Binding Behavior of Crystalline and Noncrystalline Phases: Evaluation of the Enthalpic and Entropic Contributions to the Separation Selectivity of Nonpolar Solutes with a Novel Chromatographic Sorbent

In this paper, we describe studies of the retention characteristics of nonpolar molecules with a novel liquidcrystalline, silica-supported, comb-shaped polymer chromatographic phase, Sil-ODA 18 . These results extend and amplify previous reports of the roles of enthalpic-and entropic-driven processes in the modulation of the selectivity of nonpolar and polar compounds in reversed-phase high-performance liquid chromatography (RP-HPLC). The investigations reveal that phase reorganization is the most important factor controlling selectivity enhancement with silica-supported, comb-shaped polymer phases as the temperature, T, of the system is varied. Moreover, these studies demonstrate that contributions from the stationary and the mobile phases can be independently fine-tuned to achieve enhanced selectivity via partition and/or adsorption binding processes. The relevant thermodynamic parameters, namely, the changes in enthalpy, entropy, and heat capacity for various nonpolar solutes with this comb-shaped polymeric sorbent, have also been determined using recently developed analytical procedures for the evaluation of nonlinear van't Hoff plots. These investigations into the thermodynamic properties of the comb-shaped polymeric sorbent in its ordered crystalline and noncrystalline states clearly delineate the differences in binding behavior compared to conventional types of monolayer n-alkylsilica sorbents and thus should facilitate wider application of this new class of reversed-phase sorbents in the separation sciences. Introduction Reversed-phase chromatography (RPC) is currently the most widely used of all of the high-performance liquid chromatographic (HPLC) modes of separations. The evaluation of the physicochemical basis of the retention mechanisms of different classes of solutes in RPC has received extensive attention, with the experimental results often interpreted in terms of the solvophobic model proposed by Horvath et al. 1,2 A central question pertaining to all RPC separations is, What drives the retention process? This question has been the subject of considerable debate and investigation since the concept of RPC was first used in 1950 as an analytical separation method by Howard and Martin. 3 Two primary RPC mechanisms can be considered, namely, the solvation/desolvation model, 1,2 whereby expulsion of solutes from a polar mobile phase dominates the free energy of transfer with nonpolar sorbents acting as receptive but passive surfaces, and the partitioning model, 4-6 where the stationary phase contributes in a much more significant way to the overall distribution process. On the basis of solvophobic considerations that encompass the solvation/desolvation model, Horvath and co-workers 1 have proposed that the interaction between the solute and the mobile phase provides the primary driving force. According to this model, retention in the high-performance modes of RPC can then be attributed to adsorption rather than partitioning processes between the solutes and the nonpolar sorbent. 1,2 In the solvation/desolvation model, the contributio

Interacting Generalised Cosmic Chaplygin gas in Loop quantum cosmology: A singularity free universe

In this work we investigate the background dynamics when dark energy is coupled to dark matter with a suitable interaction in the universe described by Loop quantum cosmology. Dark energy in the form of Generalised Cosmic Chaplygin gas is considered. A suitable interaction between dark energy and dark matter is taken into account in order to at least alleviate (if not solve) the cosmic coincidence problem. The dynamical system of equations is solved numerically and a stable scaling solution is obtained. A significant attempt towards the solution of the cosmic coincidence problem is taken. The statefinder parameters are also calculated to classify the dark energy model. Graphs and phase diagrams are drawn to study the variations of these parameters. It is seen that the background dynamics of Generalised Cosmic Chaplygin gas is completely consistent with the notion of an accelerated expansion in the late universe. From the graphs, generalised cosmic Chaplygin gas is identified as a dark fluid with a lesser negative pressure compared to Modified Chaplygin gas, thus supporting a 'No Big Rip' cosmology. It has also been shown that in this model the universe follows the power law form of expansion around the critical point, which is consistent with the known results. Future singularities that may be formed in this model as an ultimate fate of the universe has been studied in detail. It was found that the model is completely free from any types of future singularities.Comment: 10 pages, 10 figures. arXiv admin note: text overlap with arXiv:1109.1481, arXiv:1102.275

