Vapor Pressure versus Temperature Relations of Common Elements.

The vapor pressure values of common elements are available in the literature over a limited temperature range and the accuracy and reliability of the reported data are not generally available. We evaluate the reliability and uncertainty of the available vapor pressure versus temperature data of fifty common pure elements and recommend vapor pressure versus temperature relations. By synthesizing the vapor pressure values from measurements reported in the literature with the values computed using the Clausius Clapeyron relation beyond the boiling point, we extend the vapor pressure range from 10-8 atm to 10 atm. We use a genetic algorithm to optimize the fitting of the vapor pressure data as a function of temperature over the extended vapor pressure range for each element. The recommended vapor pressure values are compared with the corresponding literature values to examine the reliability of the recommended values.

Staged complex abdominal wall hernia repair in morbidly obese patients.

PURPOSE: The repair of complex abdominal wall hernias in morbidly obese patients is often associated with a higher risk of complications and hernia recurrences. Improvement in obesity and its associated metabolic complications are hypothesized to improve hernia repair outcomes. This study analyzes outcomes from morbidly obese patients who underwent bariatric surgery with staged complex abdominal wall reconstruction at Creighton University Medical Center (CUMC). METHODS: This retrospective study included morbidly obese patients with complex abdominal wall hernia, who underwent bariatric surgery with staged abdominal wall reconstruction. Data points collected included patient demographics, obesity-related co-morbidities, pre-operative BMI, EBMIL at 12 months, hernia characteristics, postoperative complications, BMI at time of hernia repair, and hernia recurrence. RESULTS: Twelve patients with an average BMI of 48 and complex abdominal wall hernias (mean width 14.0 cm) met inclusion criteria. Seven patients (58%) had significant loss of domain. Bariatric procedures included six laparoscopic sleeve gastrectomies (LSG), three laparoscopic Roux-en-Y gastric bypasses (LRNYGB), and three revisional procedures (2 vertical band gastroplasties to LRNYGB and 1 LRNYGB revision). At 12-month follow-up, the mean excess BMI loss (EBMIL) was 64.6%. The average time to staged complex abdominal wall reconstruction was 22.3 months. Two non-elective hernia repairs were performed due to one incarceration and one strangulation. There were no recurrences after an average follow-up of 21.9 months. CONCLUSIONS: In this study, staged mesh repair of complex abdominal wall hernias after bariatric surgery in morbidly obese patients was associated with acceptable morbidity and no hernia recurrences at approximately 1.5 year follow-up.

Numerical simulations of different sectoral contributions to post monsoon pollution over Delhi.

The National Capital Region (NCR) of India, Delhi, has experienced high post-monsoon pollution along with several peak pollution episodes in recent years. Diwali, the festival of lights, which is among the biggest festivals of India celebrated during the post-monsoon season, is also considered a pollution event associated as it is with the lighting of a large number of firecrackers. 2016 Diwali pollution episode continued for a week creating severe discomfort to residents of Delhi, prompting the judiciary to ban the sale and use of firecrackers in Delhi from 2017 onwards. The current study analyzes different sectoral and temporal emissions contribution to the 2016 post monsoonal pollution episode over Delhi using a fully coupled chemical transport model. The findings of the study indicate that aerosols produced from crop residue open burning at the northwestern states contributed more than 60% of the total simulated surface concentration during the period under study. Model experimental simulations show that despite emissions from within the city, what explains the severity of pollution over Delhi during the period under consideration is an additional pollution load emanating from these intense crop open burning sessions from nearby areas. Further, model simulations show that while Diwali emissions can elevate the pollution load over Delhi, the effects do not last beyond 48 h. It is found that the stagnation of the pollutants several days beyond the 2016 Diwali day was due to favorable meteorological conditions like low surface temperature, lower boundary layer height, and weak northwesterly winds. The study shows that in order to improve air quality in Delhi during the post-monsoon period, mitigation efforts should target the adjacent rural areas, especially when there is massive burning of crop residue in those areas.

Electronic structure of twisted and planar rubrene molecules: a density functional study.

