8 research outputs found
Home spirometry for idiopathic pulmonary fibrosis: ready for prime time?
Home spirometry in IPF can be used to shorten clinical trials and may enable patient self-management in the future http://ow.ly/Jqft30dGia
Emergent Negative Differential Resistance with an Undisturbed Topological Surface State
Emergent properties in topological
insulator heterostructures offer
fresh insight not only to understand the system as a whole but also
to design new approaches to device engineering at the nanoscale. Here
we report the emergent phenomenon of negative differential resistance
(NDR) on a topological insulator substrate. Starting with the spin-bearing
cobalt fluorophthalocyanine molecule F16CoPc as the fundamental
building block and the topological insulator (TI) Bi2Se3 as the host, using scanning tunneling spectroscopy (STS)
we observe the emergence of NDR at the F16CoPc/Bi2Se3 interface at a specific negative bias. The topological
surface state is also preserved in the process. Realizing NDR at the
molecular scale presents a major advance toward designing ultrafast
electron tunneling devices as well as high speed, low power, and compact
nanoelectronic devices. The undisturbed topological surface state
of Bi2Se3 offers added tunability for computer
architectures that can be built concomitantly using the topological
surface state and NDR
Enhancing Intermolecular Interaction by Cyano Substitution in Copper Phthalocyanine
On-surface
molecular self-assembly is one of the key paradigms
for understanding intermolecular interactions and molecule–substrate
interactions at the atomic scale. Phthalocyanines are planar π-conjugated
systems capable of self-assembly and can act as versatile, robust,
and tunable templates for surface functionalization. One of the ways
to tailor the properties of phthalocyanines is by pendant group substitution.
How such a scheme brings about changes in the properties of the phthalocyanines
at the nanoscale has not been greatly explored. Here we present an
atomic-scale picture of the self-assembly of copper phthalocyanine,
CuPc, and compare it with its cyano analogue, CuPcÂ(CN)<sub>8,</sub>on Au(111) using scanning tunneling microscopy (STM) and scanning
tunneling spectroscopy (STS) in ultrahigh vacuum (UHV) at 77 K. STM
imaging reveals a tetramer unit cell to be the hallmark of each assembly.
The periodicity of herringbone reconstruction of Au(111) is unchanged
upon CuPcÂ(CN)<sub>8</sub> adsorption, whereas for CuPc adsorption
this periodicity changes. STS measurements show an increment in the
highest occupied–lowest unoccupied molecular orbital (HOMO–LUMO)
gap from CuPc to CuPcÂ(CN)<sub>8</sub>. Extensive ab initio calculations
within density functional theory (DFT) match well with the experimental
observations. STM imaging shows adsorption-induced organizational
chirality for both assemblies. For CuPcÂ(CN)<sub>8</sub> at LUMO energy,
the individual molecule exhibits an orbital-energy-dependent chirality
on top of the existing organizational chirality. It remains achiral
at HOMO energy and within the HOMO–LUMO gap. No such peculiarity
is seen in the CuPc assembly. This energy-selective chiral picture
of CuPcÂ(CN)<sub>8</sub> is ascribed to the cyano groups that participate
in antiparallel dipolar coupling, thereby enhancing intermolecular
interaction in the CuPcÂ(CN)<sub>8</sub> assembly. Thus, our atomically
resolved topographic and spectroscopic studies, supplemented by DFT
calculations, demonstrate that pendant group substitution is an effective
strategy for tweaking intermolecular interactions and for surface
functionalization
Off-Stoichiometric Nickel Cobaltite Nanoparticles: Thermal Stability, Magnetization, and Neutron Diffraction Studies
In the present investigation, we
report a detailed examination of the effect of off-stoichiometry introduced
in NiCo<sub>2</sub>O<sub>4</sub> by adding excess cobalt. Thus, we
compare and analyze the structural and magnetic properties of the
Ni<sub>0.75</sub>Co<sub>2.25</sub>O<sub>4</sub> and NiCo<sub>2</sub>O<sub>4</sub> cubic systems. A low temperature combustion method
was utilized to synthesize stoichiometric (NiCo<sub>2</sub>O<sub>4</sub>) and off-stoichiometric (Ni<sub>0.75</sub>Co<sub>2.25</sub>O<sub>4</sub>) nanoparticles on a large scale. The X-ray diffraction pattern
for the sample annealed at high temperature (773 K) shows the presence
of a much less intense NiO phase (∼2–5%) in Ni<sub>0.75</sub>Co<sub>2.25</sub>O<sub>4</sub> as compared to that in the case of
NiCo<sub>2</sub>O<sub>4</sub> sample (∼15–20%). The
Ni 2p and Co 2p XPS spectra reveal the coexistence of Ni<sup>2+</sup>, Ni<sup>3+</sup>, Co<sup>2+</sup>, and Co<sup>3+</sup> species on
the surface of both the NiCo<sub>2</sub>O<sub>4</sub> and Ni<sub>0.75</sub>Co<sub>2.25</sub>O<sub>4</sub> samples in differing proportions.
