2,141 research outputs found
Extent of stacking disorder in diamond
Hexagonal diamond has been predicted computationally to display extraordinary
physical properties including a hardness that exceeds cubic diamond. However, a
recent electron microscopy study has shown that so-called hexagonal diamond
samples are in fact not discrete materials but faulted and twinned cubic
diamond. We now provide a quantitative analysis of cubic and hexagonal stacking
in diamond samples by analysing X-ray diffraction data with the DIFFaX software
package. The highest fractions of hexagonal stacking we find in materials which
were previously referred to as hexagonal diamond are below 60%. The remainder
of the stacking sequences are cubic. We show that the cubic and hexagonal
sequences are interlaced in a complex way and that naturally occurring
Lonsdaleite is not a simple phase mixture of cubic and hexagonal diamond.
Instead, it is structurally best described as stacking disordered diamond. The
future experimental challenge will be to prepare diamond samples beyond 60%
hexagonality and towards the so far elusive 'perfect' hexagonal diamond
Boundary of Quantum Evolution under Decoherence
Relaxation effects impose fundamental limitations on our ability to
coherently control quantum mechanical phenomena. In this letter, we establish
physical limits on how closely can a quantum mechanical system be steered to a
desired target state in the presence of relaxation. In particular, we
explicitly compute the maximum coherence or polarization that can be
transferred between coupled nuclear spins in the presence of very general
decoherence mechanisms that include cross-correlated relaxation. We give
analytical expressions for the control laws (pulse sequences) which achieve
these physical limits and provide supporting experimental evidence.
Exploitation of cross-correlation effects has recently led to the development
of powerful methods in NMR spectroscopy to study very large biomolecules in
solution. We demonstrate with experiments that the optimal pulse sequences
provide significant gains over these state of the art methods, opening new
avenues for spectroscopy of much larger proteins. Surprisingly, in spite of
very large relaxation rates, optimal control can transfer coherence without any
loss when cross-correlated relaxation rates are tuned to auto-correlated
relaxation rates
Hydrogen mean force and anharmonicity in polycrystalline and amorphous ice
The hydrogen mean force from experimental neutron Compton profiles is derived
using deep inelastic neutron scattering on amorphous and polycrystalline ice.
The formalism of mean force is extended to probe its sensitivity to
anharmonicity in the hydrogen-nucleus effective potential. The shape of the
mean force for amorphous and polycrystalline ice is primarily determined by the
anisotropy of the underlying quasi-harmonic effective potential. The data from
amorphous ice show an additional curvature reflecting the more pronounced
anharmonicity of the effective potential with respect to that of ice Ih.Comment: 12 pages, 7 figures, original researc
Broadband Relaxation-Optimized Polarization Transfer in Magnetic Resonance
Many applications of magnetic resonance are limited by rapid loss of spin
coherence caused by large transverse relaxation rates. In nuclear magnetic
resonance (NMR) of large proteins, increased relaxation losses lead to poor
sensitivity of experiments and increased measurement time. In this paper we
develop broadband relaxation optimized pulse sequences (BB-CROP) which approach
fundamental limits of coherence transfer efficiency in the presence of very
general relaxation mechanisms that include cross-correlated relaxation. These
broadband transfer schemes use new techniques of chemical shift refocusing
(STAR echoes) that are tailored to specific trajectories of coupled spin
evolution. We present simulations and experimental data indicating significant
enhancement in the sensitivity of multi-dimensional NMR experiments of large
molecules by use of these methods
Benchmarking acid and base dopants with respect to enabling the ice V to XIII and ice VI to XV hydrogen-ordering phase transitions
Doping the hydrogen-disordered phases of ice V, VI and XII with hydrochloric
acid (HCl) has led to the discovery of their hydrogen-ordered counterparts ices
XIII, XV and XIV. Yet, the mechanistic details of the hydrogen-ordering phase
transitions are still not fully understood. This includes in particular the
role of the acid dopant and the defect dynamics that it creates within the
ices. Here we investigate the effects of several acid and base dopants on the
hydrogen ordering of ices V and VI with calorimetry and X-ray diffraction. HCl
is found to be most effective for both phases which is attributed to a
favourable combination of high solubility and strong acid properties which
create mobile H3O+ defects that enable the hydrogen-ordering processes.
Hydrofluoric acid (HF) is the second most effective dopant highlighting that
the acid strengths of HCl and HF are much more similar in ice than they are in
liquid water. Surprisingly, hydrobromic acid doping facilitates hydrogen
ordering in ice VI whereas only a very small effect is observed for ice V.