X-ray absorption spectra (XAS), the density of states (DOS) and the electron density distribution of the HOMO and LUMO for flat and twisted rubrene molecules have been calculated using density functional theory (DFT). The simulated XAS spectra are validated by experimental C K-edge near-edge X-ray absorption fine structure (NEXAFS) data. We demonstrate that the NEXAFS spectra of rubrene thin films of different thicknesses can be explained in terms of different combinations of spectral intensity from the twisted and the flat randomly oriented molecules. All the fine structure of the NEXAFS spectra is well reproduced and the energetic positions of the resonances agree within a window of ±0.3 eV with the calculated XAS. Our calculation reveals that the peak at lowest photon energy (α') of the NEXAFS spectra at the lower coverage of rubrene molecules appears only from the twisted molecules. Other peaks in the case of the flat molecules appear either from the backbone or the wings, whereas, for the twisted molecules, the backbone and the wings contribute somewhat equally. Lowering of the HOMO-LUMO gap, as well as redistribution of the electron density of both the frontier orbitals, is found to take place in the case of the twisted molecule. The redistribution explains the reduction in conductivity for the twisted molecule compared to the flat one despite the lower band gap for the former. This finding will further strengthen the progress of rubrene thin film based devices.

A Comparison of Practice Pattern and Outcome of Twice-weekly and Thrice-weekly Hemodialysis Patients.

Renal replacement therapy (RRT) options and practice varies in countries worldwide and is influenced by patients' choice, nephrologists' practice patterns, health system, payer practice, public policy, and socioeconomic factors. In India, hemodialysis (HD) remains the dominant RRT modality, and the practice is largely influenced by socioeconomics of the region of practice since third party payer is limited. Resource stretch to maximize outcome benefit is essential and HD session twice weekly is an improvized and cost-effective clinical practice. However, within the country, the patient characteristics, practice patterns, and outcomes of twice-weekly HD compared against patients dialyzed thrice weekly remain unclear. We did a retrospective analysis of patients who underwent twice- and thrice-weekly HD in a single center under similar settings. The patients on thrice a week dialysis were older and with a higher proportion of diabetics and were insured by private payers. Weight gain, ultrafiltration rates, blood pressures, and hemoglobin remained more favorable in the thrice-weekly patients. There was no significant difference in the hospitalization rates or mortality rates in the two groups. Patients who undergo twice-weekly HD have poorer intermediate measures of the outcome; although, morbidity and survival were not different in a small study population with short follow-up. The small sample size and the short duration of follow-up may limit the scope of findings of our study.

Non-canonical NFκB mutations reinforce pro-survival TNF response in multiple myeloma through an autoregulatory RelB:p50 NFκB pathway.

Environmental drug resistance constitutes a serious impediment for therapeutic intervention in multiple myeloma. Tumor-promoting cytokines, such as tumor necrosis factor (TNF), induce nuclear factor-κB (NFκB)- driven expression of pro-survival factors, which confer resistance in myeloma cells to apoptotic insults from TNF-related apoptosis-inducing ligand (TRAIL) and other chemotherapeutic drugs. It is thought that RelA:p50 dimer, activated from IκBα-inhibited complex in response to TNF-induced canonical NFκB signal, mediates the pro-survival NFκB function in cancerous cells. Myeloma cells additionally acquire gain-of-function mutations in the non-canonical NFκB module, which induces partial proteolysis of p100 into p52 to promote RelB:p52/NFκB activation from p100-inhibited complex during immune cell differentiation. However, role of non-canonical NFκB signaling in the drug resistance in multiple myeloma remains unclear. Here we report that myeloma-associated non-canonical aberrations reinforce pro-survival TNF signaling in producing a protracted TRAIL-refractory state. These mutations did not act through a typical p52 NFκB complex, but completely degraded p100 to reposition RelB under IκBα control, whose degradation during TNF signaling induced an early RelB:p50 containing NFκB activity. More so, autoregulatory RelB synthesis prolonged this TNF-induced RelB:p50 activity in myeloma cells harboring non-canonical mutations. Intriguingly, TNF-activated RelB:p50 dimer was both necessary and sufficient, and RelA was not required, for NFκB-dependent pro-survival gene expressions and suppression of apoptosis. Indeed, high RelB mRNA expressions in myeloma patients correlated with the augmented level of pro-survival factors and resistance to therapeutic intervention. In sum, we provide evidence that cancer-associated mutations perpetuate TNF-induced pro-survival NFκB activity through autoregulatory RelB control and thereby exacerbate environmental drug resistance in multiple myeloma.

