Center for NanoScience

Rising atmospheric levels of carbon dioxide and the depletion of fossil fuel reserves raise serious concerns about the ensuing effects on the global climate and future energy supply. Utilizing the abundant solar energy to convert CO2 into fuels such as methane or methanol could address both problems simultaneously as well as provide a convenient means of energy storage. In this Review, current approaches for the heterogeneous photocatalytic reduction of CO2 on TiO2 and other metal oxide, oxynitride, sulfide, and phosphide semiconductors are presented. Research in this field is focused primarily on the development of novel nanostructured photocatalytic materials and on the investigation of the mechanism of the process, from light absorption through charge separation and transport to CO2 reduction pathways. The measures used to quantify the efficiency of the process are also discussed in detail.

Quantum-state engineering, i.e., active control over the coherent dynamics of suitable quantum-mechanical systems, has become a fascinating prospect of modern physics. With concepts developed in atomic and molecular physics and in the context of NMR, the field has been stimulated further by the perspectives of quantum computation and communication. Low-capacitance Josephson tunneling junctions offer a promising way to realize quantum bits (qubits) for quantum information processing. The article reviews the properties of these devices and the practical and fundamental obstacles to their use. Two kinds of device have been proposed, based on either charge or phase (flux) degrees of freedom. Single- and two-qubit quantum manipulations can be controlled by gate voltages in one case and by magnetic fields in the other case. Both kinds of device can be fabricated with present technology. In flux qubit devices, an important milestone, the observation of superpositions of different flux states in the system eigenstates, has been achieved. The Josephson charge qubit has even demonstrated coherent superpositions of states readable in the time domain. There are two major problems that must be solved before these devices can be used for quantum information processing. One must have a long phase coherence time, which requires that external sources of dephasing be minimized. The review discusses relevant parameters and provides estimates of the decoherence time. Another problem is in the readout of the final state of the system. This issue is illustrated with a possible realization by a single-electron transistor capacitively coupled to the Josephson device, but general properties of measuring devices are also discussed. Finally, the review describes how the basic physical manipulations on an ideal device can be combined to perform useful operations.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic asymmetric epoxidation and kinetic resolution: modified procedures including in situ derivatizationYun Gao, Janice M. Klunder, Robert M. Hanson, Hiroko Masamune, Soo Y. Ko, and K. Barry SharplessCite this: J. Am. Chem. Soc. 1987, 109, 19, 5765–5780Publication Date (Print):September 1, 1987Publication History Published online1 May 2002Published inissue 1 September 1987https://pubs.acs.org/doi/10.1021/ja00253a032https://doi.org/10.1021/ja00253a032research-articleACS PublicationsRequest reuse permissionsArticle Views17663Altmetric-Citations1735LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Metal halide perovskites represent a flourishing area of research, which is driven by both their potential application in photovoltaics and optoelectronics and by the fundamental science behind their unique optoelectronic properties. The emergence of new colloidal methods for the synthesis of halide perovskite nanocrystals, as well as the interesting characteristics of this new type of material, has attracted the attention of many researchers. This review aims to provide an up-to-date survey of this fast-moving field and will mainly focus on the different colloidal synthesis approaches that have been developed. We will examine the chemistry and the capability of different colloidal synthetic routes with regard to controlling the shape, size, and optical properties of the resulting nanocrystals. We will also provide an up-to-date overview of their postsynthesis transformations, and summarize the various solution processes that are aimed at fabricating halide perovskite-based nanocomposites. Furthermore, we will review the fundamental optical properties of halide perovskite nanocrystals by focusing on their linear optical properties, on the effects of quantum confinement, and on the current knowledge of their exciton binding energies. We will also discuss the emergence of nonlinear phenomena such as multiphoton absorption, biexcitons, and carrier multiplication. Finally, we will discuss open questions and possible future directions.

