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Surfaces and Interfaces

Self-ordered surface wrinkling patternsInterfaces and surfaces are where the action happens. Catalysis, molecular recognition, charge transfer, polymerization and many other critical processes take place at the boundary between one medium and another. With the need to integrate new materials into devices, and applications ranging from catalysis to sensors, medicine to self-cleaning surfaces, and displays to lasers, fundamental and applied studies of surface and interface processes and optimization are of critical importance in developing new technology to meet today's challenges. The selection of recent research articles presented below illustrates the vast potential of this field.

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Recent Articles

Nataliya Kalashnyk, Praveen Ganesh Nagaswaran, Simon Kervyn, Massimo Riello, Ben Moreton, Tim S. Jones, Alessandro De Vita, Davide Bonifazi, Giovanni Costantini
Self-Assembly of Decoupled Borazines on Metal Surfaces: The Role of the Peripheral Groups [Full Paper]

Self-Assembly of Decoupled Borazines on Metal Surfaces: The Role of the Peripheral Groups

On the surface: The influence of lateral groups on the self-assembly of two borazine derivatives on metal substrates is studied by scanning tunnelling microscopy and theoretical simulations (see figure). Although the precisely targeted strategy adopted in the synthesis of the two borazines ensures a very effective decoupling of the central BN core for both molecules, the molecule-substrate interaction is observed to depend on the length and flexibility of the peripheral substituents and on the reactivity of the surface.

Chem. Eur. J. 2014, 20, No. 37, 11856-11862

Lirong Xu, Xin Zhou, Wei Quan Tian, Teng Gao, Yan Feng Zhang, Shengbin Lei, Zhong Fan Liu
Surface-Confined Single-Layer Covalent Organic Framework on Single-Layer Graphene Grown on Copper Foil [Communication]

Surface-Confined Single-Layer Covalent Organic Framework on Single-Layer Graphene Grown on Copper Foil

Co-condensation between benzene-1,3,5-tricarbaldehyde and p-phenylenediamine on a graphene surface leads to a surface covalent organic framework (COF) with single-layer thickness. Strong coupling between the surface COF and graphene was confirmed by the significant mixing of states and the relatively large interaction energy revealed by STM and DFT simulation.

Angew. Chem. Int. Ed. 2014, 53, No. 36, 9564-9568

Rüdiger Scheu, Blake M. Rankin, Yixing Chen, Kailash C. Jena, Dor Ben-Amotz, Sylvie Roke
Charge Asymmetry at Aqueous Hydrophobic Interfaces and Hydration Shells [Communication]

Charge Asymmetry at Aqueous Hydrophobic Interfaces and Hydration Shells

Guilty as charged: Water is often modeled as a dielectric continuum, but the molecular structure of water is asymmetric. Two ions that have a virtually identical size, shape, and structure, but an opposite charge sign have been investigated to see whether charge makes a fundamental difference to water structuring. The spectroscopic data for the hydration and interface structures are found to be remarkably different for opposite charges.

Angew. Chem. Int. Ed. 2014, 53, No. 36, 9560-9563

Si Yu Tan, Chung Yen Ang, Peizhou Li, Qi Ming Yap, Yanli Zhao
Drug Encapsulation and Release by Mesoporous Silica Nanoparticles: The Effect of Surface Functional Groups [Communication]

Drug Encapsulation and Release by Mesoporous Silica Nanoparticles: The Effect of Surface Functional Groups

Maximizing drug release from drug carriers is important to achieve better therapeutic efficiency. Using glutathione (GSH)-triggered drug-release systems as a case study, the effect of the nature of surface functional groups on mesoporous silica nanoparticles on drug-loading and drug-release capabilities was investigated.

Chem. Eur. J. 2014, 20, No. 36, 11276-11282

Chemoselective Phototransformation of C-H Bonds on a Polymer Surface through a Photoinduced Cerium Recycling Redox Reaction

Recycling itself! A bio-inspired artificial recycling reaction system has been constructed based on the strategic design of a photoinduced Ce3+–Ce4+ recycling redox reaction, leading to efficient photorecovery of reactants to achieve a reactant-loss-free direct transformation of alkyl C-H bonds on polymer surfaces to form small-molecule groups and polymer brushes (see scheme).

Chem. Eur. J. 2014, 20, No. 36, 11421-11427

Olaf Nachtigall, Christian Kördel, Leonhard H. Urner, Rainer Haag
Photoresponsive Switches at Surfaces Based on Supramolecular Functionalization with Azobenzene–Oligoglycerol Conjugates [Communication]

Photoresponsive Switches at Surfaces Based on Supramolecular Functionalization with Azobenzene–Oligoglycerol Conjugates

The thermal and light-induced photoisomerization of bifunctional azobenzene–oligoglycerol conjugates was examined in solution and on supramolecularly functionalized gold nanoparticles and planar gold surfaces. The wettability of the functionalized gold surfaces could be reversibly switched with light. Thermal half-lives of Z-isomers were determined for different environments to provide information about the stability of the functional switches for further applications.