Developing the 'gripes' tool for junior doctors to report concerns: a pilot study.

BACKGROUND: Junior doctors often have concerns about quality and safety but show low levels of engagement with incident reporting systems. We aimed to develop and pilot a web-based reporting tool for junior doctors to proactively report concerns about quality and safety of care, and optimise it for future use. METHODS: We developed the gripes tool with input from junior doctors and piloted it at a large UK teaching hospital trust. We evaluated the tool through an analysis of concerns reported over a 3-month pilot period, and through interviews with five stakeholders and two focus groups with medical students and junior doctors about their views of the tool. RESULTS: Junior doctors reported 111 concerns during piloting, including a number of problems previously unknown to the trust. Junior doctors felt the tool was easy to use and encouraged them to report. Barriers to engagement included lack of motivation of junior doctors to report concerns, and fear of repercussions. Ensuring transparency about who would see reported concerns, and providing feedback across whole cohorts of junior doctors about concerns raised and how these had been addressed to improve patient safety at the trust, were seen having the potential to mitigate against these barriers. Sustainability of the tool was seen as requiring a revised model of staffing to share the load for responding to concerns and ongoing efforts to integrate the tool and data with other local systems for gathering intelligence about risks and incidents. Following piloting the trust committed to continuing to operate the gripes tool on an ongoing basis. CONCLUSIONS: The gripes tool has the potential to enable trusts to proactively monitor and address risks to patient safety, but sustainability is likely to be dependent on organisational commitment to staffing the system and perceptions of added value over the longer term.

Printability of alloys for additive manufacturing.

Although additive manufacturing (AM), or three dimensional (3D) printing, provides significant advantages over existing manufacturing techniques, metallic parts produced by AM are susceptible to distortion, lack of fusion defects and compositional changes. Here we show that the printability, or the ability of an alloy to avoid these defects, can be examined by developing and testing appropriate theories. A theoretical scaling analysis is used to test vulnerability of various alloys to thermal distortion. A theoretical kinetic model is used to examine predisposition of different alloys to AM induced compositional changes. A well-tested numerical heat transfer and fluid flow model is used to compare susceptibilities of various alloys to lack of fusion defects. These results are tested and validated with independent experimental data. The findings presented in this paper are aimed at achieving distortion free, compositionally sound and well bonded metallic parts.

Oxidation of rubrene thin films: an electronic structure study.

The performances of organic semiconductor devices are crucially linked with their stability at the ambient atmosphere. The evolution of electronic structures of 20 nm thick rubrene films exposed to ambient environment with time has been studied by UV and X-ray photoemission spectroscopy (UPS and XPS), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, and density functional theory (DFT). XPS, NEXAFS data, and DFT calculated values suggest the formation of rubrene-epoxide and rubrene-endoperoxide through reaction of tetracene backbone with oxygen of ambient environment. Angle dependent XPS measurement indicates that the entire probed depth of the films reacts with oxygen by spending only about 120 min in ambient environment. The HOMO peak of pristine rubrene films almost disappears by exposure of 120 min to ambient environment. The evolution of the valence band (occupied states) and NEXAFS (unoccupied states) spectra indicates that the films become more insulating with exposure as the HOMO-LUMO gap increases on oxidation. Oxygen induced chemical reaction completely destroys the delocalized nature of the electron distribution in the tetracene backbone of rubrene. The results are relevant to the performance and reliability of rubrene based devices in the environment.

Investigation on the adsorption characteristics of anserine on the surface of colloidal silver nanoparticles.