Organic and inorganic hybrid perovskites (e.g., CH(3)NH(3)PbI(3)), with advantages of facile processing, tunable bandgaps, and superior charge-transfer properties, have emerged as a new class of revolutionary optoelectronic semiconductors promising for various applications. Perovskite solar cells constructed with a variety of configurations have demonstrated unprecedented progress in efficiency, reaching about 20% from multiple groups after only several years of active research. A key to this success is the development of various solution-synthesis and film-deposition techniques for controlling the morphology and composition of hybrid perovskites. The rapid progress in material synthesis and device fabrication has also promoted the development of other optoelectronic applications including light-emitting diodes, photodetectors, and transistors. Both experimental and theoretical investigations on organic-inorganic hybrid perovskites have enabled some critical fundamental understandings of this material system. Recent studies have also demonstrated progress in addressing the potential stability issue, which has been identified as a main challenge for future research on halide perovskites. Here, we review recent progress on hybrid perovskites including basic chemical and crystal structures, chemical synthesis of bulk/nanocrystals and thin films with their chemical and physical properties, device configurations, operation principles for various optoelectronic applications (with a focus on solar cells), and photophysics of charge-carrier dynamics. We also discuss the importance of further understanding of the fundamental properties of hybrid perovskites, especially those related to chemical and structural stabilities.

Abstract Covalent organic frameworks (COFs) are crystalline porous polymers formed by a bottom‐up approach from molecular building units having a predesigned geometry that are connected through covalent bonds. They offer positional control over their building blocks in two and three dimensions. This control enables the synthesis of rigid porous structures with a high regularity and the ability to fine‐tune the chemical and physical properties of the network. This Feature Article provides a comprehensive overview over the structures realized to date in the fast growing field of covalent organic framework development. Different synthesis strategies to meet diverse demands, such as high crystallinity, straightforward processability, or the formation of thin films are discussed. Furthermore, insights into the growing fields of COF applications, including gas storage and separations, sensing, electrochemical energy storage, and optoelectronics are provided.

Rhodamine dyes are widely used as fluorescent probes owing to their high absorption coefficient and broad fluorescence in the visible region of electromagnetic spectrum, high fluorescence quantum yield and photostability. A great interest in the development of new synthetic procedures for preparation of Rhodamine derivatives has arisen in recent years because for most applications the probe must be covalently linked to another (bio)molecule or surface. In this critical review the strategies for modification of Rhodamine dyes and a discussion on the variety of applications of these new derivatives as fluorescent probes are given (108 references).

A direct HF algorithm using the resolution of identity for Coulomb and exchange integrals (RI-HF) was implemented within the program system TURBOMOLE. A variational procedure for the optimisation of auxiliary functions is presented as well as optimised auxiliary basis sets for large basis sets up to Br. The accuracy of RI-HF energies and of MP2 energies based on RI-HF wave functions is demonstrated for a large test set of molecules. Accuracy of first order properties is documented for selected cases. The size dependency of the RI errors and the efficiency of the method are investigated for closo-boranes [BnHn]2− (n = 4–12).

van der Waals heterostructures assembled from atomically thin crystalline layers of diverse two-dimensional solids are emerging as a new paradigm in the physics of materials. We used infrared nanoimaging to study the properties of surface phonon polaritons in a representative van der Waals crystal, hexagonal boron nitride. We launched, detected, and imaged the polaritonic waves in real space and altered their wavelength by varying the number of crystal layers in our specimens. The measured dispersion of polaritonic waves was shown to be governed by the crystal thickness according to a scaling law that persists down to a few atomic layers. Our results are likely to hold true in other polar van der Waals crystals and may lead to new functionalities.

We present a quantum-mechanical theory of the cooling of a cantilever coupled via radiation pressure to an illuminated optical cavity. Applying the quantum noise approach to the fluctuations of the radiation pressure force, we derive the optomechanical cooling rate and the minimum achievable phonon number. We find that reaching the quantum limit of arbitrarily small phonon numbers requires going into the good-cavity (resolved phonon sideband) regime where the cavity linewidth is much smaller than the mechanical frequency and the corresponding cavity detuning. This is in contrast to the common assumption that the mechanical frequency and the cavity detuning should be comparable to the cavity damping.

The effects of annealing and fullerene loading in regioregular poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM) based bulk heterojunction photovoltaics have been investigated. Under specific loading and annealing conditions, a combination of morphological and electronic factors can be brought to play to achieve optimal filling factors, open-circuit voltage (Voc), and short-circuit current density (Jsc). We demonstrate that this occurs at surprisingly low loadings of PCBM and annealing temperatures nearing the melting point of the polymer. Further, we report power conversion efficiencies approaching 5% in the P3HT:PCBM system.

The amalgamation of different disciplines is at the heart of reticular chemistry and has broadened the boundaries of chemistry by opening up an infinite space of chemical composition, structure, and material properties. Reticular design has enabled the precise prediction of crystalline framework structures, tunability of chemical composition, incorporation of various functionalities onto the framework backbone, and as a consequence, fine-tuning of metal-organic framework (MOF) and covalent organic framework (COF) properties beyond that of any other material class. Leveraging the unique properties of reticular materials has resulted in significant advances from both a fundamental and an applied perspective. Here, we wish to review the milestones in MOF and COF research and give a critical view on progress in their real-world applications. Finally, we briefly discuss the major challenges in the field that need to be addressed to pave the way for industrial applications.

Superior cathode material: Spherical ordered mesoporous carbon nanoparticles featuring very high inner porosity (pore volume of 2.32 cm3 g−1 and surface area of 2445 m2 g−1) were synthesized in a two-step casting process. They were successfully applied as cathode material in Li-S batteries, where they showed high reversible capacity up to 1200 mA h g−1 and excellent cycling efficiency.

This review addresses the fabrication and properties of novel polyelectrolyte microcapsules, with an emphasis on their mechanical and permeability properties. Ease of preparation through layer-by-layer self assembly, accurate control over wall thickness as well as flexibility in the choice of constituents make these capsules very promising for numerous applications in materials and life science. Moreover, by engineering the inner and outer interfaces, these capsules can be used as microreactors for precipitation, crystallization, and polymerization reactions, as well as enzymatic, and heterogeneous catalysis.

Generation of thick vascularized tissues that fully match the patient still remains an unmet challenge in cardiac tissue engineering. Here, a simple approach to 3D-print thick, vascularized, and perfusable cardiac patches that completely match the immunological, cellular, biochemical, and anatomical properties of the patient is reported. To this end, a biopsy of an omental tissue is taken from patients. While the cells are reprogrammed to become pluripotent stem cells, and differentiated to cardiomyocytes and endothelial cells, the extracellular matrix is processed into a personalized hydrogel. Following, the two cell types are separately combined with hydrogels to form bioinks for the parenchymal cardiac tissue and blood vessels. The ability to print functional vascularized patches according to the patient's anatomy is demonstrated. Blood vessel architecture is further improved by mathematical modeling of oxygen transfer. The structure and function of the patches are studied in vitro, and cardiac cell morphology is assessed after transplantation, revealing elongated cardiomyocytes with massive actinin striation. Finally, as a proof of concept, cellularized human hearts with a natural architecture are printed. These results demonstrate the potential of the approach for engineering personalized tissues and organs, or for drug screening in an appropriate anatomical structure and patient-specific biochemical microenvironment.

Nanoparticles of noble metals belong to the most extensively studied colloidal systems in the field of nanoscience and nanotechnology. Due to continuing progress in the synthesis of nanoparticles with controlled morphologies, the exploration of unique morphology-dependent properties has gained momentum. Anisotropic features in nonspherical nanoparticles make them ideal candidates for enhanced chemical, catalytic, and local field related applications. Nonspherical plasmon resonant nanoparticles offer favorable properties for their use as analytical tools, or as diagnostic and therapeutic agents. This Review highlights morphology-dependent properties of nonspherical noble metal nanoparticles with a focus on localized surface plasmon resonance and local field enhancement, as well as their applications in various fields including Raman spectroscopy, fluorescence enhancement, analytics and sensing, photothermal therapy, (bio-)diagnostics, and imaging.