Angew. Chem. Int. Ed. 2014, 53, No. 36, 9669-9673

Amphiphilic Janus Gold Nanoparticles Prepared by Interface-Directed Self-Assembly: Synthesis and Self-Assembly

Two-faced: Polystyrene colloidal particles with gold nanoparticles (AuNPs) on the surfaces were prepared by self-assembly of AuNPs. The colloidal particles were used as templates for the synthesis of Janus AuNPs. After surface-initiated atom-transfer radical polymerization (ATRP; see picture), Janus AuNPs with two different polymer brushes on two hemispheres were obtained.

Chem. Asian J. 2014, 9, No. 09, 2597-2603

Verónica Montes-García, Jorge Pérez-Juste, Isabel Pastoriza-Santos, Luis M. Liz-Marzán
Metal Nanoparticles and Supramolecular Macrocycles: A Tale of Synergy [Minireview]

Metal Nanoparticles and Supramolecular Macrocycles: A Tale of Synergy

Nanoparticles and macrocycles: Recent literature regarding the combination of supramolecular macrocycles and metal nanoparticles is reviewed, with particular emphasis on the synthesis, surface modification and assembly, as well as the potential applications of the obtained nanocomposites (SERS = surface-enhanced Raman spectroscopy).

Chem. Eur. J. 2014, 20, No. 35, 10874-10883

Artem Kovalenko, Prasad Polavarapu, Jean-Louis Gallani, Geneviève Pourroy, Gilles Waton, Marie Pierre Krafft
Super-Elastic Air/Water Interfacial Films Self-Assembled from Soluble Surfactants [Communication]

Super-Elastic Air/Water Interfacial Films Self-Assembled from Soluble Surfactants

Second skin: In spite of being water-soluble, monosodic salts of (perfluoroalkyl)alkyl phosphates self-assemble at the surface of water into Gibbs films that display exceptional elasticity (∼900 mN m−1) in their condensed phases.

ChemPhysChem 2014, 15, No. 12, 2440-2444

Carbon Monoxide-Induced Dynamic Metal-Surface Nanostructuring

Nanoparticles and reactive surfaces: This Minireview provides an overview of selected CO-induced nanostructuring (see scheme). Recent examples of metal-surface and nanoparticle restructuring as a consequence of exposure to CO are discussed and show that nanoscale structures can be obtained under fairly mild conditions. Several cases of mono- and bimetallic compounds are described that show a range of behaviours in relation with the metal–CO interaction strength.

Chem. Eur. J. 2014, 20, No. 34, 10616-10625

Davide Vione, Marco Minella, Valter Maurino, Claudio Minero
Indirect Photochemistry in Sunlit Surface Waters: Photoinduced Production of Reactive Transient Species [Review]

Indirect Photochemistry in Sunlit Surface Waters: Photoinduced Production of Reactive Transient Species

Shine a light on your chemistry! This paper gives an overview of the reactive transient species that are produced in surface waters by sunlight irradiation of photoactive molecules (photosensitizers), such as nitrate, nitrite, and chromophoric dissolved organic matter (CDOM) (see scheme). The main transient species (.OH, CO3−., 1O2, and CDOM triplet states) are involved in the indirect phototransformation of a very wide range of organic pollutants in surface waters.

Chem. Eur. J. 2014, 20, No. 34, 10590-10606

Rutger A. van Santen
Catalytic Paradigms: A Riddle and a Puzzle [Essay]

Control of Solid Catalysts Down to the Atomic Scale: Where is the Limit?

Down to the last detail: Nanostructured solid catalysts were already known in the early 20th century, but their exact structure was unclear. Nowadays, the arrangement of atoms and particles in solids can be manipulated and analyzed down to the atomic scale (see image). The use of specific highly active catalysts enables industrially relevant reactions to be performed at room temperature.

Angew. Chem. Int. Ed. 2014, 53, No. 33, 8599-8604

Yudie Sun, Honglin Liu, Fei Zhou, Liangbao Yang, Shengnan He, Bai Sun, Jinhuai Liu
Unravelling the Relationship between Raman Enhancement and Photocatalytic Activity on Single Anisotropic Au Microplates [Full Paper]

Unravelling the Relationship between Raman Enhancement and Photocatalytic Activity on Single Anisotropic Au Microplates

Profiling characteristics: Anisotropic spatial distribution of Raman enhancement and photocatalytic activity is presented for the first time at the level of single nanometer-thin gold microplates (see figure). Our strategy excludes, to a certain extent, concentration effects and chemical contributions in noble-metal photocatalysis, thus illustrating plasmon-enhanced characteristics.

Chem. Eur. J. 2014, 20, No. 33, 10414-10424

Breakthroughs in Hard X-ray Diffraction: Towards a Multiscale Science Approach in Heterogeneous Catalysis

Diffraction at hard work: Modern heterogeneous catalysis would benefit from a multiscale science approach bridging the molecular world with the macroscopic world. Because of recent breakthroughs in X-ray diffraction methods, including the surface X-ray diffraction of atomically flat model catalysts, X-ray diffraction tomography of catalyst bodies, and X-ray profiling of an active catalyst in a chemical reactor, such an approach is now within reach.

Angew. Chem. Int. Ed. 2014, 53, No. 33, 8556-8558

Victor Malgras, Priyanka Jood, Ziqi Sun, Shi Xue Dou, Yusuke Yamauchi, Jung Ho Kim
Channelled Porous TiO2 Synthesized with a Water-in-Oil Microemulsion [Full Paper]

Channelled Porous TiO2 Synthesized with a Water-in-Oil Microemulsion

Porous materials with stacked conical channels were synthesized by a water-in-oil microemulsion based on water/dioctyl sodium sulfoccinate (AOT) and a lecithin/isooctane template. The active surface area can be modified by alkoxide precursor concentration, and oil phase viscosity widens the pore aperture, decreasing the active surface area. Changing the phase proportions alters the microemulsion integrity and disrupts channel formation.

