Jens Ulstrup

Bio: Jens Ulstrup is an academic researcher from Technical University of Denmark. The author has contributed to research in topics: Electron transfer & Scanning tunneling microscope. The author has an hindex of 43, co-authored 257 publications receiving 5606 citations.

Gold nanoparticle assisted assembly of a heme protein for enhancement of long-range interfacial electron transfer

Abstract: Interfacial electron transfer (ET) of biological macromolecules such as metalloproteins is the key process in bioelectrochemistry, enzymatic electrocatalysis, artificial ET chains, single-molecule electronic amplification and rectification, and other phenomena associated with the area of bioelectronics. A key challenge in molecular bioelectronics is to improve the efficiency of long-range charge transfer. The present work shows that this can be achieved by nanoparticle (NP) assisted assembly of cytochrome c (cyt c) on macroscopic single-crystalline electrode surfaces. We present the synthesis and characterization of water-soluble gold nanoparticles (AuNPs) with core diameter 3−4 nm and their application for the enhancement of long-range interfacial ET of a heme protein. Gold nanoparticles were electrostatically conjugated with cyt c to form nanoparticle−protein hybrid ET systems with well-defined stoichiometry. The systems were investigated in homogeneous solution and at liquid/solid interface. Conjugatio...

Thermal gating of the single molecule conductance of alkanedithiols.

Abstract: The temperature dependence of the single molecule conductance (SMC) of α,ω-alkanedithiols has been investigated using a scanning tunnelling microscopy (STM) method. This is based on trapping molecules between a gold STM tip and a gold substrate and measuring directly the current across the molecule under different applied potentials. A pronounced temperature dependence of the conductance, which scales logarithmically with T−1, is observed in the temperature range between 293 and 353 K. It is proposed that the origin of this dependence is the change in distribution between molecular conformers rather than changes in either the conduction mechanism or the electronic structure of the molecule. For alkanedithiols the time averaged conformer distribution shifts to less elongated conformers at higher temperatures thus giving rise to higher conductance across the molecular bridges. This is analysed by first calculating energy differences between different conformers and then calculating their partition distribution. A simple tunnelling model is then used to calculate the temperature dependent conductance based on the conformer distribution. These findings demonstrate that charge transport through single organic molecules at ambient temperatures is a subtle and highly dynamic process that cannot be described by analysing only one molecular conformation corresponding to the lowest energy geometry of the molecule.

Structure-Property Relationships in Redox-Gated Single Molecule Junctions - A Comparison of Pyrrolo-Tetrathiafulvalene and Viologen Redox Groups

Abstract: We demonstrate that the electrical “switching” behavior of single molecules connected between two electrode contacts can be controlled by altering their structure and electrochemical characteristics. The electrical properties of gold|molecule|gold single molecule junctions incorporating HS(CH2)6−X−(CH2)6SH, where X = viologen (4,4′-bipyridinium) or pyrrolotetrathiafulvalene, are determined using a scanning tunneling microscopy based technique. The switching behavior, controlled through a tuneable electrochemical gate, changes from an on−off response (viologen) to an off−on−off response (pyrrolotetrathiafulvalene) on changing the central redox group. In contrast, the electrical properties of junctions incorporating redox-inactive HS(CH2)6−1,4-C6H4−(CH2)6SH do not alter significantly as a function of applied potential.

Graphene Paper Doped with Chemically Compatible Prussian Blue Nanoparticles as Nanohybrid Electrocatalyst

Abstract: Along with reduced graphene oxide (RGO), water soluble Prussian blue nanoparticles (PBNPs, around 6 nm) are synthesized and broadly characterized. These two types of highly stable, low-cost and chemically compatible nanomaterials are exploited as building ingredients to prepare electrically enhanced and functionally endorsed nanohybrid electrocatalysts, which are further transformed into free-standing graphene papers. PBNPs doped graphene papers show highly efficient electrocatalysis towards reduction of hydrogen peroxide and can be used alone as flexible chemical sensors for potential applications in detection of hydrogen peroxide or/and other organic peroxides. The as-prepared PBNPs–RGO papers are further capable of biocompatible accommodation of enzymes for development of free-standing enzyme based biosensors. In this regard, glucose oxidase is used as an example for electrocatalytic oxidation and detection of glucose. The present work demonstrates a facile and highly reproducible way to construct free-standing and flexible graphene paper doped with electroactive catalyst. Thanks to high stability, low-cost and efficient electrocatalytic characteristics, this kind of nanohybrid material has potential to be produced on a large scale, and offers a broad range of possible applications, particularly in the fabrication of flexible sensing devices and as a platform for electrocatalytic energy conversion.

I and i

Abstract: There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality. Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

Fast parallel algorithms for short-range molecular dynamics

Abstract: Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

Combining theory and experiment in electrocatalysis: Insights into materials design

Abstract: BACKGROUND With a rising global population, increasing energy demands, and impending climate change, major concerns have been raised over the security of our energy future. Developing sustainable, fossil-free pathways to produce fuels and chemicals of global importance could play a major role in reducing carbon dioxide emissions while providing the feedstocks needed to make the products we use on a daily basis. One prospective goal is to develop electrochemical conversion processes that can convert molecules in the atmosphere (e.g., water, carbon dioxide, and nitrogen) into higher-value products (e.g., hydrogen, hydrocarbons, oxygenates, and ammonia) by coupling to renewable energy. Electrocatalysts play a key role in these energy conversion technologies because they increase the rate, efficiency, and selectivity of the chemical transformations involved. Today’s electrocatalysts, however, are inadequate. The grand challenge is to develop advanced electrocatalysts with the enhanced performance needed to enable widespread penetration of clean energy technologies. ADVANCES Over the past decade, substantial progress has been made in understanding several key electrochemical transformations, particularly those that involve water, hydrogen, and oxygen. The combination of theoretical and experimental studies working in concert has proven to be a successful strategy in this respect, yielding a framework to understand catalytic trends that can ultimately provide rational guidance toward the development of improved catalysts. Catalyst design strategies that aim to increase the number of active sites and/or increase the intrinsic activity of each active site have been successfully developed. The field of hydrogen evolution, for example, has seen important breakthroughs over the years in the development of highly active non–precious metal catalysts in acid. Notable advancements have also been made in the design of oxygen reduction and evolution catalysts, although there remains substantial room for improvement. The combination of theory and experiment elucidates the remaining challenges in developing further improved catalysts, often involving scaling relations among reactive intermediates. This understanding serves as an initial platform to design strategies to circumvent technical obstacles, opening up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions. OUTLOOK A systematic framework of combining theory and experiment in electrocatalysis helps to uncover broader governing principles that can be used to understand a wide variety of electrochemical transformations. These principles can be applied to other emerging and promising clean energy reactions, including hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, among others. Although current paradigms for catalyst development have been helpful to date, a number of challenges need to be successfully addressed in order to achieve major breakthroughs. One important frontier, for example, is the development of both experimental and computational methods that can rapidly elucidate reaction mechanisms on broad classes of materials and in a wide range of operating conditions (e.g., pH, solvent, electrolyte). Such efforts would build on current frameworks for understanding catalysis to provide the deeper insights needed to fine-tune catalyst properties in an optimal manner. The long-term goal is to continue improving the activity and selectivity of these catalysts in order to realize the prospects of using renewable energy to provide the fuels and chemicals that we need for a sustainable energy future.

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Abstract: : The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg