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A diuranium carbide cluster stabilized inside a C80 fullerene cage.
Unsupported non-bridged uranium-carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing Ih(7)-C80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@Ih(7)-C80. This endohedral fullerene was prepared utilizing the Krätschmer-Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@Ih(7)-C80·[NiII-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium-carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@Ih(7)-C80 and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses
On the Upper Limits of Oxidation States in Chemistry.
The concept of oxidation state (OS) is based on the concept of Lewis electron pairs, in which the bonding electrons are assigned to the more electronegative element. This approach is useful for keeping track of the electrons, predicting chemical trends, and guiding syntheses. Experimental and quantum-chemical results reveal a limit near +8 for the highest OS in stable neutral chemical substances under ambient conditions. OS=+9 was observed for the isolated [IrO4 ]+ cation in vacuum. The prediction of OS=+10 for isolated [PtO4 ]2+ cations is confirmed computationally for low temperatures only, but hasn't yet been experimentally verified. For high OS species, oxidation of the ligands, for example, of O-2 with formation of . O-1 and O-O bonds, and partial reduction of the metal center may be favorable, possibly leading to non-Lewis type structures
Expression of Foxp3 in colorectal cancer but not in Treg cells correlates with disease progression in patients with colorectal cancer
Background: Regulatory T cells (Treg) expressing the transcription factor forkhead-box protein P3 (Foxp3) have been identified to counteract anti-tumor immune responses during tumor progression. Besides, Foxp3 presentation by cancer cells itself may also allow them to evade from effector T-cell responses, resulting in a survival benefit of the tumor. For colorectal cancer (CRC) the clinical relevance of Foxp3 has not been evaluated in detail. Therefore the aim of this study was to study its impact in colorectal cancer (CRC).
Methods and Findings: Gene and protein analysis of tumor tissues from patients with CRC was performed to quantify the expression of Foxp3 in tumor infiltrating Treg and colon cancer cells. The results were correlated with clinicopathological parameters and patients overall survival. Serial morphological analysis demonstrated Foxp3 to be expressed in cancer cells. High Foxp3 expression of the cancer cells was associated with poor prognosis compared to patients with low Foxp3 expression. In contrast, low and high Foxp3 level in tumor infiltrating Treg cells demonstrated no significant differences in overall patient survival.
Conclusions: Our findings strongly suggest that Foxp3 expression mediated by cancer cells rather than by Treg cells contribute to disease progression
Global data for ecology and epidemiology: a novel algorithm for temporal Fourier processing MODIS data
Background. Remotely-sensed environmental data from earth-orbiting satellites are increasingly used to model the distribution and abundance of both plant and animal species, especially those of economic or conservation importance. Time series of data from the MODerate-resolution Imaging Spectroradiometer (MODIS) sensors on-board NASA's Terra and Aqua satellites offer the potential to capture environmental thermal and vegetation seasonality, through temporal Fourier analysis, more accurately than was previously possible using the NOAA Advanced Very High Resolution Radiometer (AVHRR) sensor data. MODIS data are composited over 8- or 16-day time intervals that pose unique problems for temporal Fourier analysis. Applying standard techniques to MODIS data can introduce errors of up to 30% in the estimation of the amplitudes and phases of the Fourier harmonics. Methodology/Principal Findings. We present a novel spline-based algorithm that overcomes the processing problems of composited MODIS data. The algorithm is tested on artificial data generated using randomly selected values of both amplitudes and phases, and provides an accurate estimate of the input variables under all conditions. The algorithm was then applied to produce layers that capture the seasonality in MODIS data for the period from 2001 to 2005. Conclusions/Significance. Global temporal Fourier processed images of 1 km MODIS data for Middle Infrared Reflectance, day- and night-time Land Surface Temperature (LST), Normalised Difference Vegetation Index (NDVI), and Enhanced Vegetation Index (EVI) are presented for ecological and epidemiological applications. The finer spatial and temporal resolution, combined with the greater geolocational and spectral accuracy of the MODIS instruments, compared with previous multi-temporal data sets, mean that these data may be used with greater confidence in species' distribution modelling
Comparison of tricuspid inflow and superior vena caval Doppler velocities in acute simulated hypovolemia: new non-invasive indices for evaluating right ventricular preload
BACKGROUND: Assessment of cardiac preload is important for clinical management of some emergencies related to hypovolemia. Effects of acute simulated hypovolemia on Doppler blood flow velocity indices of tricuspid valve (TV) and superior vena cava (SVC) were investigated in order to find sensitive Doppler indices for predicting right ventricular preload. METHODS: Doppler flow patterns of SVC and TV in 12 healthy young men were examined by transthoracic echocardiography (TTE) during graded lower body negative pressure (LBNP) of up to -60 mm Hg which simulated acute hypovolemia. Peak velocities of all waves and their related ratios (SVC S/D and tricuspid E/A) were measured, calculated and statistically analyzed. RESULTS: Except for the velocity of tricuspid A wave, velocities of all waves and their related ratios declined during volume decentralization. Of all indices measured, the peak velocities of S wave and AR wave in SVC correlated most strongly with levels of LBNP (r = -0.744 and -0.771, p < 0.001). CONCLUSION: The S and AR velocities are of good values in assessing right ventricular preload. Monitoring SVC flow may provide a relatively noninvasive means to assess direct changes in right ventricular preload
Intraoperative device closure of atrial septal defects in the Older Population