Conversely, lithium hydroxide (LiOH) doping achieves a performance comparable
to HF-doping in ice V but it is ineffective in the case of ice VI. Sodium
hydroxide, potassium hydroxide (as previously shown) and perchloric acid doping
are ineffective for both phases. These findings highlight the need for future
computational studies but also raise the question why LiOH-doping achieves
hydrogen-ordering of ice V whereas potassium hydroxide doping is most effective
for the 'ordinary' ice Ih.Comment: 18 pages, 7 figures, 1 tabl
Graphene Nanoflake Antibody Conjugates for Multimodal Imaging of Tumors
Graphene-based materials are promising scaffolds for use in the design of tailored-made nanomedicines. Herein, the synthesis and characterization of a series of multifunctional carboxylated graphene nanoflakes (GNFs) conjugated to monoclonal antibodies (mAbs) for tumor-specific binding and modulation of pharmacokinetics is presented. GNFâmAb constructs are coupled to a fluorophore (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene [BODIPY]) for applications in optical imaging, a paramagnetic Gd3+ complex, [GdDOTAGA(H2O)]â, and the hexadentate chelate desferrioxamine B (DFO) for radiolabeling with 89Zr4+ (t1/2â=â78.41âh) ions and applications in dual-modality positron emission tomography/magnetic resonance imaging (PET/MRI). Experimental properties of [89Zr]GdDOTAGAâZrDFOâGNFâtrastuzumab are tested in extensive chemical, spectroscopic, radiochemical, and cellular assays inâvitro, and assessment of the pharmacokinetics by PET imaging in mice bearing a human ovarian cancer model illustrates the potential of using GNFâmAbs to develop multifunctional PET/MRI probes
Local structure and orientational ordering in liquid bromoform
The neutron diffraction data of liquid bromoform (CHBr3) at 25°C was analysed using the Empirical Potential Structure Refinement technique in combination with H/D isotopic substitution. Compared to liquid chloroform (CHCl3), CHBr3 displays more spatially defined intermolecular contacts. A preference for polar stacking with collinear alignment of dipole moments is observed for the most closely approaching CHBr3 molecules, although to a lesser extent than in chloroform. Consistent with this, and in line with dielectric spectroscopy, the Kirkwood correlation factor from the structural model of CHBr3 is smaller than that of CHCl3. The net antiparallel alignment of dipole moments in CHBr3, as suggested by dielectric spectroscopy, must be due to weak but persistent long-range orientation correlations in CHBr3, which counteract the local polar stacking
Cloud system resolving model study of the roles of deep convection for photo-chemistry in the TOGA COARE/CEPEX region
International audienceA cloud system resolving model including photo-chemistry (CSRMC) has been developed based on a prototype version of the Weather Research and Forecasting (WRF) model and is used to study influences of deep convection on chemistry in the TOGA COARE/CEPEX region. Lateral boundary conditions for trace gases are prescribed from global chemistry-transport simulations, and the vertical advection of trace gases by large scale dynamics, which is not reproduced in a limited area cloud system resolving model, is taken into account. The influences of deep convective transport and of lightning on NOx, O3, and HOx(=HO2+OH), in the vicinity of the deep convective systems are investigated in a 7-day 3-D 248Ă248 km2 horizontal domain simulation and several 2-D sensitivity runs with a 500 km horizontal domain. Mid-tropospheric entrainment is more important on average for the upward transport of O3 in the 3-D run than in the 2-D runs, but at the same time undiluted O3-poor air from the marine boundary layer reaches the upper troposphere more frequently in the 3-D run than in the 2-D runs, indicating the presence of undiluted convective cores. In all runs, in situ lightning is found to have only minor impacts on the local O3 budget. Near zero O3 volume mixing ratios due to the reaction with lightning-produced NO are only simulated in a 2-D sensitivity run with an extremely high number of NO molecules per flash, which is outside the range of current estimates. The fraction of NOx chemically lost within the domain varies between 20 and 24% in the 2-D runs, but is negligible in the 3-D run, in agreement with a lower average NOx concentration in the 3-D run despite a greater number of flashes. Stratosphere to troposphere transport of O3 is simulated to occur episodically in thin filaments in the 2-D runs, but on average net upward transport of O3 from below ~16 km is simulated in association with mean large scale ascent in the region. Ozone profiles in the TOGA COARE/CEPEX region are suggested to be strongly influenced by the intra-seasonal (Madden-Julian) oscillation
Modelling tracer transport by a cumulus ensemble: lateral boundary conditions and large-scale ascent
International audienceThe vertical transport of tracers by a cumulus ensemble at the TOGA-COARE site is modelled during a 7 day episode using 2-D and 3-D cloud-resolving setups of the Weather Research and Forecast (WRF) model. Lateral boundary conditions (LBC) for tracers, water vapour, and wind are specified and the horizontal advection of trace gases across the lateral domain boundaries is considered. Furthermore, the vertical advection of trace gases by the large-scale motion (short: vertical large-scale advection of tracers, VLSAT) is considered. It is shown, that including VLSAT partially compensates the calculated net downward transport from the middle and upper troposphere (UT) due to the mass balancing mesoscale subsidence induced by deep convection. Depending on whether the VLSAT term is added or not, modelled domain averaged vertical tracer profiles can differ significantly. Differences between a 2-D and a 3-D model run were mainly attributed to an increase in horizontal advection across the lateral domain boundaries due to the meridional wind component not considered in the 2-D setup
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