In addition to the basic magnetic characterizations using PPMS, these
were also analyzed by neutron diffraction. The off-stoichiometric
Ni<sub>0.75</sub>Co<sub>2.25</sub>O<sub>4</sub> sample shows an interesting
magnetic phase conversion from frustrated dipolar system to an enhanced
magnetic ordering upon annealing. Local moments on the lattice sites
of NiCo<sub>2</sub>O<sub>4</sub> and Ni<sub>0.75</sub>Co<sub>2.25</sub>O<sub>4</sub> samples are further compared by neutron diffraction
confirming stronger ordered moments and enhanced structural and thermal
stability for the Ni<sub>0.75</sub>Co<sub>2.25</sub>O<sub>4</sub> sample
Self-Assembly and Photopolymerization of Sub‑2 nm One-Dimensional Organic Nanostructures on Graphene
While graphene has attracted significant attention from
the research
community due to its high charge carrier mobility, important issues
remain unresolved that prevent its widespread use in technologically
significant applications such as digital electronics. For example,
the chemical inertness of graphene hinders integration with other
materials, and the lack of a bandgap implies poor switching characteristics
in transistors. The formation of ordered organic monolayers on graphene
has the potential to address each of these challenges. In particular,
functional groups incorporated into the constituent molecules enable
tailored chemical reactivity, while molecular-scale ordering within
the monolayer provides sub-2 nm templates with the potential to tune
the electronic band structure of graphene via quantum confinement
effects. Toward these ends, we report here the formation of well-defined
one-dimensional organic nanostructures on epitaxial graphene via the
self-assembly of 10,12-pentacosadiynoic acid (PCDA) in ultrahigh vacuum
(UHV). Molecular resolution UHV scanning tunneling microscopy (STM)
images confirm the one-dimensional ordering of the as-deposited PCDA
monolayer and show domain boundaries with symmetry consistent with
the underlying graphene lattice. In an effort to further stabilize
the monolayer, in situ ultraviolet photopolymerization induces covalent
bonding between neighboring PCDA molecules in a manner that maintains
one-dimensional ordering as verified by UHV STM and ambient atomic
force microscopy (AFM). Further quantitative insights into these experimental
observations are provided by semiempirical quantum chemistry calculations
that compare the molecular structure before and after photopolymerization
Templating Sub-10 nm Atomic Layer Deposited Oxide Nanostructures on Graphene via One-Dimensional Organic Self-Assembled Monolayers
Molecular-scale control over the
integration of disparate materials
on graphene is a critical step in the development of graphene-based
electronics and sensors. Here, we report that self-assembled monolayers
of 10,12-pentacosadiynoic acid (PCDA) on epitaxial graphene can be
used to template the reaction and directed growth of atomic layer
deposited (ALD) oxide nanostructures with sub-10 nm lateral resolution.
PCDA spontaneously assembles into well-ordered domains consisting
of one-dimensional molecular chains that coat the entire graphene
surface in a manner consistent with the symmetry of the underlying
graphene lattice. Subsequently, zinc oxide and alumina ALD precursors
are shown to preferentially react with the functional moieties of
PCDA, resulting in templated oxide nanostructures. The retention of
the original one-dimensional molecular ordering following ALD is dependent
on the chemical reaction pathway and the stability of the monolayer,
which can be enhanced via ultraviolet-induced molecular cross-linking
Association of epicardial adipose tissue with early structural and functional cardiac changes in Type 2 diabetes
Background
Dysregulated epicardial adipose tissue (EAT) may contribute to the development of heart failure in Type 2 diabetes (T2D). This study aimed to evaluate the associations between EAT volume and composition with imaging markers of subclinical cardiac dysfunction in people with T2D and no prevalent cardiovascular disease.