Chem. Eur. J. 2014, 20, No. 33, 10451-10455

María José Heras-Ojea, Daniel Reta Mañeru, Lidia Rosado, Juan Rubio Zuazo, German R. Castro, Subrata Tewary, Gopalan Rajaraman, Guillem Aromí, Erika Jiménez, E. Carolina Sañudo
Characterization of a Robust CoII Fluorescent Complex Deposited Intact On HOPG [Full Paper]

Characterization of a Robust CoII Fluorescent Complex Deposited Intact On HOPG

Molecules intact on surfaces: The new fluorescent ligand ACRI-1 is reported along with its coordination complex [Co2(ACRI-1)2] (1), a fluorescent weak ferromagnet. Complex 1 has been deposited on highly ordered pyrolitic graphite (HOGP) from solution. The prepared thin films have been characterized and the data show that the complex is robust and remains intact on the surface of graphite (see figure).

Chem. Eur. J. 2014, 20, No. 33, 10439-10445

Zhi-Gang Gu, Jochen Bürck, Angela Bihlmeier, Jinxuan Liu, Osama Shekhah, Peter G. Weidler, Carlos Azucena, Zhengbang Wang, Stefan Heissler, Hartmut Gliemann, Wim Klopper, Anne S. Ulrich, Christof Wöll
Oriented Circular Dichroism Analysis of Chiral Surface-Anchored Metal–Organic Frameworks Grown by Liquid-Phase Epitaxy and upon Loading with Chiral Guest Compounds [Communication]

Oriented Circular Dichroism Analysis of Chiral Surface-Anchored Metal–Organic Frameworks Grown by Liquid-Phase Epitaxy and upon Loading with Chiral Guest Compounds

Oriented circular dichroism (OCD) is used to conveniently determine the alignment of α-helical peptides in oriented lipid bilayers. Here, OCD is applied in an analogous way to investigate oriented chiral surface-anchored metal–organic frameworks (SURMOFs). It reveals both the orientation of the chiral linkers of the enantiopure host lattice and the quantitative loading ratio of enantiomeric guest molecules that are offered as a racemic mixture.

Chem. Eur. J. 2014, 20, No. 32, 9879-9882

Jianlei Shen, Lifeng Xu, Chunpeng Wang, Hao Pei, Renzhong Tai, Shiping Song, Qing Huang, Chunhai Fan, Gang Chen
Dynamic and Quantitative Control of the DNA-Mediated Growth of Gold Plasmonic Nanostructures [Communication]

Dynamic and Quantitative Control of the DNA-Mediated Growth of Gold Plasmonic Nanostructures

A heart of gold: A quantitative approach to intercept the evolution of size, surface morphology, and the optical properties of Au plasmonic nanostructures is demonstrated by dynamic control of the DNA-mediated growth. The structural parameters of these nanostructures correlate well with their optical properties, obtained from small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM).

Angew. Chem. Int. Ed. 2014, 53, No. 32, 8338-8342

Tanchen Ren, Zhengwei Mao, Sergio Enrique Moya, Changyou Gao
Immobilization of Enzymes on 2-Hydroxyethyl Methacrylate and Glycidyl Methacrylate Copolymer Brushes [Full Paper]

Immobilization of Enzymes on 2-Hydroxyethyl Methacrylate and Glycidyl Methacrylate Copolymer Brushes

Brushwork: Poly(2-hydroxyethyl methacrylate)-block-poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) (PHEMA-block-P (HEMA-co-GMA)) block copolymer brushes were prepared. The density of the polymer brushes and length of the blocks, as well as the subsequent enzyme-immobilization ability was easily tuned. The stability of lysozymes was largely enhanced after being immobilized on the brushes, which retained 64 % of the enzyme activity after storage at 4 °C for 30 days.

Chem. Asian J. 2014, 9, No. 08, 2132-2139

Recent Progress in Biointerfaces with Controlled Bacterial Adhesion by Using Chemical and Physical Methods

Stick or twist: Recent progress in biointerfaces based on smart-responsive molecules or surface topographies has led to efficient approaches for controlling the adhesive behavior of bacteria.

Chem. Asian J. 2014, 9, No. 08, 2004-2016

Jinhye Bae, Thomas P. Russell, Ryan C. Hayward
Osmotically Driven Formation of Double Emulsions Stabilized by Amphiphilic Block Copolymers [Communication]

Osmotically Driven Formation of Double Emulsions Stabilized by Amphiphilic Block Copolymers

Water-in-oil-in-water (w/o/w) double emulsions are spontaneously generated from o/w single emulsions by the osmotic pressure provided by salt species initially dispersed in the oil phase. This phenomenon provides a simple route to tailor block copolymer self-assembly, yielding multi-vesicular structures and hierarchically structured porous films after solvent evaporation.

