In-depth critical analysis of complications following robot-assisted radical cystectomy with intracorporeal urinary diversion

Background: Robot-assisted radical cystectomy with intracorporeal urinary diversion (iRARC) is an attractive option to open cystectomy, but the benefit in terms of improved outcomes is not established. Objective: To evaluate the early postoperative morbidity and mortality of patients undergoing iRARC and conduct a critical analysis of complications using standardised reporting criteria as stratified according to urinary diversion. Design, setting, and participants: A total of 134 patients underwent iRARC for bladder cancer at a single centre between June 2011 and July 2015. Intervention: Radical cystectomy with iRARC. Outcome measurements and statistical analysis: Patient demographics, pathologic data, and 90-d perioperative mortality and complications were recorded. Complications were reported according to the Clavien-Dindo (CD) classification and stratified according to urinary diversion type and either surgical or medical complications. The chi-square test and t test were used for categorical and continuous variables respectively. Multivariable logistic regression was performed on variables with significance in univariate analysis. Results and limitations: The 90-d all complication rate following ileal conduit and continent diversion was 68% and 82.4%, and major complications were 21.0% and 20.6% respectively. The 90-d mortality was 3% and 2.9% for ileal conduit and continent diversion patients, respectively. On multivariate analysis, the blood transfusion requirement was independently associated with major complications (p = 0.002) and all 30-d (p = 0.002) and 90-d (p = 0.012) major complications. Male patients were associated with 90-d major complications (p = 0.015). Critical analysis identified that surgical complications were responsible for 39.4% of all 90-d major complications. The incidence of surgical complications did not decline with increasing number of iRARC cases performed (p = 0.742, r = 0.31). Limitations of this study include its retrospective nature, limited sample size, and limited multivariate analysis due to the low number of major complications events. Conclusions: Although complications following iRARC are common, most are low grade. A critical analysis identified surgical complications as a cause of major complications. Addressing this issue could have a significant impact on lowering the morbidity associated with iRARC. Patient summary: We looked at the surgical outcomes in bladder cancer patients treated with minimally invasive robotic surgery. We found that surgical complications account for most major complications and previous surgical experience may be a confounding factor when interpreting results from a different centre even in a randomised trial setting

The Poisson-Boltzmann model for implicit solvation of electrolyte solutions: Quantum chemical implementation and assessment via Sechenov coefficients.

We present the theory and implementation of a Poisson-Boltzmann implicit solvation model for electrolyte solutions. This model can be combined with arbitrary electronic structure methods that provide an accurate charge density of the solute. A hierarchy of approximations for this model includes a linear approximation for weak electrostatic potentials, finite size of the mobile electrolyte ions, and a Stern-layer correction. Recasting the Poisson-Boltzmann equations into Euler-Lagrange equations then significantly simplifies the derivation of the free energy of solvation for these approximate models. The parameters of the model are either fit directly to experimental observables-e.g., the finite ion size-or optimized for agreement with experimental results. Experimental data for this optimization are available in the form of Sechenov coefficients that describe the linear dependence of the salting-out effect of solutes with respect to the electrolyte concentration. In the final part, we rationalize the qualitative disagreement of the finite ion size modification to the Poisson-Boltzmann model with experimental observations by taking into account the electrolyte concentration dependence of the Stern layer. A route toward a revised model that captures the experimental observations while including the finite ion size effects is then outlined. This implementation paves the way for the study of electrochemical and electrocatalytic processes of molecules and cluster models with accurate electronic structure methods

Electron spin relaxation of N@C60 in CS2

We examine the temperature dependence of the relaxation times of the molecules N@C60 and N@C70 (which comprise atomic nitrogen trapped within a carbon cage) in liquid CS2 solution. The results are inconsistent with the fluctuating zero field splitting (ZFS) mechanism, which is commonly invoked to explain electron spin relaxation for S > 1/2 spins in liquid solution, and is the mechanism postulated in the literature for these systems. Instead, we find a clear Arrhenius temperature dependence for N@C60, indicating the spin relaxation is driven primarily by an Orbach process. For the asymmetric N@C70 molecule, which has a permanent non-zero ZFS, we resolve an additional relaxation mechanism caused by the rapid reorientation of its ZFS. We also report the longest coherence time (T2) ever observed for a molecular electron spin, being 0.25 ms at 170K.Comment: 6 pages, 6 figures V2: Updated to published versio

Electron spin coherence in metallofullerenes: Y, Sc and La@C82

Endohedral fullerenes encapsulating a spin-active atom or ion within a carbon cage offer a route to self-assembled arrays such as spin chains. In the case of metallofullerenes the charge transfer between the atom and the fullerene cage has been thought to limit the electron spin phase coherence time (T2) to the order of a few microseconds. We study electron spin relaxation in several species of metallofullerene as a function of temperature and solvent environment, yielding a maximum T2 in deuterated o-terphenyl greater than 200 microseconds for Y, Sc and La@C82. The mechanisms governing relaxation (T1, T2) arise from metal-cage vibrational modes, spin-orbit coupling and the nuclear spin environment. The T2 times are over 2 orders of magnitude longer than previously reported and consequently make metallofullerenes of interest in areas such as spin-labelling, spintronics and quantum computing.Comment: 5 pages, 4 figure