Mortality and pulmonary complications in patients undergoing surgery with perioperative sars-cov-2 infection: An international cohort study

Background The impact of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) on postoperative recovery needs to be understood to inform clinical decision making during and after the COVID-19 pandemic. This study reports 30-day mortality and pulmonary complication rates in patients with perioperative SARS-CoV-2 infection. Methods This international, multicentre, cohort study at 235 hospitals in 24 countries included all patients undergoing surgery who had SARS-CoV-2 infection confirmed within 7 days before or 30 days after surgery. The primary outcome measure was 30-day postoperative mortality and was assessed in all enrolled patients. The main secondary outcome measure was pulmonary complications, defined as pneumonia, acute respiratory distress syndrome, or unexpected postoperative ventilation. Findings This analysis includes 1128 patients who had surgery between Jan 1 and March 31, 2020, of whom 835 (740%) had emergency surgery and 280 (248%) had elective surgery. SARS-CoV-2 infection was confirmed preoperatively in 294 (261%) patients. 30-day mortality was 238% (268 of 1128). Pulmonary complications occurred in 577 (512%) of 1128 patients; 30-day mortality in these patients was 380% (219 of 577), accounting for 817% (219 of 268) of all deaths. In adjusted analyses, 30-day mortality was associated with male sex (odds ratio 175 [95% CI 128-240], p<00001), age 70 years or older versus younger than 70 years (230 [165-322], p<00001), American Society of Anesthesiologists grades 3-5 versus grades 1-2 (235 [157-353], p<00001), malignant versus benign or obstetric diagnosis (155 [101-239], p=0046), emergency versus elective surgery (167 [106-263], p=0026), and major versus minor surgery (152 [101-231], p=0047). Interpretation Postoperative pulmonary complications occur in half of patients with perioperative SARS-CoV-2 infection and are associated with high mortality. Thresholds for surgery during the COVID-19 pandemic should be higher than during normal practice, particularly in men aged 70 years and older. Consideration should be given for postponing non-urgent procedures and promoting non-operative treatment to delay or avoid the need for surgery. Funding National Institute for Health Research (NIHR), Association of Coloproctology of Great Britain and Ireland, Bowel and Cancer Research, Bowel Disease Research Foundation, Association of Upper Gastrointestinal Surgeons, British Association of Surgical Oncology, British Gynaecological Cancer Society, European Society of Coloproctology, NIHR Academy, Sarcoma UK, Vascular Society for Great Britain and Ireland, and Yorkshire Cancer Research

Mortality and pulmonary complications in patients undergoing surgery with perioperative SARS-CoV-2 infection: an international cohort study

Background: The impact of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) on postoperative recovery needs to be understood to inform clinical decision making during and after the COVID-19 pandemic. This study reports 30-day mortality and pulmonary complication rates in patients with perioperative SARS-CoV-2 infection. Methods: This international, multicentre, cohort study at 235 hospitals in 24 countries included all patients undergoing surgery who had SARS-CoV-2 infection confirmed within 7 days before or 30 days after surgery. The primary outcome measure was 30-day postoperative mortality and was assessed in all enrolled patients. The main secondary outcome measure was pulmonary complications, defined as pneumonia, acute respiratory distress syndrome, or unexpected postoperative ventilation. Findings: This analysis includes 1128 patients who had surgery between Jan 1 and March 31, 2020, of whom 835 (74·0%) had emergency surgery and 280 (24·8%) had elective surgery. SARS-CoV-2 infection was confirmed preoperatively in 294 (26·1%) patients. 30-day mortality was 23·8% (268 of 1128). Pulmonary complications occurred in 577 (51·2%) of 1128 patients; 30-day mortality in these patients was 38·0% (219 of 577), accounting for 81·7% (219 of 268) of all deaths. In adjusted analyses, 30-day mortality was associated with male sex (odds ratio 1·75 [95% CI 1·28–2·40], p\textless0·0001), age 70 years or older versus younger than 70 years (2·30 [1·65–3·22], p\textless0·0001), American Society of Anesthesiologists grades 3–5 versus grades 1–2 (2·35 [1·57–3·53], p\textless0·0001), malignant versus benign or obstetric diagnosis (1·55 [1·01–2·39], p=0·046), emergency versus elective surgery (1·67 [1·06–2·63], p=0·026), and major versus minor surgery (1·52 [1·01–2·31], p=0·047). Interpretation: Postoperative pulmonary complications occur in half of patients with perioperative SARS-CoV-2 infection and are associated with high mortality. Thresholds for surgery during the COVID-19 pandemic should be higher than during normal practice, particularly in men aged 70 years and older. Consideration should be given for postponing non-urgent procedures and promoting non-operative treatment to delay or avoid the need for surgery. Funding: National Institute for Health Research (NIHR), Association of Coloproctology of Great Britain and Ireland, Bowel and Cancer Research, Bowel Disease Research Foundation, Association of Upper Gastrointestinal Surgeons, British Association of Surgical Oncology, British Gynaecological Cancer Society, European Society of Coloproctology, NIHR Academy, Sarcoma UK, Vascular Society for Great Britain and Ireland, and Yorkshire Cancer Research