Methods
Prospective case-control study enrolling participants with and without T2D and no known cardiovascular disease. Two hundred and fifteen people with T2D (median age 63 years, 60 % male) and thirty-nine non-diabetics (median age 59 years, 62 % male) were included. Using computed tomography (CT), total EAT volume and mean CT attenuation, as well as, low attenuation (Hounsfield unit range −190 to −90) EAT volume were quantified by a deep learning method and volumes indexed to body surface area. Associations with cardiac magnetic resonance-derived left ventricular (LV) volumes and strain indices were assessed using linear regression.
Results
T2D participants had higher LV mass/volume ratio (median 0.89 g/mL [0.82–0.99] vs 0.79 g/mL [0.75–0.89]) and lower global longitudinal strain (GLS; 16.1 ± 2.3 % vs 17.2 ± 2.2 %). Total indexed EAT volume correlated inversely with mean CT attenuation. Low attenuation indexed EAT volume was 2-fold higher (18.8 cm3/m2 vs. 9.4 cm3/m2, p
Conclusions
Higher EAT volumes seen in T2D are associated with a lower mean CT attenuation. Low attenuation indexed EAT volume is independently, but only weakly, associated with markers of subclinical cardiac dysfunction in T2D.</p
Constructing custom-made radiotranscriptomic signatures of vascular inflammation from routine CT angiograms: a prospective outcomes validation study in COVID-19.
BackgroundDirect evaluation of vascular inflammation in patients with COVID-19 would facilitate more efficient trials of new treatments and identify patients at risk of long-term complications who might respond to treatment. We aimed to develop a novel artificial intelligence (AI)-assisted image analysis platform that quantifies cytokine-driven vascular inflammation from routine CT angiograms, and sought to validate its prognostic value in COVID-19.MethodsFor this prospective outcomes validation study, we developed a radiotranscriptomic platform that uses RNA sequencing data from human internal mammary artery biopsies to develop novel radiomic signatures of vascular inflammation from CT angiography images. We then used this platform to train a radiotranscriptomic signature (C19-RS), derived from the perivascular space around the aorta and the internal mammary artery, to best describe cytokine-driven vascular inflammation. The prognostic value of C19-RS was validated externally in 435 patients (331 from study arm 3 and 104 from study arm 4) admitted to hospital with or without COVID-19, undergoing clinically indicated pulmonary CT angiography, in three UK National Health Service (NHS) trusts (Oxford, Leicester, and Bath). We evaluated the diagnostic and prognostic value of C19-RS for death in hospital due to COVID-19, did sensitivity analyses based on dexamethasone treatment, and investigated the correlation of C19-RS with systemic transcriptomic changes.FindingsPatients with COVID-19 had higher C19-RS than those without (adjusted odds ratio [OR] 2·97 [95% CI 1·43-6·27], p=0·0038), and those infected with the B.1.1.7 (alpha) SARS-CoV-2 variant had higher C19-RS values than those infected with the wild-type SARS-CoV-2 variant (adjusted OR 1·89 [95% CI 1·17-3·20] per SD, p=0·012). C19-RS had prognostic value for in-hospital mortality in COVID-19 in two testing cohorts (high [≥6·99] vs low [InterpretationRadiotranscriptomic analysis of CT angiography scans introduces a potentially powerful new platform for the development of non-invasive imaging biomarkers. Application of this platform in routine CT pulmonary angiography scans done in patients with COVID-19 produced the radiotranscriptomic signature C19-RS, a marker of cytokine-driven inflammation driving systemic activation of coagulation and responsible for adverse clinical outcomes, which predicts in-hospital mortality and might allow targeted therapy.FundingEngineering and Physical Sciences Research Council, British Heart Foundation, Oxford BHF Centre of Research Excellence, Innovate UK, NIHR Oxford Biomedical Research Centre, Wellcome Trust, Onassis Foundation