MacDiarmid Institute for Advanced Materials and Nanotechnology

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

This paper presents an in-depth study of Surface Enhanced Raman Scattering (SERS) enhancement factors (EFs) and cross-sections, including several issues often overlooked. In particular, various possible rigorous definitions of the SERS EFs are introduced and discussed in the context of SERS applications, such as analytical chemistry and single molecule SERS. These definitions highlight the importance of a careful characterization of the non-SERS cross-sections of the probes under consideration. This aspect is illustrated by experimental results for the non-SERS cross-sections of representative SERS probes along with average SERS EFs for the same probes. In addition, the accurate experimental determination of single molecule enhancement factors is tackled with two recently developed techniques, namely: bi-analyte SERS (BiASERS) and temperature-dependent SERS vibrational pumping. We demonstrate that SERS EFs as low as 107, as opposed to the figure of 1014 often claimed in the literature, are sufficient for the observation of single molecule SERS signals, with maximum single molecule EFs typically on the order of 1010. I.

A simple aqueous solution route has been developed for the preparation of luminescent carbogenic dots from carbohydrates. The optical properties of the carbogenic dots can be tuned by differing the starting materials or the duration of nitric acid treatment. The multicolor emission capability and potential nontoxic nature of these carbogenic dots should enable them to find a wide range of applications in life sciences research.

A simple analytic model for the optical properties of gold is proposed. The model includes a minimum set of parameters necessary to represent the complex dielectric function of gold in the visible and near-uv regions. Explicit values for the parameters to reproduce the Johnson and Christy data [Phys. Rev. B 6, 4370 (1972)] on the optical properties of gold are provided.

A general overview of the field of single-molecule (SM) surface-enhanced Raman spectroscopy (SERS) as it stands today is provided. After years of debates on the basic aspects of SM-SERS, the technique is emerging as a well-established subfield of spectroscopy and SERS. SM-SERS is allowing the observation of subtle spectroscopic phenomena that were not hitherto accessible. Examples of the latter are natural isotopic substitutions in single molecules, observation of the true homogeneous broadening of Raman peaks, Raman excitation profiles of individual molecules, and SM electrochemistry. With background examples of the contributions produced by our group, properly interleaved with results by other practitioners in the field, we present some of the latest developments and promising new leads in this new field of spectroscopy.

In TiO2-based dye-sensitized nanocrystalline solar cells, efficiencies of up to 11% have been obtained using Ru dyes, but the limited availability of these dyes together with their undesirable environmental impact have led to the search for cheaper and safer organic-based dyes. In this Letter, we report the synthesis, electronic, and photovoltaic properties of novel green porphyrin sensitizers. All six porphyrin dyes give solar cell efficiencies of ≥5%, but the best performing dye under standard global AM 1.5 solar conditions gives a short circuit photocurrent density (jsc) of 14.0 ± 0.20 mA/cm2, an open circuit voltage of 680 ± 30 mV, and a fill factor of 0.74, corresponding to an overall conversion efficiency of 7.1%, which, for porphyrin-based sensitizers, is unprecedented. This same dye gives an efficiency of 3.6% in a solid-state cell with spiro-MeOTAD as the hole transporting component, comparable to solid-state cells incorporating the best performing ruthenium dyes.

This special issue of Dalton Transactions is to mark the 60th birthday of Professor Dr. Annie K. Powell. The issue highlights advances in Modern Coordination Chemistry.

Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼ 1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a 'phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon-impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance.

The observation of spin crossover with thermal hysteresis loops of more than a few Kelvin remains relatively uncommon and unpredictable, so is a relatively underdeveloped, but important, area of spin crossover, particularly for memory applications. Lessons learnt regarding the origins, and the practicalities of the proper study and reporting, of thermal hysteresis loops are considered and explained, from a synthetic chemists perspective, after a general introduction to the field of spin crossover.

Bacteria produce a wide range of exopolysaccharides which are synthesized via different biosynthesis pathways. The genes responsible for synthesis are often clustered within the genome of the respective production organism. A better understanding of the fundamental processes involved in exopolysaccharide biosynthesis and the regulation of these processes is critical toward genetic, metabolic and protein-engineering approaches to produce tailor-made polymers. These designer polymers will exhibit superior material properties targeting medical and industrial applications. Exploiting the natural design space for production of a variety of biopolymer will open up a range of new applications. Here, we summarize the key aspects of microbial exopolysaccharide biosynthesis and highlight the latest engineering approaches toward the production of tailor-made variants with the potential to be used as valuable renewable and high-performance products for medical and industrial applications.