The surface-enhanced Raman scattering (SERS) studies of anserine (beta-alanyl-N-methylhistidine) was carried out on colloidal silver nanoparticles to understand its adsorption characteristics. The experimentally observed Raman bands were assigned based on the results of DFT calculations. The studies suggest that the interaction of anserine is primarily through the carboxylate group with the imidazole ring in an upright position with respect to the silver surface. Concentration dependent SERS studies suggest a change in orientation at sub-monolayer concentration.

Tumour necrosis factor-alpha and nitric oxide response in different categories of tuberculosis patients.

OBJECTIVE: To compare the magnitude of tumour necrosis factor alpha (TNF-α) and nitric oxide (NO) response in different categories of active tuberculosis (TB) patients by ex vivo experiment. DESIGN: New, relapsed (recurrent), miliary and pleural effusion TB cases were recruited with matched healthy controls. TNF-α and NO were measured from the culture supernatant of peripheral blood monocytes derived from cases and controls with and without challenge with live Mycobacterium tuberculosis H37Rv. RESULTS: TNF-α and NO production varied significantly among the different categories of TB patients. The magnitude was highest among patients with pleural effusion and lowest in miliary TB cases. In between, progressive decreases in response were noted in new and relapse cases. Overall, positive correlations between TNF-α and NO were noted among the diseased and healthy groups. CONCLUSION: Distinct TNF-α and NO levels appear to be associated with different clinical forms of TB and might help to assess prognosis and contribute to a better understanding of underlying immunopathological mechanisms.

Observation of 2p3d(1Po)→1s3d(1De) radiative transition in He-like Si, S, and Cl ions.

We present an experimental determination of the 2p3d(1Po)→1s3d(1De) x-ray line emitted from He-like Si, S, and Cl projectile ions, excited in collisions with thin carbon foils, using a high-resolution bent-crystal spectrometer. A good agreement between the observation and state-of-the-art relativistic calculations using the multiconfiguration Dirac-Fock formalism including the Breit interaction and QED effects implies the dominance of fluorescent decay over the autoionization process for the 2p3d(^{1}P^{o}) state of He-like heavy ions. This is the first observation of the fluorescence-active doubly excited states in He-like Si, S, and Cl ions.

Genetic analysis of fibroblast growth factor signaling in the Drosophila eye.

The development of eyes in Drosophila involves intricate epithelial reorganization events for accurate positioning of cells and proper formation and organization of ommatidial clusters. We demonstrate that Branchless (Bnl), the fibroblast growth factor ligand, regulates restructuring events in the eye disc primordium from as early as the emergence of clusters from a morphogenetic front to the cellular movements during pupal eye development. Breathless (Btl) functions as the fibroblast growth factor receptor to mediate Bnl signal, and together they regulate expression of DE-cadherin, Crumbs, and Actin. In addition, in the eye Bnl regulates the temporal onset and extent of retinal basal glial cell migration by activating Btl in the glia. We hypothesized that the Bnl functions in the eye are Hedgehog dependent and represent novel aspects of Bnl signaling not explored previously.

Core dysfunction in schizophrenia: electrophysiology trait biomarkers.

OBJECTIVE: Core symptoms of schizophrenia, particularly in the cognitive domain are hypothesized to be due to an abnormality in neural connectivity. Biomarkers of connectivity may therefore be a promising tool in exploring the aetiology of schizophrenia. We used electrophysiological methods to demonstrate abnormal visual information processing during in patients performing a simple cognitive task. METHOD: Electrophysiological recordings were acquired from 20 chronically ill, medicated patients diagnosed with either schizophrenia or schizo-affective disorder and 20 healthy volunteers while they conducted a working memory (WM) task. RESULTS: The patient group had significantly lower accuracy on the WM task and a trend for slower responses. An early visual evoked response potential was reduced in patients. Analysis of the electroencephalographic oscillations showed a decreased phase-locking factor (in the theta, beta and gamma bands) and signal power (theta frequency band). The beta and gamma oscillatory abnormalities were confined to two sets of correlated fronto and occipital electrodes. CONCLUSION: The findings of event-related potential and oscillatory abnormalities in patients with schizophrenia confirm the sensitivity of early visual information processing measurements for identification of schizophrenia phenotype. The fronto-occipital distribution of the oscillatory abnormalities replicates our findings from a schizotypal sample and implicates a possible top-down dysfunction as a vulnerability trait.

Antioxidant activity and free radical scavenging reactions of gentisic acid: in-vitro and pulse radiolysis studies.

Abstract Antioxidant activity of gentisic acid has been studied using fast chemical kinetics and two in vitro models, namely the isolated rat liver mitochondria (RLM) and the human erythrocytes. The presence of gentisic acid (GA) during irradiation significantly reduced the levels of gamma radiation induced damages to lipids and proteins in RLM. Further, GA imparted protection to the human erythrocytes against exposure to gamma radiation. Molecular mechanism of free radical scavenging reactions has been evaluated with the help of rate constants and transients obtained from gentisic acid using pulse radiolysis technique. GA efficiently scavenged hydroxyl radical (k = 1.1 × 10(10) dm(3)mol(-1)s(-1)) to produce reducing adduct radical (~76%) and oxidizing phenoxyl radical (~24%). GA has also scavenged organohaloperoxyl radical (k = 9.3 × 10(7) dm(3) mol(-1)s(-1)). Ascorbate has been found to repair phenoxyl radical of GA (k = 1.0 × 10(7) dm(3)mol(-1)s(-1)). Redox potential value of GA(•)/GA couple (0.774 V vs NHE) obtained by cyclic voltammetry is less than those of physiologically important oxidants, which supports the observed antioxidant capacity of GA. We, therefore, propose that the antioxidant and radioprotective properties of GA are exerted by its phenoxyl group.

Instability range of microsolvated multiply charged negative ions: prediction from detachment energy of stable hydrated clusters.

We have presented a first-principle theory-based derivation of an exact expression for the solvent number-dependent electron-detachment energy of a solvated species in the thermodynamic limit. We also propose a generalized equation bridging the electron detachment energies for small and infinitely large clusters, thus providing a new route to calculate the ionization potential of a negatively charged ion from the electron-detachment energies of its stable hydrated clusters. Most importantly, it has the ability to predict the instability range of microhydrated anions. The calculated results for the ionization potential for a number of ions are found to be in good agreement with the available experimental results, and the predicted instability range for the doubly charged anions SO4²â» and C2O4²â» is also consistent with experimental and ab initio results.

Structure and IR spectra of microhydrated Cl2 with an excess electron: experiment versus theory.

A working methodology to generate theoretical IR spectra following ab initio electronic structure methods is reported. Theoretical IR spectra of Cl(2)(•-)·nH(2)O clusters (n = 1-5) are generated as a case study. Excellent agreement between the calculated and the reported experimental IR spectra based on size-selected spectroscopy is observed. It is shown that uniform scaling of calculated harmonic frequencies of these hydrated clusters fail to produce accurate IR spectra. Two different scaling factors in two different regions of O-H stretching of solvent water molecules are needed to account for the anharmonic contribution. This observation is also true for Br(2)(•-)·nH(2)O and I(2)(•-)·nH(2)O systems.

Free radical reactions with the extract of brassica family.

Using different extraction protocols, the antioxidant properties of green and red cabbage extracts were evaluated in terms of the total antioxidant capacities using the 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulphonic acid) (ABTS) radical scavenging method. The results demonstrate that the total antioxidant capacity of green and red cabbages correlated well with the total phenolics and total flavonoids content present in the extracts. The ABTS radical scavenging capacity of red cabbage was much higher than that of green cabbage extract. Using time resolved absorption kinetic spectrophotometry, free radical reactions with the extracts of green and red cabbages were established. The reactions of extracts were examined using a pulse radiolysis technique. Kinetic studies indicated that extracts may act as free radical scavengers for O2(-), OH radicals and as an antioxidant to repair free-radical damage to biologically important guanosine radical.