Angew. Chem. Int. Ed. 2014, 53, No. 31, 8240-8245

Christin Büchner, Leonid Lichtenstein, Xin Yu, J. Anibal Boscoboinik, Bing Yang, William E. Kaden, Markus Heyde, Shamil K. Shaikhutdinov, Radosław Włodarczyk, Marek Sierka, Joachim Sauer, Hans-Joachim Freund
Ultrathin Silica Films: The Atomic Structure of Two-Dimensional Crystals and Glasses [Minireview]

Ultrathin Silica Films: The Atomic Structure of Two-Dimensional Crystals and Glasses

Polishing up the crystal glasses: An overview of the preparation and characterization of ordered silica films on metal supports is reported. In particular, the specific case of a silica bilayer, which exists in a crystalline and a vitreous variety, is discussed and a model of the vitreous silica structure proposed by William Zachariasen in 1932 is verified. Beyond this, the possibility to prepare the crystalline and the glassy structure on the same support leads to the study of the crystal–glass phase transition in real space (see figure).

Chem. Eur. J. 2014, 20, No. 30, 9176-9183

Barry Arkles, Youlin Pan, Gerald L. Larson, Mani Singh
Enhanced Hydrolytic Stability of Siliceous Surfaces Modified with Pendant Dipodal Silanes [Full Paper]

Enhanced Hydrolytic Stability of Siliceous Surfaces Modified with Pendant Dipodal Silanes

Two feet are better than one! Nonfunctional and functional dipodal silanes with structures containing “pendant” rather than “bridged” organofunctionality were synthesized. Surfaces modified with pendant dipodal silanes were found to be more resistant to hydrolysis than the bridged structure with single-carbon separated (disilapropyl)silanes, demonstrating the greatest resistance to hydrolysis and best stability (see figure).

Chem. Eur. J. 2014, 20, No. 30, 9442-9450

Gary A. Attard, Ashley Brew, Jin-Yu Ye, David Morgan, Shi-Gang Sun
Oxygen Reduction Reaction Activity on Pt{111} Surface Alloys [Article]

Oxygen Reduction Reaction Activity on Pt{111} Surface Alloys

PtM overlayers (M=Fe, Co or Ni) supported on a Pt{111} electrode are prepared via thermal annealing of aqueous droplets containing MZ+ cations directly attached to the electrode. When a hydrogen ambient is used for thermal annealing, highly active oxygen reduction electrocatalysts are formed. A positive potential shift in PtM oxide formation is seen compared to Pt{111}, which correlates with increased oxygen reduction reaction activity.

ChemPhysChem 2014, 15, No. 10, 2044-2051

Nicolas Dupré, Marine Cuisinier, Jean-Frederic Martin, Dominique Guyomard
Interphase Evolution at Two Promising Electrode Materials for Li-Ion Batteries: LiFePO4 and LiNi1/2Mn1/2O2 [Review]

Interphase Evolution at Two Promising Electrode Materials for Li-Ion Batteries: LiFePO4 and LiNi1/2Mn1/2O2

The importance of the chemical history of the electrode surface before electrochemical cycling as well as the correlation between interface phenomena, the formation/evolution of an interphase, and the electrochemical behavior of LiFePO4 and LiNi1/2Mn1/2O2 electrodes are investigated by magic-angle-spinning nuclear magnetic resonance, electron energy loss spectroscopy, and X-ray photoelectron spectroscopy. These techniques allow the study of interface aging and failure mechanisms.

ChemPhysChem 2014, 15, No. 10, 1922-1938

Joseph S. DuChene, Brendan C. Sweeny, Aaron C. Johnston-Peck, Dong Su, Eric A. Stach, Wei David Wei
Prolonged Hot Electron Dynamics in Plasmonic-Metal/Semiconductor Heterostructures with Implications for Solar Photocatalysis [Communication]

Prolonged Hot Electron Dynamics in Plasmonic-Metal/Semiconductor Heterostructures with Implications for Solar Photocatalysis

Harvesting hot electrons: Plasmon-mediated electron transfer (PMET) in plasmonic (Au/TiO2) photoanodes provides a unique pathway for procuring excited-state electrons that exhibit lifetimes commensurate with the prolonged timescales required for solar photochemistry. These long-lived electrons were harnessed for visible-light-driven hydrogen evolution from water (see picture).

Angew. Chem. Int. Ed. 2014, 53, No. 30, 7887-7891

Josephine Selvaraj, Satyajit Gupta, Steven DelaCruz, Vaidyanathan (Ravi) Subramanian
Role of Reduced Graphene Oxide in the Critical Components of a CdS-Sensitized TiO2-Based Photoelectrochemical Cell [Article]

Role of Reduced Graphene Oxide in the Critical Components of a CdS-Sensitized TiO2-Based Photoelectrochemical Cell

Top of the PECs: N-doped reduced graphene oxide (nRGO) is systematically incorporated into the photoanode, cathode, and redox electrolyte of a photoelectrochemical cell and was shown to favorably influence the cell performance.

ChemPhysChem 2014, 15, No. 10, 2010-2018

Charles Peureux, Viatcheslav Jouikov
Covalent Grafting of Silatranes to Carbon Interfaces [Full Paper]

Covalent Grafting of Silatranes to Carbon Interfaces

Organosilicon electrodes were prepared by silatrane Si-C grafting to a glassy carbon interface to give a benzyl-like system in which a 3 c–4 e orbital is conjugated to the macroscopic π-type substituent (graphite Csp2 network). This process allows one to build carbon-based conducting interfaces with electronically conjugated molecular extensions. Grafting of alkyl silatrane provides stable functional interfaces enabling electrochemical spin-writing.

