech Republic
§ Research Center for Compact Chemical System, National Institute of Advanced Industrial Science and Technology (AIST), Sendai 983-8551, Japan
Chem. Rev., 2015, 115 (13), pp 6491–6533
DOI: 10.1021/acs.chemrev.5b00018
Publication Date (Web): May 29, 2015
 Table of Contents:
  • 1. Introduction
  • 2. Heme-Based O2 Sensors
    • 2.1. Heme-Bound PAS Domain-Containing O2 Sensors
      • 2.1.1. FixL
      • 2.1.2. EcDOS (or EcDosP)
      • 2.1.3. AxPDEA1
      • 2.1.4. Aer2
      • 2.1.5. Gyc-88E
      • 2.1.6. ThkA
    • 2.2. Heme-Bound GAF Domain-Containing O2 Sensors
      • 2.2.1. DosS (or DevS)
      • 2.2.2. DosT
    • 2.3. Heme-Bound Globin Domain-Containing O2 Sensors: Globin-Coupled O2 Sensor (GCS)
      • 2.3.1. HemAT
      • 2.3.2. YddV (or EcDosC)
      • 2.3.3. AfGcHK
      • 2.3.4. HemDGC
      • 2.3.5. AvGReg
      • 2.3.6. BpeGReg
      • 2.3.7. GsGCS
      • 2.3.8. HemAC-Lm
    • 2.4. AppA: Heme Sensor Domain with a Central SCHIC Fold
  • 3. Heme-Based NO Sensors
    • 3.1. The Eukaryotic NO Sensor sGC
      • 3.1.1. Protein Structure
      • 3.1.2. Coordination Structures of the Heme Fe(II) Complex
      • 3.1.3. Catalytic Enhancement of sGC by Chemical Simulators and Activators
    • 3.2. Crystal Structures of the Heme-Bound, NO-Sensing H-NOX Domain of Bacterial NO Sensors: Stand-Alone Type
      • 3.2.1. TtH-NOX
      • 3.2.2. NsH-NOX
      • 3.2.3. SoH-NOX
    • 3.3. Functions of Bacterial NO Sensors
      • 3.3.1. SoH-NOX: Stand-Alone Type
      • 3.3.2. SwH-NOX: Stand-Alone Type
      • 3.3.3. H-NOX from Pseudoalteromonas atlantica: Stand-Alone Type
      • 3.3.4. H-NOX from Vibrio fischeri: Stand-Alone Type
      • 3.3.5. H-NOX in Vibrio harveyi: Stand-Alone Type
      • 3.3.6. DNR: Fused Type
      • 3.3.7. YybT: Fused Type
    • 3.4. Insect E75: Fused Type
    • 3.5. Human Cystathionine β-Synthase: Fused Type
  • 4. Heme-Based CO Sensors
    • 4.1. CooA
    • 4.2. RcoM
    • 4.3. Cystathionine β-Synthase
    • 4.4. BK (Slo1) and Kv1.4 K+ Channels, Nav1.5 Na+ Channel, and Connexin Hemichannels
    • 4.5. NPAS2, CLOCK, Rev-erbα, Rev-erbβ, E75, Per1, and Per2
  • 5. Heme Redox Sensors with c-Type and Non-c-Type Heme Iron Complexes
    • 5.1. MA4561
    • 5.2. GSU582 and GSU935
    • 5.3. DcrA
    • 5.4. NtrY/NtrX
    • 5.5. OxdB
    • 5.6. Insect E75
    • 5.7. EcDOS
  • 6. Heme-Based H2S Sensors
  • 7. Common Characteristics of Heme-Based Gas Sensors
  • 8. Concerns That Need To Be Addressed
  • 9. Perspectives

Solvation Thermodynamics of Organic Molecules by the Molecular Integral Equation Theory: Approaching Chemical Accuracy