We present an overview of a some of the basic principles underlying current research in single-molecule surface-enhanced Raman scattering (SM-SERS). We summarize, by the same token, a series of conditions and characteristics that are common to most SM-SERS conditions, and discuss their implications for the understanding of data and for the comparison among different methods. We try to emphasize aspects of the problem that are not conventionally discussed in detail in the literature. In particular, we provide a full length discussion on the topics of: (i) the minimum SERS enhancement necessary to observe a single molecule, and (ii) the spatial distribution of the enhancement factor (EF) around hot-spots (which affects the statistics of SM-SERS events). A brief outlook into future perspectives of the different techniques used in SM-SERS and a few outstanding questions are also provided.

A method is proposed to pin down unambiguous proof for single-molecule sensitivity in surface enhanced Raman spectroscopy (SERS). The simultaneous use of two analyte molecules enables a clear confirmation of the single (or few)-molecule nature of the signals. This method eliminates most of the uncertainties associated with low dye concentrations in previous experiments. It further shows that single- or few-molecule signals are very common in SERS, both in liquids and on dry substrates.

Single-molecule surface-enhanced Raman scattering (SERS) detection of nonresonant molecules is demonstrated experimentally using the bianalyte SERS method. To this end, bianalyte SERS is performed at 633 nm excitation using the nonresonant molecule 1,2-di-(4-pyridyl)-ethylene (BPE) in combination with a benzotriazole derivative as a partner. The results are then extended to the even more challenging case of a small nonresonant molecule, adenine, using an isotopically substituted adenine as bianalyte SERS partners. In addition, SERS cross sections of single-molecule events are quantified, thus providing estimates of the enhancement factors needed to see them. It turns out that an enhancement factor on the order of approximately 5 x 10(9) was sufficient for single-molecule detection of BPE, while maximum enhancement factors of approximately 5 x 10(10) were observed in extreme cases. In the case of adenine, single-molecule detection was only possible in the rare cases with enhancement factors of approximately 10(11). This study constitutes a quantitative fundamental test into the lowest detection limits (in terms of differential cross sections) for single-molecule SERS.

Strong photoluminescence in the blue region of the visible spectrum was observed for a dispersion of allylamine-capped silicon quantum dots in water. Their ease of synthesis and optical properties make them excellent candidates for biomedical applications, as demonstrated by their incorporation inside the cytosol of HeLa cells (see microscopy image, the inset shows the fluorescence from the silicon quantum dots on excitation with UV light).

A series of novel zinc metalloporphyrins, cyano-3-(2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-acrylic acid (Zn-3), 3-(trans-2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-acrylic acid (Zn-5), 2-cyano-5-(2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-penta-2,4-dienoic acid (Zn-8), 4-(trans-2'-(2' '-(5' ',10' ',15' ',20' '-tetraphenylporphyrinato zinc(II))yl)ethen-1'-yl))-1,2-benzenedicarboxylic acid (Zn-11), and 2-cyano-3-[4'-(trans-2' '-(2' ''-(5' '',10' '',15' '',20' ''-tetraphenylporphyrinato zinc(II))yl) ethen-1' '-yl)-phenyl]-acrylic acid (Zn-13) were synthesized and characterized by using various spectroscopic techniques. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that key molecular orbitals (MOs) of porphyrins Zn-5 and Zn-3 are stabilized and extended out onto the substituent by pi-conjugation, causing enhancement and red shifts of visible transitions and increasing the possibility of electron transfer from the substituent. The porphyrins were investigated for conversion of sunlight into electricity by constructing dye-sensitized TiO(2) solar cells using an I(-)/I(3)(-) electrolyte. The cells yield close to 85% incident photon-to-current efficiencies (IPCEs), and under standard AM 1.5 sunlight, the Zn-3-sensitized solar cell demonstrates a short circuit photocurrent density of 13.0 +/- 0.5 mA/cm(2), an open-circuit voltage of 610 +/- 50 mV, and a fill factor of 0.70 +/- 0.03. This corresponds to an overall conversion efficiency of 5.6%, making it the most efficient porphyrin-sensitized solar cell reported to date.