A realignment of marine biogeographic provinces with particular reference to fish distributions

Marine provinces, founded on contrasting floras or faunas, have been recognized for more than 150 years but were not consistently defined by endemism until 1974. At that time, provinces were based on at least a 10% endemism and nested within biogeographic regions that covered large geographic areas with contrasting biotic characteristics. Over time, some minor adjustments were made but the overall arrangement remained essentially unaltered. In many provinces, data on endemism were still not available, or available only for the most widely-studied vertebrates (fishes), an ongoing problem. In this report we propose a realignment for three reasons. First, recent works have provided new information to modify or redefine the various divisions and to describe new ones, including the Mid-Atlantic Ridge, Southern Ocean, Tropical East Pacific, and Northeast Pacific. Second, phylogeographic studies have demonstrated genetic subdivisions within and between species that generally corroborated provinces based on taxonomic partitions, with a notable exception at the Indian-Pacific oceanic boundary. Third, the original separation of the warm-temperate provinces from the adjoining tropical ones has distracted from their close phylogenetic relationships. Here we propose uniting warm-temperate and tropical regions into a single warm region within each ocean basin, while still recognizing provinces within the warm-temperate and tropical zones. These biogeographic subdivisions are based primarily on fish distribution but utilize other marine groups for comparison. They are intended to demonstrate the evolutionary relationships of the living marine biota, and to serve as a framework for the establishment of smaller ecological units in a conservation context.This is the author's manuscript version. The published article is copyrighted by John Wiley & Sons, Inc. and can be found at: http://onlinelibrary.wiley.com/journal/10.1111/%28ISSN%291365-2699.Keywords: Speciation, Fishes, Marine biogeography, Zoogeography., Endemism, Evolution, Regions, Phylogeography, Province

A quasi classical approach to fully differential ionization cross sections

A classical approximation to time dependent quantum mechanical scattering in the M\o{}ller formalism is presented. Numerically, our approach is similar to a standard Classical-Trajectory-Monte-Carlo calculation. Conceptually, however, our formulation allows one to release the restriction to stationary initial distributions. This is achieved by a classical forward-backward propagation technique. As a first application and for comparison with experiment we present fully differential cross sections for electron impact ionization of atomic hydrogen in the Erhardt geometry.Comment: 6 pages, 2 figure

Coherent state transfer between an electron- and nuclear spin in 15N@C60

Electron spin qubits in molecular systems offer high reproducibility and the ability to self assemble into larger architectures. However, interactions between neighbouring qubits are 'always-on' and although the electron spin coherence times can be several hundred microseconds, these are still much shorter than typical times for nuclear spins. Here we implement an electron-nuclear hybrid scheme which uses coherent transfer between electron and nuclear spin degrees of freedom in order to both controllably turn on/off dipolar interactions between neighbouring spins and benefit from the long nuclear spin decoherence times (T2n). We transfer qubit states between the electron and 15N nuclear spin in 15N@C60 with a two-way process fidelity of 88%, using a series of tuned microwave and radiofrequency pulses and measure a nuclear spin coherence lifetime of over 100 ms.Comment: 5 pages, 3 figures with supplementary material (8 pages

Towards a fullerene-based quantum computer

Molecular structures appear to be natural candidates for a quantum technology: individual atoms can support quantum superpositions for long periods, and such atoms can in principle be embedded in a permanent molecular scaffolding to form an array. This would be true nanotechnology, with dimensions of order of a nanometre. However, the challenges of realising such a vision are immense. One must identify a suitable elementary unit and demonstrate its merits for qubit storage and manipulation, including input / output. These units must then be formed into large arrays corresponding to an functional quantum architecture, including a mechanism for gate operations. Here we report our efforts, both experimental and theoretical, to create such a technology based on endohedral fullerenes or 'buckyballs'. We describe our successes with respect to these criteria, along with the obstacles we are currently facing and the questions that remain to be addressed.Comment: 20 pages, 13 figs, single column forma

Providing Nuclear Criticality Safety Analysis Education through Benchmark Experiment Evaluation

One of the challenges that today's new workforce of nuclear criticality safety engineers face is the opportunity to provide assessment of nuclear systems and establish safety guidelines without having received significant experience or hands-on training prior to graduation. Participation in the International Criticality Safety Benchmark Evaluation Project (ICSBEP) and/or the International Reactor Physics Experiment Evaluation Project (IRPhEP) provides students and young professionals the opportunity to gain experience and enhance critical engineering skills

Violation of a Leggett-Garg inequality with ideal non-invasive measurements

The quantum superposition principle states that an entity can exist in two different states simultaneously, counter to our 'classical' intuition. Is it possible to understand a given system's behaviour without such a concept? A test designed by Leggett and Garg can rule out this possibility. The test, originally intended for macroscopic objects, has been implemented in various systems. However to-date no experiment has employed the 'ideal negative result' measurements that are required for the most robust test. Here we introduce a general protocol for these special measurements using an ancillary system which acts as a local measuring device but which need not be perfectly prepared. We report an experimental realisation using spin-bearing phosphorus impurities in silicon. The results demonstrate the necessity of a non-classical picture for this class of microscopic system. Our procedure can be applied to systems of any size, whether individually controlled or in a spatial ensemble.Comment: 6+4 pages. Supplementary Methods section include