Impact of opioid-free analgesia on pain severity and patient satisfaction after discharge from surgery: multispecialty, prospective cohort study in 25 countries

Background: Balancing opioid stewardship and the need for adequate analgesia following discharge after surgery is challenging. This study aimed to compare the outcomes for patients discharged with opioid versus opioid-free analgesia after common surgical procedures.Methods: This international, multicentre, prospective cohort study collected data from patients undergoing common acute and elective general surgical, urological, gynaecological, and orthopaedic procedures. The primary outcomes were patient-reported time in severe pain measured on a numerical analogue scale from 0 to 100% and patient-reported satisfaction with pain relief during the first week following discharge. Data were collected by in-hospital chart review and patient telephone interview 1 week after discharge.Results: The study recruited 4273 patients from 144 centres in 25 countries; 1311 patients (30.7%) were prescribed opioid analgesia at discharge. Patients reported being in severe pain for 10 (i.q.r. 1-30)% of the first week after discharge and rated satisfaction with analgesia as 90 (i.q.r. 80-100) of 100. After adjustment for confounders, opioid analgesia on discharge was independently associated with increased pain severity (risk ratio 1.52, 95% c.i. 1.31 to 1.76; P < 0.001) and re-presentation to healthcare providers owing to side-effects of medication (OR 2.38, 95% c.i. 1.36 to 4.17; P = 0.004), but not with satisfaction with analgesia (beta coefficient 0.92, 95% c.i. -1.52 to 3.36; P = 0.468) compared with opioid-free analgesia. Although opioid prescribing varied greatly between high-income and low- and middle-income countries, patient-reported outcomes did not.Conclusion: Opioid analgesia prescription on surgical discharge is associated with a higher risk of re-presentation owing to side-effects of medication and increased patient-reported pain, but not with changes in patient-reported satisfaction. Opioid-free discharge analgesia should be adopted routinely

Chickpea

The narrow genetic base of cultivated chickpea warrants systematic collection, documentation and evaluation of chickpea germplasm and particularly wild Cicer species for effective and efficient use in chickpea breeding programmes. Limiting factors to crop production, possible solutions and ways to overcome them, importance of wild relatives and barriers to alien gene introgression and strategies to overcome them and traits for base broadening have been discussed. It has been clearly demonstrated that resistance to major biotic and abiotic stresses can be successfully introgressed from the primary gene pool comprising progenitor species. However, many desirable traits including high degree of resistance to multiple stresses that are present in the species belonging to secondary and tertiary gene pools can also be introgressed by using special techniques to overcome pre- and post-fertilization barriers. Besides resistance to various biotic and abiotic stresses, the yield QTLs have also been introgressed from wild Cicer species to cultivated varieties. Status and importance of molecular markers, genome mapping and genomic tools for chickpea improvement are elaborated. Because of major genes for various biotic and abiotic stresses, the transfer of agronomically important traits into elite cultivars has been made easy and practical through marker-assisted selection and marker-assisted backcross. The usefulness of molecular markers such as SSR and SNP for the construction of high-density genetic maps of chickpea and for the identification of genes/QTLs for stress resistance, quality and yield contributing traits has also been discussed