Electrochemical reduction of the diazonium salts of 4-nitrobenzene and 4-nitroazobenzene-4'- has been investigated in aqueous acid and acetonitrile media at carbon surfaces. Using pyrolyzed photoresist films as the substrate, we have examined the deposited films using electrochemistry and atomic force microscopy (AFM). Film thicknesses were measured by scratching through the film with an AFM tip. The procedure employed two AFM cantilevers with different lengths, located on the one device. When the shorter cantilever engages the surface in tapping mode, the longer cantilever (which is not resonating) imbeds into the surface with a constant force. For both modifiers and modification media, film thicknesses increase with deposition time to a limiting value. With equivalent modification conditions, films prepared in aqueous acid medium have lower limiting thicknesses than those prepared in acetonitrile. For nitrophenyl (NP) films, the same trends are found when calculating surface coverages from the charge associated with the reduction of surface -Ar-NO2 groups. Lower limiting film thicknesses and surface coverages for films prepared in aqueous conditions is attributed to growth of inherently more blocking films and is supported by examination of the response of the Fe(CN)6(3-/4-) couple at NP-modified surfaces. Combination of voltammetrically determined surface coverage and film thickness data yields a surface coverage of -Ar-NO2 groups of (2.5 +/- 0.5) x 10(-10) mol cm(-2) for a film thickness equivalent to a monolayer of NP groups.

Five polymer donors with distinct chemical structures and different electronic properties are surveyed in a planar and narrow-bandgap fused-ring electron acceptor (IDIC)-based organic solar cells, which exhibit power conversion efficiencies of up to 11%. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

We provide the theoretical framework to understand the phenomenology and statistics of single molecule (SM) signals arising in surface enhanced Raman scattering (SERS) under the presence of so-called electromagnetic hot spots. We show that most characteristics of the SM-SERS phenomenon can be tracked down to the presence of a tail-like (power law) distribution of enhancements and we propose a specific model for it. We analyze, in the light of this, the phenomenology of SM-SERS and show how the different experimental manifestations of the effect reported in the literature can be analyzed and understood under a unified "universal" framework with a minimum set of parameters.

The separation of ethane from ethylene is of prime importance in the purification of chemical feedstocks for industrial manufacturing. However, differentiating these compounds is notoriously difficult due to their similar physicochemical properties. High-performance porous adsorbents provide a solution. Conventional adsorbents trap ethylene in preference to ethane, but this incurs multiple steps in separation processes. Alternatively, high-purity ethylene can be obtained in a single step if the adsorbent preferentially adsorbs ethane over ethylene. We herein report a metal-organic framework, MUF-15 (MUF, Massey University Framework), constructed from inexpensive precursors that sequesters ethane from ethane/ethylene mixtures. The productivity of this material is exceptional: 1 kg of MOF produces 14 L of polymer-grade ethylene gas in a single adsorption step starting from an equimolar ethane/ethylene mixture. Computational simulations illustrate the underlying mechanism of guest adsorption. The separation performance was assessed by measuring multicomponent breakthrough curves, which illustrate that the separation performance is maintained over a wide range of feed compositions and operating pressures. MUF-15 is robust, maintains its performance in the presence of acetylene, and is easily regenerated by purging with inert gas or by placing under reduced pressure.

Abstract Uranium extraction from seawater provides an opportunity for sustainable fuel supply to nuclear power plants. Herein, an adsorption–electrocatalysis strategy is demonstrated for efficient uranium extraction from seawater using a functionalized iron–nitrogen–carbon (Fe–N x –C–R) catalyst, comprising N‐doped carbon capsules supporting FeN x single‐atom sites and surface chelating amidoxime groups (R). The amidoxime groups bring hydrophilicity to the adsorbent and offer surface‐specific binding sites for UO 2 2+ capture. The site‐isolated FeN x centres reduce adsorbed UO 2 2+ to UO 2 + . Subsequently, through electrochemical reduction of the FeN x sites, unstable U(V) ions are reoxidized to U(VI) in the presence of Na + resulting in the generation of solid Na 2 O(UO 3 ·H 2 O) x , which can easily be collected. Fe–N x –C–R reduced the uranium concentration in seawater from ≈ 3.5 ppb to below 0.5 ppb with a calculated capacity of ≈ 1.2 mg g ‐1 within 24 h. To the best of the knowledge, the developed system is the first to use the adsorption of uranyl ions and electrodeposition of solid Na 2 O(UO 3 .H 2 O) x for the extraction of uranium from seawater. The important discoveries guide technology development for the efficient extraction of uranium from seawater.