Chem. Eur. J. 2014, 20, No. 30, 9290-9294

Mrinal K. Bera, Travis H. Bray, Ross J. Ellis, Mark R. Antonio
Redox Chemistry of Heteropolyacid Microemulsions [Article]

Redox Chemistry of Heteropolyacid Microemulsions

Face-POM: Three-phase-electrode electrochemistry of polyoxometalate third phases formed by solvent extraction and dissolution of heteropolyacid salts, including 12-phosphotungstic acid (H3PT), by using paraffinic solutions of tri-n-butyl phosphate (TBP) reveal redox events that are markedly shifted and less resolved than the responses in the corresponding aqueous electrolytes due to solubilization of the charge-neutral acids.

ChemElectroChem 2014, 1, No. 07, 1173-1181

Guillaume Durand, Samuele Lisi, Corinne Ravelet, Eric Dausse, Eric Peyrin, Jean-Jacques Toulmé
Riboswitches Based on Kissing Complexes for the Detection of Small Ligands [Communication]

Riboswitches Based on Kissing Complexes for the Detection of Small Ligands

Switch and kiss: Hairpin aptamers (gray) were engineered to switch between unfolded and folded conformations upon binding to their cognate ligand (orange). The folded conformation but not the unfolded one is recognized by a second hairpin termed the aptakiss (yellow) through loop–loop or kissing interactions (red). The detection of the aptakiss–aptamer–ligand ternary complex by SPR or fluorescence anisotropy signals the presence of the target ligand.

Angew. Chem. Int. Ed. 2014, 53, No. 27, 6942-6945

J. Xue, P. T. Lee, R. G. Compton
Electrochemical Detection of Melamine [Full Paper]

Sidharam P. Pujari, Luc Scheres, Antonius T. M. Marcelis, Han Zuilhof
Covalent Surface Modification of Oxide Surfaces [Review]

Covalent Surface Modification of Oxide Surfaces

Not just scratching the surface: Covalently attached monolayers on oxide surfaces are reviewed with an eye to improved robustness, increased functionalization, understanding structural details, and the resulting potential for applications. Such monolayers, provided they are robust enough, provide a way of improving the properties of the bulk oxide material.

Angew. Chem. Int. Ed. 2014, 53, No. 25, 6322-6356

Yanxi Zhang, Zhiyuan Zhao, Davide Fracasso, Ryan C. Chiechi
Bottom-Up Molecular Tunneling Junctions Formed by Self-Assembly [Review]

Surface-Enhanced Raman Spectroscopy: Concepts and Chemical Applications

Expanding vibrational spectroscopy: Since its first observation in 1973, surface-enhanced Raman scattering (SERS) has developed into a mature vibrational spectroscopic technique. The number of applications in chemistry as well as the material and life sciences is increasing rapidly. This Review summarizes the key concepts behind SERS and provides an overview of current applications in chemistry.

Angew. Chem. Int. Ed. 2014, 53, No. 19, 4756-4795

Patricio Ramirez, Javier Cervera, Mubarak Ali, Wolfgang Ensinger, Salvador Mafe
Logic Functions with Stimuli-Responsive Single Nanopores [Concept]

Logic Functions with Stimuli-Responsive Single Nanopores

Porefection: Electrochemical transducers based on single stimuli-responsive polymeric nanopores can support a complete set of logic functions. Thermal, chemical, electrical, and optical stimuli are the input signals required to externally tune the pore conductance (i.e. the logical output).

ChemElectroChem 2014, 1, No. 04, 698-705

Erik M. J. Johansson, Rebecka Lindblad, Hans Siegbahn, Anders Hagfeldt, Håkan Rensmo
Atomic and Electronic Structures of Interfaces in Dye-Sensitized, Nanostructured Solar Cells [Review]

Atomic and Electronic Structures of Interfaces in Dye-Sensitized, Nanostructured Solar Cells

Core of the matter: Key processes in nanostructured dye-sensitized solar cells (DSC) occur at material interfaces containing, for example, oxides, dye molecules, and hole conductors (see picture). The implementation of X-ray-based spectroscopic methods for atomic-level understanding of such properties is reviewed. Examples include energy matching, binding configurations, and molecular orbital composition.

ChemPhysChem 2014, 15, No. 06, 1006-1017

Steven E. F. Kleijn, Stanley C. S. Lai, Marc T. M. Koper, Patrick R. Unwin
Electrochemistry of Nanoparticles [Review]

Electrochemistry of Nanoparticles

Revealing electrochemistry: Key issues related to the electrochemistry of nanoparticles are being uncovered through innovative techniques capable of relating activity and structure, ultimately at the level of a single nanoparticle. Recent advances in experimental approaches are discussed and assessed, with particular emphasis on those that enhance the fundamental understanding of electrocatalysis and nanoscale electrochemistry.

