59 research outputs found
Towards Quantum Sensing of Chiral-Induced Spin Selectivity: Probing Donor-Bridge-Acceptor Molecules with NV Centers in Diamond
Photoexcitable donor-bridge-acceptor (D-B-A) molecules that support
intramolecular charge transfer are ideal platforms to probe the influence of
chiral-induced spin selectivity (CISS) in electron transfer and resulting
radical pairs. In particular, the extent to which CISS influences spin
polarization or spin coherence in the initial state of spin-correlated radical
pairs following charge transfer through a chiral bridge remains an open
question. Here, we introduce a quantum sensing scheme to measure directly the
hypothesized spin polarization in radical pairs using shallow nitrogen-vacancy
(NV) centers in diamond at the single- to few-molecule level. Importantly, we
highlight the perturbative nature of the electron spin-spin dipolar coupling
within the radical pair, and demonstrate how Lee-Goldburg decoupling can
preserve spin polarization in D-B-A molecules for enantioselective detection by
a single NV center. The proposed measurements will provide fresh insight into
spin selectivity in electron transfer reactions.Comment: 7 pages and 4 pages appendix including an extensive description of
the initial spin state of photo-generated radical pair
Spatially resolved surface dissipation over metal and dielectric substrates
We report spatially resolved measurements of static and fluctuating electric
fields over conductive (Au) and non-conductive (SiO2) surfaces. Using an
ultrasensitive `nanoladder' cantilever probe to scan over these surfaces at
distances of a few tens of nanometers, we record changes in the probe resonance
frequency and damping that we associate with static and fluctuating fields,
respectively. We find that the two quantities are spatially correlated and of
similar magnitude for the two materials. We quantitatively describe the
observed effects on the basis of trapped surface charges and dielectric
fluctuations in an adsorbate layer. Our results provide direct, spatial
evidence for surface dissipation in adsorbates that affects nanomechanical
sensors, trapped ions, superconducting resonators, and color centers in
diamond
Single Nitrogen-Vacancy-NMR of Amine-Functionalized Diamond Surfaces
Nuclear magnetic resonance (NMR) imaging with shallow nitrogen-vacancy (NV)
centers in diamond offers an exciting route toward sensitive and localized
chemical characterization at the nanoscale. Remarkable progress has been made
to combat the degradation in coherence time and stability suffered by
near-surface NV centers using suitable chemical surface termination. However,
approaches that also enable robust control over adsorbed molecule density,
orientation, and binding configuration are needed. We demonstrate a diamond
surface preparation for mixed nitrogen- and oxygen-termination that
simultaneously improves NV center coherence times for emitters <10-nm-deep and
enables direct and recyclable chemical functionalization via amine-reactive
crosslinking. Using this approach, we probe single NV centers embedded in
nanopillar waveguides to perform NMR sensing of covalently
bound trifluoromethyl tags in the ca. 50-100 molecule regime. This work
signifies an important step toward nuclear spin localization and structure
interrogation at the single-molecule level.Comment: 21 pages and 16 pages supporting informatio
Diamond surface engineering for molecular sensing with nitrogen-vacancy centers
Quantum sensing using optically addressable atomic-scale defects, such as the
nitrogen--vacancy (NV) center in diamond, provides new opportunities for
sensitive and highly localized characterization of chemical functionality.
Notably, near-surface defects facilitate detection of the minute magnetic
fields generated by nuclear or electron spins outside of the diamond crystal,
such as those in chemisorbed and physisorbed molecules. However, the promise of
NV centers is hindered by a severe degradation of critical sensor properties,
namely charge stability and spin coherence, near surfaces (< ca. 10 nm deep).
Moreover, applications in the chemical sciences require methods for covalent
bonding of target molecules to diamond with robust control over density,
orientation, and binding configuration. This forward-looking Review provides a
survey of the rapidly converging fields of diamond surface science and
NV-center physics, highlighting their combined potential for quantum sensing of
molecules. We outline the diamond surface properties that are advantageous for
NV-sensing applications, and discuss strategies to mitigate deleterious effects
while simultaneously providing avenues for chemical attachment. Finally, we
present an outlook on emerging applications in which the unprecedented
sensitivity and spatial resolution of NV-based sensing could provide unique
insight into chemically functionalized surfaces at the single-molecule level.Comment: Review paper, 36 page
SAD phasing using iodide ions in a high-throughput structural genomics environment
The Seattle Structural Genomics Center for Infectious Disease (SSGCID) focuses on the structure elucidation of potential drug targets from class A, B, and C infectious disease organisms. Many SSGCID targets are selected because they have homologs in other organisms that are validated drug targets with known structures. Thus, many SSGCID targets are expected to be solved by molecular replacement (MR), and reflective of this, all proteins are expressed in native form. However, many community request targets do not have homologs with known structures and not all internally selected targets readily solve by MR, necessitating experimental phase determination. We have adopted the use of iodide ion soaks and single wavelength anomalous dispersion (SAD) experiments as our primary method for de novo phasing. This method uses existing native crystals and in house data collection, resulting in rapid, low cost structure determination. Iodide ions are non-toxic and soluble at molar concentrations, facilitating binding at numerous hydrophobic or positively charged sites. We have used this technique across a wide range of crystallization conditions with successful structure determination in 16 of 17 cases within the first year of use (94% success rate). Here we present a general overview of this method as well as several examples including SAD phasing of proteins with novel folds and the combined use of SAD and MR for targets with weak MR solutions. These cases highlight the straightforward and powerful method of iodide ion SAD phasing in a high-throughput structural genomics environment
A Chirality-Based Quantum Leap
There is increasing interest in the study of chiral degrees of freedom occurring in matter and in electromagnetic fields. Opportunities in quantum sciences will likely exploit two main areas that are the focus of this Review: (1) recent observations of the chiral-induced spin selectivity (CISS) effect in chiral molecules and engineered nanomaterials and (2) rapidly evolving nanophotonic strategies designed to amplify chiral light-matter interactions. On the one hand, the CISS effect underpins the observation that charge transport through nanoscopic chiral structures favors a particular electronic spin orientation, resulting in large room-temperature spin polarizations. Observations of the CISS effect suggest opportunities for spin control and for the design and fabrication of room-temperature quantum devices from the bottom up, with atomic-scale precision and molecular modularity. On the other hand, chiral-optical effects that depend on both spin- and orbital-angular momentum of photons could offer key advantages in all-optical and quantum information technologies. In particular, amplification of these chiral light-matter interactions using rationally designed plasmonic and dielectric nanomaterials provide approaches to manipulate light intensity, polarization, and phase in confined nanoscale geometries. Any technology that relies on optimal charge transport, or optical control and readout, including quantum devices for logic, sensing, and storage, may benefit from chiral quantum properties. These properties can be theoretically and experimentally investigated from a quantum information perspective, which has not yet been fully developed. There are uncharted implications for the quantum sciences once chiral couplings can be engineered to control the storage, transduction, and manipulation of quantum information. This forward-looking Review provides a survey of the experimental and theoretical fundamentals of chiral-influenced quantum effects and presents a vision for their possible future roles in enabling room-temperature quantum technologies.ISSN:1936-0851ISSN:1936-086
Broadly reactive human CD8 T cells that recognize an epitope conserved between VZV, HSV and EBV
Human herpesviruses are important causes of potentially severe chronic infections for which T cells are believed to be necessary for control. In order to examine the role of virus-specific CD8 T cells against Varicella Zoster Virus (VZV), we generated a comprehensive panel of potential epitopes predicted in silico and screened for T cell responses in healthy VZV seropositive donors. We identified a dominant HLA-A*0201-restricted epitope in the VZV ribonucleotide reductase subunit 2 and used a tetramer to analyze the phenotype and function of epitope-specific CD8 T cells. Interestingly, CD8 T cells responding to this VZV epitope also recognized homologous epitopes, not only in the other α-herpesviruses, HSV-1 and HSV-2, but also the Îł-herpesvirus, EBV. Responses against these epitopes did not depend on previous infection with the originating virus, thus indicating the cross-reactive nature of this T cell population. Between individuals, the cells demonstrated marked phenotypic heterogeneity. This was associated with differences in functional capacity related to increased inhibitory receptor expression (including PD-1) along with decreased expression of co-stimulatory molecules that potentially reflected their stimulation history. Vaccination with the live attenuated Zostavax vaccine did not efficiently stimulate a proliferative response in this epitope-specific population. Thus, we identified a human CD8 T cell epitope that is conserved in four clinically important herpesviruses but that was poorly boosted by the current adult VZV vaccine. We discuss the concept of a âpan-herpesvirusâ vaccine that this discovery raises and the hurdles that may need to be overcome in order to achieve this
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Controlling Motion at the Nanoscale: Rise of the Molecular Machines.
As our understanding and control of intra- and intermolecular interactions evolve, ever more complex molecular systems are synthesized and assembled that are capable of performing work or completing sophisticated tasks at the molecular scale. Commonly referred to as molecular machines, these dynamic systems comprise an astonishingly diverse class of motifs and are designed to respond to a plethora of actuation stimuli. In this Review, we outline the conditions that distinguish simple switches and rotors from machines and draw from a variety of fields to highlight some of the most exciting recent examples of opportunities for driven molecular mechanics. Emphasis is placed on the need for controllable and hierarchical assembly of these molecular components to display measurable effects at the micro-, meso-, and macroscales. As in Nature, this strategy will lead to dramatic amplification of the work performed via the collective action of many machines organized in linear chains, on functionalized surfaces, or in three-dimensional assemblies
Recommended from our members
Controlling Motion at the Nanoscale: Rise of the Molecular Machines.
As our understanding and control of intra- and intermolecular interactions evolve, ever more complex molecular systems are synthesized and assembled that are capable of performing work or completing sophisticated tasks at the molecular scale. Commonly referred to as molecular machines, these dynamic systems comprise an astonishingly diverse class of motifs and are designed to respond to a plethora of actuation stimuli. In this Review, we outline the conditions that distinguish simple switches and rotors from machines and draw from a variety of fields to highlight some of the most exciting recent examples of opportunities for driven molecular mechanics. Emphasis is placed on the need for controllable and hierarchical assembly of these molecular components to display measurable effects at the micro-, meso-, and macroscales. As in Nature, this strategy will lead to dramatic amplification of the work performed via the collective action of many machines organized in linear chains, on functionalized surfaces, or in three-dimensional assemblies
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