We study the conductivity $\ensuremath{\sigma}(T)$ of interacting electrons in a low-dimensional disordered system at low temperature $T$. For weak interactions, the weak-localization regime crosses over with lowering $T$ into a dephasing-induced ``power-law hopping.'' As $T$ is further decreased, the Anderson localization in Fock space crucially affects $\ensuremath{\sigma}(T)$, inducing a transition at $T={T}_{c}$, so that $\ensuremath{\sigma}(T<{T}_{c})=0$. The critical behavior of $\ensuremath{\sigma}(T)$ above ${T}_{c}$ is $\mathrm{ln}\ensuremath{\sigma}(T)\ensuremath{\propto}\ensuremath{-}(T\ensuremath{-}{T}_{c}{)}^{\ensuremath{-}1/2}$. The mechanism of transport in the critical regime is many-particle transitions between distant states in Fock space.

Single-molecule localization microscopy (SMLM) describes a family of powerful imaging techniques that dramatically improve spatial resolution over standard, diffraction-limited microscopy techniques and can image biological structures at the molecular scale. In SMLM, individual fluorescent molecules are computationally localized from diffraction-limited image sequences and the localizations are used to generate a super-resolution image or a time course of super-resolution images, or to define molecular trajectories. In this Primer, we introduce the basic principles of SMLM techniques before describing the main experimental considerations when performing SMLM, including fluorescent labelling, sample preparation, hardware requirements and image acquisition in fixed and live cells. We then explain how low-resolution image sequences are computationally processed to reconstruct super-resolution images and/or extract quantitative information, and highlight a selection of biological discoveries enabled by SMLM and closely related methods. We discuss some of the main limitations and potential artefacts of SMLM, as well as ways to alleviate them. Finally, we present an outlook on advanced techniques and promising new developments in the fast-evolving field of SMLM. We hope that this Primer will be a useful reference for both newcomers and practitioners of SMLM.

DNA origami is a powerful method for the programmable assembly of nanoscale molecular structures. For applications of these structures as functional biomaterials, the study of reaction kinetics and dynamic processes in real time and with high spatial resolution becomes increasingly important. We present a single-molecule assay for the study of binding and unbinding kinetics on DNA origami. We find that the kinetics of hybridization to single-stranded extensions on DNA origami is similar to isolated substrate-immobilized DNA with a slight position dependence on the origami. On the basis of the knowledge of the kinetics, we exploit reversible specific binding of labeled oligonucleotides to DNA nanostructures for PAINT (points accumulation for imaging in nanoscale topography) imaging with <30 nm resolution. The method is demonstrated for flat monomeric DNA structures as well as multimeric, ribbon-like DNA structures.

Organometal halide perovskites have recently emerged displaying a huge potential for not only photovoltaic, but also light emitting applications. Exploiting the optical properties of specifically tailored perovskite nanocrystals could greatly enhance the efficiency and functionality of applications based on this material. In this study, we investigate the quantum size effect in colloidal organometal halide perovskite nanoplatelets. By tuning the ratio of the organic cations used, we can control the thickness and consequently the photoluminescence emission of the platelets. Quantum mechanical calculations match well with the experimental values. We find that not only do the properties of the perovskite, but also those of the organic ligands play an important role. Stacking of nanoplatelets leads to the formation of minibands, further shifting the bandgap energies. In addition, we find a large exciton binding energy of up to several hundreds of meV for nanoplatelets thinner than three unit cells, partially counteracting the blueshift induced by quantum confinement. Understanding of the quantum size effects in perovskite nanoplatelets and the ability to tune them provide an additional method with which to manipulate the optical properties of organometal halide perovskites.