Angew. Chem. Int. Ed. 2014, 53, No. 14, 3558-3586

Lu Han, Tetsu Ohsuna, Zheng Liu, Viveka Alfredsson, Tomas Kjellman, Shunsuke Asahina, Mitsuo Suga, Yanhang Ma, Peter Oleynikov, Keiichi Miyasaka, Alvaro Mayoral, Isabel Díaz, Yasuhiro Sakamoto, Sam M. Stevens, Michael W. Anderson, Changhong Xiao, Nobuhisa Fujita, Alfonso Garcia-Bennett, Kyung Byung Yoon, Shunai Che, Osamu Terasaki
Structures of Silica-Based Nanoporous Materials Revealed by Microscopy [Review]

Kota Shiba, Motohiro Tagaya, Sadaki Samitsu, Satoshi Motozuka
Effective Surface Functionalization of Carbon Fibers for Fiber/Polymer Composites with Tailor-Made Interfaces [Minireview]

Effective Surface Functionalization of Carbon Fibers for Fiber/Polymer Composites with Tailor-Made Interfaces

High in fiber: Carbon fibers (CFs), which are widely utilized in fields ranging from fundamental research to industry, can be functionalized by both thin-layer coating and nanoparticle immobilization (see scheme). In this Minireview, these techniques and some practical applications of functionalized CFs, such as carbon fiber reinforced plastic (CFRP), are overviewed after briefly describing the basic properties of CFs.

ChemPlusChem 2014, 79, No. 02, 197-210

Towards Design Rules for Covalent Nanostructures on Metal Surfaces

Rational design at the nanoscale: Covalent assembly of molecular building blocks is a promising strategy to obtain functional nanostructures in one and two dimensions. This Concept article discusses how computational modeling could be used to obtain design rules that will advance this field towards the predictive design of specific functionalities on specific surfaces (see figure).

Chem. Eur. J. 2014, 20, No. 04, 928-934

Anna Maria Coclite, Rachel M. Howden, David C. Borrelli, Christy D. Petruczok, Rong Yang, Jose Luis Yagüe, Asli Ugur, Nan Chen, Sunghwan Lee, Won Jun Jo, Andong Liu, Xiaoxue Wang, Karen K. Gleason
">25th Anniversary Article: CVD Polymers: A New Paradigm for Surface Modifi cation and Device Fabrication [Review]

25th Anniversary Article: CVD Polymers: A New Paradigm for Surface Modifi cation and Device Fabrication

The deposition of functional polymers from the vapor phase enables new frontiers for device fabrication and technological development. Chemical vapor deposition (CVD) methods have a marked footprint in a wide range of applications from biotechnology to conducting polymers for solar cells. Finally, CVD process implementation to an industrial scale and commercialization are also discussed.

">Adv. Mater. 2013, 25, No. 38, 5392-5423

Mark R. Langille, Michelle L. Personick, Chad A. Mirkin
Plasmon-Mediated Syntheses of Metallic Nanostructures [Review]

Plasmon-Mediated Syntheses of Metallic Nanostructures

Power of the light: Plasmon-mediated synthetic methods are excellent techniques for controlling the growth and final shape of metal nanostructures. These reactions use visible light irradiation and excitation of plasmonic seeds to drive the chemical reduction of metal ions, usually Ag+, by citrate. The underlying physical and chemical factors that influence structural selection are outlined along with some important design considerations for controlling particle shape.

Angew. Chem. Int. Ed. 2013, 52, No. 52, 13910-13940

Single-Molecule Chemical Reactions Tracked at the Atomic-Bond Level

On the right track: Recent advances in noncontact atomic force microscopy (nc-AFM) have enabled the bond-resolved imaging of reaction pathways. In particular, unprecedented insights into complex enediyne cyclization cascades on silver surfaces were gained by single-molecule imaging.

Angew. Chem. Int. Ed. 2013, 52, No. 51, 13521-13523

Where Does It Vibrate? Raman Spectromicroscopy on a Single Molecule

Tip-enhanced Raman spectroscopy combines scanning probe techniques with Raman spectroscopy. Latest developments permit the chemical mapping of individual adsorbed molecules by monitoring molecular vibrations with sub-nanometer resolution. Increased efficiency and reduced photodegradation make this method suitable for studies of adsorbed organic and biomolecules in surface science, catalysis, biochemistry, and related fields.

Angew. Chem. Int. Ed. 2013, 52, No. 43, 11202-11204

Benjamin P. Brown, Loren Picco, Mervyn J. Miles, Charl F. J. Faul
Opportunities in High-Speed Atomic Force Microscopy [Review]

Opportunities in High-Speed Atomic Force Microscopy

Developments in instrumentation for “high-speed AFM” (HSAFM) have been ongoing since the 1990s, and now nanometer resolution imaging and lithography at video rate is readily achievable. This review provides a summary of different approaches to and advances in the development of high-speed AFMs, highlights important discoveries made with new instruments, and discusses new possibilities for HSAFM in materials science.

Small 2013, 9, No. 19, 3201-3211

Cell–Material Interactions Revealed Via Material Techniques of Surface Patterning

Various cellular and extracellular matrix's cues are decoupled via surface patterning to elucidate the role of each factor, such as the effect of cell shape on differentiation of stem cells. The pertinent patterning techniques are introduced. Chemical contrast, surface topography, matrix stiffness, and nanoscaled features of substrate surfaces to regulate cell fate are summarized. The cell geometry cues on cell adhesion and differentiation are highlighted.