<p>Abstract</p> <p>Objective</p> <p>This study sought to prove the safety and feasibility of intraoperative device closure of atrial septal defect (ASD) with transthoracic minimal invasion in the older patients.</p> <p>Methods</p> <p>From January 2006 to December 2009, 47 patients aged 50 years or more and suffered from atrial septal defect were enrolled in our institution. Patients were divided into two groups, 27 of which in group I with intraoperative device closure and the other 20 in group II with surgical closure. In group I, the method involved a minimal intercostal incision, which was performed after full evaluation of the atrial septal defect by transthoracic echocardiography, and the insertion of the device through the delivery sheath to occlude the atrial septal defect.</p> <p>Results</p> <p>In group I, implantation was ultimately successful in all patients. The complete closure rate at 24 hours and 1 year were 81.5% and 100% respectively. In 6 of 27 patients, minor complications occurred: transient arrhythmia (n = 5) and blood transfusion (n = 3). In group II, all patients were closured successfully; almost all of them needed blood transfusion and suffered from various minor complications though. During a follow-up period of 1 to 5 years, no residual shunt, noticeable mitral regurgitation, significant arrhythmias, thrombosis, or device failure were found. In our comparative studies, group II had significantly longer ICU stay and hospital stay than group I (p < 0.05). The cost of group I was less than that of group II(p < 0.05).</p> <p>Conclusions</p> <p>Minimally invasive transthoracic device closure of the atrial septal defect at advanced age with a domestically made device without cardiopulmonary bypass is safe and feasible under transthoracic echocardiographic guidance. It was cost-savings, yielding better cosmetic results and leaving fewer traumas than surgical closure. Early and mid-term results are encouraging. However, it is necessary to evaluate the long-term results.</p
A stochastic model of Escherichia coli AI-2 quorum signal circuit reveals alternative synthesis pathways
Quorum sensing (QS) is an important determinant of bacterial phenotype. Many cell functions are regulated by intricate and multimodal QS signal transduction processes. The LuxS/AI-2 QS system is highly conserved among Eubacteria and AI-2 is reported as a ‘universal' signal molecule. To understand the hierarchical organization of AI-2 circuitry, a comprehensive approach incorporating stochastic simulations was developed. We investigated the synthesis, uptake, and regulation of AI-2, developed testable hypotheses, and made several discoveries: (1) the mRNA transcript and protein levels of AI-2 synthases, Pfs and LuxS, do not contribute to the dramatically increased level of AI-2 found when cells are grown in the presence of glucose; (2) a concomitant increase in metabolic flux through this synthesis pathway in the presence of glucose only partially accounts for this difference. We predict that ‘high-flux' alternative pathways or additional biological steps are involved in AI-2 synthesis; and (3) experimental results validate this hypothesis. This work demonstrates the utility of linking cell physiology with systems-based stochastic models that can be assembled de novo with partial knowledge of biochemical pathways
Second law, entropy production, and reversibility in thermodynamics of information
We present a pedagogical review of the fundamental concepts in thermodynamics
of information, by focusing on the second law of thermodynamics and the entropy
production. Especially, we discuss the relationship among thermodynamic
reversibility, logical reversibility, and heat emission in the context of the
Landauer principle and clarify that these three concepts are fundamentally
distinct to each other. We also discuss thermodynamics of measurement and
feedback control by Maxwell's demon. We clarify that the demon and the second
law are indeed consistent in the measurement and the feedback processes
individually, by including the mutual information to the entropy production.Comment: 43 pages, 10 figures. As a chapter of: G. Snider et al. (eds.),
"Energy Limits in Computation: A Review of Landauer's Principle, Theory and
Experiments
Wettability of amorphous and nanocrystalline Fe78B13Si9 substrates by molten Sn and Bi
The wettability of amorphous and annealing-induced nanocrystalline Fe78B13Si9 ribbons by molten Sn and Bi at 600 K was measured using an improved sessile drop method. The results demonstrate that the structural relaxation and crystallization in the amorphous substrates do not substantially change the wettability with molten Bi because of their invariable physical interaction, but remarkably deteriorate the wettability and interfacial bonding with molten Sn as a result of changing a chemical interaction to a physical one for the atoms at the interface
Evaluation of Pseudo-Haptic Interactions with Soft Objects in Virtual Environments
This paper proposes a pseudo-haptic feedback method conveying simulated soft surface stiffness information through a visual interface. The method exploits a combination of two feedback techniques, namely visual feedback of soft surface deformation and control of the indenter avatar speed, to convey stiffness information of a simulated surface of a soft object in virtual environments. The proposed method was effective in distinguishing different sizes of virtual hard nodules integrated into the simulated soft bodies. To further improve the interactive experience, the approach was extended creating a multi-point pseudo-haptic feedback system. A comparison with regards to (a) nodule detection sensitivity and (b) elapsed time as performance indicators in hard nodule detection experiments to a tablet computer incorporating vibration feedback was conducted. The multi-point pseudo-haptic interaction is shown to be more time-efficient than the single-point pseudo-haptic interaction. It is noted that multi-point pseudo-haptic feedback performs similarly well when compared to a vibration-based feedback method based on both performance measures elapsed time and nodule detection sensitivity. This proves that the proposed method can be used to convey detailed haptic information for virtual environmental tasks, even subtle ones, using either a computer mouse or a pressure sensitive device as an input device. This pseudo-haptic feedback method provides an opportunity for low-cost simulation of objects with soft surfaces and hard inclusions, as, for example, occurring in ever more realistic video games with increasing emphasis on interaction with the physical environment and minimally invasive surgery in the form of soft tissue organs with embedded cancer nodules. Hence, the method can be used in many low-budget applications where haptic sensation is required, such as surgeon training or video games, either using desktop computers or portable devices, showing reasonably high fidelity in conveying stiffness perception to the user
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