Ekaterina L. Ratkova , David S. Palmer §, and Maxim V. Fedorov *
 Chem. Rev., 2015, 115 (13), pp 6312–6356
DOI: 10.1021/cr5000283
Publication Date (Web): June 15, 2015
Table of Contents:
  • 1. Introduction
  • 2. Solvation Thermodynamics: General Concepts
    • 2.1. Solvation Free Energy (SFE) and Its Key Role in Solvation Thermodynamics
      • 2.1.1. SFE and Partition Coefficients
      • 2.1.2. SFE and Association/Dissociation Constants
      • 2.1.3. SFE and Intrinsic Solubility
      • 2.1.4. Enthalpic and Entropic Terms
      • 2.1.5. Free Energy Profiles
    • 2.2. Experimental Methods To Measure SFE
      • 2.2.1. Direct Methods
      • 2.2.2. Indirect Methods
      • 2.2.3. Available Experimental SFE Data
    • 2.3. SFE Calculations: Brief Overview of Main Approaches
      • 2.3.1. “Top Down” Methods: Cheminformatics and QSPR Approaches
      • 2.3.2. “Bottom Up” Methods: Implicit vs Explicit Solvent
  • 3. Integral Equation Theory (IET) of Molecular Liquids
    • 3.1. Ornstein–Zernike (OZ) Equation for Simple Fluids
    • 3.2. Molecular OZ (MOZ) Equation
    • 3.3. Reference Interaction Site Model (RISM): Main Formulas
      • 3.3.1. 1D-RISM
      • 3.3.2. 3D-RISM
  • 4. RISM: Practical Aspects
    • 4.1. Numerical Algorithms for Solving RISM Equations
    • 4.2. Hybridization of RISM with Other Methods (QM and MM)
      • 4.2.1. RISM–QM
      • 4.2.2. RISM–MM
    • 4.3. Examples of RISM Implementation in Molecular Modeling Software
  • 5. Thermodynamic Parameters within RISM
    • 5.1. Partial Molar Volume (PMV) Calculations
    • 5.2. Enthalpy and Entropy of Solvation in 1D- and 3D-RISM
    • 5.3. SFE Functionals: Large Variety of Expressions
      • 5.3.1. End-Point SFE Functionals in 1D-RISM
      • 5.3.2. End-Point SFE Functionals in 3D-RISM
    • 5.4. Semiempirical SFE Functionals
      • 5.4.1. Improvement of SFE Predictions with a Volume Correction
      • 5.4.2. Structural Descriptors Correction (SDC) Functional: Structural Corrections as a Tool to Further Improve SFE Calculations
    • 5.5. Initial State Correction SFE Functionals
  • 6. RISM Coming into Laboratories: Selected Examples of Recent Applications
    • 6.1. Solvation Phenomena at Complex Molecular Interfaces
      • 6.1.1. Mapping of Solvent and Cosolute Binding Sites on the Surface of Biological Macromolecules
      • 6.1.2. Molecule–Surface Recognition and Supramolecular Interactions
    • 6.2. Solvent Effects on Conformational and Configurational Properties of Biomolecules and Their Assemblies
    • 6.3. Analyzing and Predicting Phys-Chem Properties of Molecular Solvation
  • 7. Note on Alternative Distribution-Function Approaches
  • 8. Conclusion

Advances in Colloidal Assembly: The Design of Structure and Hierarchy in Two and Three Dimensions

Chem. Rev., 2015, 115 (13), pp 6265–6311
DOI: 10.1021/cr400081d
Publication Date (Web): June 22, 2015

Table of Contents
  • 1. Introduction
    • 1.1. Building Blocks
    • 1.2. Assembly Forces
      • 1.2.1. Repulsive Forces
      • 1.2.2. Attractive Forces
      • 1.2.3. External Forces
  • 2. 2D Colloidal Assemblies
    • 2.1. Close-Packed Colloidal Monolayers
      • 2.1.1. Direct Assembly Methods
      • 2.1.2. Liquid Interface-Mediated Methods
    • 2.2. Non-Close-Packed Monolayers
    • 2.3. Binary Monolayers
    • 2.4. Two-Dimensional Patterning of Colloidal Crystals
      • 2.4.1. Assembly of Monolayers on Topographically Patterned Substrates
      • 2.4.2. “Colloids on Top of Colloids”
      • 2.4.3. Assembly of Monolayers on Chemically Patterned Surfaces
      • 2.4.4. Patterning without Substrate Engineering
  • 3. 3D Colloidal Assemblies
    • 3.1. 3D Colloidal Crystals on Planar Surfaces and Interfaces
      • 3.1.1. Direct Assembly on Solid Substrates
      • 3.1.2. 3D Colloidal Crystals at Liquid Interfaces
      • 3.1.3. Defects and Cracks in Colloidal Crystals
    • 3.2. Patterning of 3D Colloidal Crystals
      • 3.2.1. Planar Patterned, Topography-Free Substrates
      • 3.2.2. Colloidal Crystals on Topographically Patterned Substrates
      • 3.2.3. 3D Patterning in Templates
    • 3.3. Colloidal Epitaxy
    • 3.4. Non-Close-Packed 3D Colloidal Crystals
  • 4. Conclusion and Outlook

Jul 7, 2015

Imidazolium Cations with Exceptional Alkaline Stability: A Systematic Study of Structure–Stability Relationships

Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.5b02879
Publication Date (Web): June 11, 2015
Copyright © 2015 American Chemical Society


Abstract Image
Highly base-stable cationic moieties are a critical component of anion exchange membranes (AEMs) in alkaline fuel cells (AFCs); however, the commonly employed organic cations have limited alkaline stability. To address this problem, we synthesized and characterized the stability of a series of imidazolium cations in 1, 2, or 5 M KOH/CD3OH at 80 °C, systematically evaluating the impact of substitution on chemical stability. The substituent identity at each position of the imidazolium ring has a dramatic effect on the overall cation stability. We report imidazolium cations that have the highest alkaline stabilities reported to date, >99% cation remaining after 30 days in 5 M KOH/CD3OH at 80 °C.