Adv. Mater. 2013, 25, No. 37, 5257-5286

Wei Li, Qin Yue, Yonghui Deng, Dongyuan Zhao
Ordered Mesoporous Materials Based on Interfacial Assembly and Engineering [Review]

Ordered Mesoporous Materials Based on Interfacial Assembly and Engineering

The interfaces derived from two phases, including liquid-solid, gas-liquid, liquid-liquid, gas-solid and solid-solid interface, provides a plentiful and crucial space for adsorption, assembly, synthesis and catalysis. In this review, we summarize recent developments in preparing mesoporous materials based on the interfacial assembly and engineering.

Adv. Mater. 2013, 25, No. 37, 5129-5152

Xue-Mei Zhang, Qing-Dao Zeng, Chen Wang
Reversible Phase Transformation at the Solid–Liquid Interface: STM Reveals [Focus Review]

Reversible Phase Transformation at the Solid–Liquid Interface: STM Reveals

Flick of the nanoswitch: STM studies on reversible supramolecular self-assemblies based on H-bonded supramolecular networks, azobenzenes, a triple-decker complex, and guanine and catechol motifs are discussed in this Focus Review. These functional structures can undergo reversible phase transformation when triggered by a suitable external stimulus at the solid–liquid interface, and thus they may be used for fabricating molecular switches and other nanomachines.

Chem. Asian J. 2013, 8, No. 10, 2330-2340

The Registry Index: A Quantitative Measure of Materials' Interfacial Commensurability

Simply sliding: The study of nanoscale tribology offers great potential in the fields of friction, wear, and lubrication. By considering a variety of hexagonal layered materials, including graphene, hexagonal boron nitride, and molybdenum disulfide, it is shown how a simple geometrical parameter, named the “registry index”, can capture the interlayer sliding energy landscape (see picture) as calculated by using advanced electronic structure methods as well as experimentally measured frictional behavior.

ChemPhysChem 2013, 14, No. 11, 2376-2391

Tailoring Cellulose Surfaces by Controlled Polymerization Methods

To expand the utilization of cellulose beyond its traditional uses, it is necessary to modify the surface of the fibers. This paper summarizes the modification of cellulose by controlled polymerization methods such as ATRP, RAFT, ROP, and ROMP. The combination of the excellent properties of cellulose with functional polymers creates new materials of great potential in advanced material applications.

Macromol. Chem. Phys. 2013, 214, No. 14, 1539-1544

X-Ray Photoelectron Spectroscopy for Characterization of Bionanocomposite Functional Materials for Energy-Harvesting Technologies

See beneath the surface! Surface analysis of biologically relevant composites leads to an improved understanding of the chemistry of nanocomposite constituents and the interactions between them (see picture).

ChemPhysChem 2013, 14, No. 10, 2071-2080

Peter Sutter, Eli Sutter
Microscopy of Graphene Growth, Processing, and Properties [Feature Article]

Microscopy of Graphene Growth, Processing, and Properties

Real-time surface microscopy and in situ spectroscopy can provide unique insight into graphene and other 2D materials on metal substrates. The power of in situ microscopy in realizing and probing important functionalities in 2D materials is illustrated by reviewing recent progress in understanding scalable graphene growth on metals, processing by selective chemistry at the graphene/metal interface, and important properties such as band structure, work function, etc.

Adv. Funct. Mater. 2013, 23, No. 20, 2617-2634

Ventsislav K. Valev, Jeremy J. Baumberg, Concita Sibilia, Thierry Verbiest
Chirality and Chiroptical Effects in Plasmonic Nanostructures: Fundamentals, Recent Progress, and Outlook [Progress Report]

Chirality and Chiroptical Effects in Plasmonic Nanostructures: Fundamentals, Recent Progress, and Outlook

Due to the recent development of bottom-up and top-down approaches for material design and fabrication at the nanoscale, giant chiroptical effects have been reported from plasmonic nanostructures. These effects are exhibited both in the linear and in the nonlinear optical regimes and are sensitive to the chirality of nanostructures, the chirality of the experiments and the chirality of light itself.

Adv. Mater. 2013, 25, No. 18, 2517-2534

Weigao Xu, Nannan Mao, Jin Zhang
Graphene: A Platform for Surface-Enhanced Raman Spectroscopy [Review]

Graphene: A Platform for Surface-Enhanced Raman Spectroscopy

Graphene is a unique platform for surface-enhanced Raman spectroscopy (SERS). The multi-role of graphene played in SERS is overviewed, including as a Raman probe, as a substrate, as an additive, and as a building block of a flat surface for SERS. Apart from versatile improvements on SERS performance towards applications, graphene-involved SERS studies are also expected to shed light on the fundamental mechanism of the SERS effect.

Small 2013, 9, No. 08, 1206-1224

David C. Kennedy, Dan Grünstein, Chian-Hui Lai, Peter H. Seeberger
Glycosylated Nanoscale Surfaces: Preparation and Applications in Medicine and Molecular Biology [Concept]

Glycosylated Nanoscale Surfaces: Preparation and Applications in Medicine and Molecular Biology

The sweet spot of nanomedicine: Carbohydrates are key to cellular signalling pathways and major contributors to molecular recognition events at the cell surface. Novel nanomaterials that probe multivalent binding events between carbohydrates and their biological binding partners are driving discovery at this interface (see figure).