Proton-Coupled Electron Transfer: Moving Together and Charging Forward

Department of Chemistry, University of Illinois at Urbana−Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801, United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.5b04087
Publication Date (Web): June 25, 2015
Copyright © 2015 American Chemical Society


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Proton-coupled electron transfer (PCET) is ubiquitous throughout chemistry and biology. This Perspective discusses recent advances and current challenges in the field of PCET, with an emphasis on the role of theory and computation. The fundamental theoretical concepts are summarized, and expressions for rate constants and kinetic isotope effects are provided. Computational methods for calculating reduction potentials and pKa’s for molecular electrocatalysts, as well as insights into linear correlations and non-innocent ligands, are also described. In addition, computational methods for simulating the nonadiabatic dynamics of photoexcited PCET are discussed. Representative applications to PCET in solution, proteins, electrochemistry, and photoinduced processes are presented, highlighting the interplay between theoretical and experimental studies. The current challenges and suggested future directions are outlined for each type of application, concluding with an overall view to the future.

Jul 2, 2015

Ultra-small Palladium Nanoparticle Decorated Carbon Nanotubes: Conductivity and Reactivity

Xiuting Li, Dr. Christopher Batchelor-McAuley, Dr. Kristina Tschulik, Prof. Dr. Lidong Shao and Prof. Dr. Richard G. Compton
Article first published online: 10 JUN 2015 | DOI: 10.1002/cphc.201500404
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Small but mighty: Individual multiwalled carbon nanotubes decorated with ultra-small palladium nanoparticles are detected by using the nano-impacts method through studying the proton-reduction reaction for the underpotential deposition of hydrogen on palladium nanoparticles. The high conductivity and reactivity of the decorated carbon nanotubes is directly evidenced.

Jul 1, 2015

Highly Active, Nonprecious Metal Perovskite Electrocatalysts for Bifunctional Metal–Air Battery Electrodes


 Highly Active, Nonprecious Metal Perovskite Electrocatalysts for Bifunctional Metal–Air Battery Electrodes

Department of Chemical Engineering (1 University Station C0400), Department of Chemistry and Biochemistry (1 University Station A5300), §Center for Electrochemistry, and Texas Materials Institute, The University of Texas at Austin, Austin, Texas 78712, United States
# Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
J. Phys. Chem. Lett., 2013, 4 (8), pp 1254–1259
DOI: 10.1021/jz400595z
Publication Date (Web): March 27, 2013
Copyright © 2013 American Chemical Society
*E-mail: stevenson@cm.utexas.edu (K.J.S.); kpj@che.utexas.edu (K.P.J.).


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Perovskites are of great interest as replacements for precious metals and oxides used in bifunctional air electrodes involving the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, we report the synthesis and activity of a phase-pure nanocrystal perovskite catalyst that is highly active for the OER and ORR. The OER mass activity of LaNiO3, synthesized by the calcination of a rapidly dried nanoparticle dispersion and supported on nitrogen-doped carbon, is demonstrated to be nearly 3-fold that of 6 nm IrO2 and exhibits no hysteresis during oxygen evolution. Moreover, strong OER/ORR bifunctionality is shown by the low total overpotential (1.02 V) between the reactions, on par or better than that of noble metal catalysts such as Pt (1.16 V) and Ir (0.92 V). These results are examined in the context of surface hydroxylation, and a new OER cycle is proposed that unifies theory and the unique surface properties of LaNiO3.

Jun 26, 2015

Ultrafast Transient Absorption Study of the Nature of Interaction between Oppositely Charged Photoexcited CdTe Quantum Dots and Cresyl Violet

Ultrafast Transient Absorption Study of the Nature of Interaction between Oppositely Charged Photoexcited CdTe Quantum Dots and Cresyl Violet by M. Chandra Sekhar and Anunay Samanta via The Journal of Physical Chemistry C: Latest Articles (ACS Publications) http://ift.tt/1J2QAcM http://pubs.acs.org