Chem. Eur. J. 2013, 19, No. 12, 3794-3800

Erica Ueda, Pavel A. Levkin
Emerging Applications of Superhydrophilic-Superhydrophobic Micropatterns [Progress Report]

Emerging Applications of Superhydrophilic-Superhydrophobic Micropatterns

Creating patterns of extreme wettability on surfaces leads to new functionalities and possibilities in a wide variety of applications. We highlight novel applications of superhydrophilic-superhydrophobic patterned surfaces that are currently being explored, from miniaturized cell and chemical screening platforms to surface tension confined microchannels for separation and diagnostic devices, and give an outlook on the progress in this field.

Adv. Mater. 2013, 25, No. 09, 1234-1247

Engineering Hierarchical Nanostructures by Elastocapillary Self-Assembly

New insights in capillary interactions between nanofilaments have led to versatile and scalable methods to build complex structures that cannot be achieved by any other processing technique. Understanding the control of this process is conducive to the development of high-performance battery and capacitor electrodes as well as photovoltaics, electrical interconnects, and other smart materials.

Angew. Chem. Int. Ed. 2013, 52, No. 09, 2412-2425

Jose Luis Yagüe, Anna Maria Coclite, Christy Petruczok, Karen K. Gleason
Chemical Vapor Deposition for Solvent-Free Polymerization at Surfaces [Talents & Trends]

Josep Sedó, Javier Saiz-Poseu, Felix Busqué, Daniel Ruiz-Molina
Catechol-Based Biomimetic Functional Materials [Review]

Catechol-Based Biomimetic Functional Materials

Catechols participate in several natural processes and functions that range from the adhesive properties of marine organisms to the storage of certain metals ions. Accordingly, many scientists worldwide have been studying and mimicking these natural systems to develop new active materials and coatings. A detailed revision of a wide variety of relevant studies in this field is discussed in this Review.

Adv. Mater. 2013, 25, No. 05, 653-701

Xiaoli Liu, Yajun Xu, Zhaoqiang Wu, Hong Chen
Poly(N-vinylpyrrolidone)-Modified Surfaces for Biomedical Applications [Review]

Poly(N-vinylpyrrolidone)-Modified Surfaces for Biomedical Applications

In this review, a brief introduction to surface modification using poly(N-vinylpyrrolidone) and its copolymers and their potential biomedical applications is presented. Some perspectives on future research in the areas are also discussed.

Macromol. Biosci. 2013, 13, No. 02, 147-154

Francesco Zerbetto
Reverse Engineering of Monolayers and Nanopatterns [Research News]

Reverse Engineering of Monolayers and Nanopatterns

In a molecularly decorated surface, the molecular tiles are “glued” to the surface by binding constants and possibly further “glued” to each other by cooperativity factors. At odds with mosaics, these “glues” come with the tiles and cannot be removed or supplemented. Binding polynomials quantify glue amounts from experimental data and may predict molecular self-organization on surfaces that can be exploited in organic (opto-)electronics.

Adv. Mater. 2013, 25, No. 03, 449-455

Self-Assembled Monolayers with Dynamicity Stemming from (Bio)Chemical Conversions: From Construction to Application

Dynamic surfaces: Construction and applications of dynamic surfaces on which surface properties can be modulated by an external stimulus on user demand are reviewed, with focus on self-assembled monolayers with dynamicity that stems from (bio)chemical conversions on the surface in response to stimuli such as electrical potential, light, enzymes, and pH (see picture).

ChemPhysChem 2013, 14, No. 01, 55-69

Metal-Supported Aluminosilicate Ultrathin Films as a Versatile Tool for Studying the Surface Chemistry of Zeolites

Monolayer zeolite? The application of a variety of “surface-science” techniques to elucidate the surface structures and mechanisms of chemical reactions at zeolite surfaces has long been considered as almost impossible. The growth of a thin aluminosilicate film on a metal single crystal under controlled conditions results in adequate and well-defined model systems for zeolite surfaces.

ChemPhysChem 2013, 14, No. 01, 71-77

Small but Strong Lessons from Chemistry for Nanoscience

In a different light: In a provocative look at nanoscience, Nobel Laureate Roald Hoffmann considers the structural and electronic perplexities of dimensionality, the consequences of bond severance in nano-object formation, the implications of simple acid-base chemistry for stabilization of nanostructures, and what lessons might be learned from surface science on structural relaxation and reconstruction.

Angew. Chem. Int. Ed. 2013, 52, No. 01, 93-103

Michèle Vignes-Adler
The Fizzling Foam of Champagne [Essay]

The Fizzling Foam of Champagne

Bubble, bubble: Why does champagne bubble? Why does it stop bubbling? Does the vintage affect its fizz? Chemistry can answer these and other questions about the wine that is so often associated with celebrations and anniversaries.

Angew. Chem. Int. Ed. 2013, 52, No. 01, 187-190

Molecules at Surfaces: 100 Years of Physical Chemistry in Berlin-Dahlem

Scratching the surface: For over 100 years the interactions of molecules at surfaces have been studied at the Fritz Haber Institute of the Max Planck Society, Berlin. Nobel Laureate Gerhard Ertl looks back at some of the key developments in this time, and the people who made them.

Angew. Chem. Int. Ed. 2013, 52, No. 01, 52-60

© Wiley-VCH 2013.