Ab initio investigation of ground and excited states of ScH molecule.

The theoretical study of the electronic structure of Scandium Hydride ScH has been carried out using ab-initio methods. By employing (MRCI-SD/SA-CASSCF) and by using basis sets involving contribution of all electrons of both Scandium and Hydrogen atoms, 18 singlet and 15 triplet low-lying electronic states have been calculated below 28803 cm-1. Potential energy curves have been plotted and the term values at equilibrium Te, the vibrational constants ωe and ωeχe of ScH electronic states have been fitted. In addition, we calculated the permanent electric dipole moments for all these predicted states, the transition dipole moments TDMs within states at a range of internuclear distance around the equilibrium, the vibronic intensities FCF and the radiative lifetime. The calculated spectroscopic constants are in excellent consistency with the available experimental results and with other previous theoretical works. These calculations also predicted many excited states unobserved experimentally. The observed perturbations in D1Π and C1Σ+ have been investigated in this work.

Prospective study of urinary function and analysis of risk factors after rectal cancer surgery.

BACKGROUND: Alterations in urinary function are complications of rectal cancer surgery. The aim of this study was to prospectively analyze the changes in urinary function in patients operated on for rectal cancer, and to identify risk factors that may have an impact on the deterioration of postoperative urinary function. METHODS: A prospective study of urinary function in rectal cancer patients who had elective oncological resection with curative intention at the Arnau de Vilanova Hospital in Valencia, Spain, from January 2017 to March 2019. The evaluation of urinary function was performed using the International Prostate Symptom Score (IPSS) preoperatively, at 6 and 12 months after surgery. Predictive factors of urinary dysfunction were identified by univariate and multivariate analysis. RESULTS: Ninety-four patients were enrolled in the study. Eighty-seven of them completed all the follow-up assessments (48 men and 39 women, mean age 65.74 ± 10.95 years,). The mean IPSS was 7.96 ± 7.59 preoperatively, 9.01 ± 6.81 at 6 months, and 8.63 ± 5.59 at 12 months, without statistically significant differences. There were no differences in IPSS between males and females. Preoperative urinary dysfunction was 39% and at 12 months, a deterioration occurred in 23 patients (26.4%). IPSS analysis of symptoms showed a statistically significant worsening of nocturia at 6 months (p = 0.002) and 1 year after surgery (p = 0.037) in women. American Society of Anesthesiologists (ASA) class (OR: 11, [95% CI2.4-53]; p = 0.010), surgical difficulty (OR: 4.5, [95% CI 1-19]; p = 0.027) and anastomotic leakage (OR: 14, [95% CI 1.6-117]; p = 0.010), were identified as independent risk factors for deterioration of urinary function after surgery. CONCLUSIONS: Our study showed worsening urinary dysfunction after rectal cancer surgery in 26.4% of the patients. However, there were no statistically significant differences in mean IPSS scores at the three assessment times (preoperatively, 6 months, 12 months). ASA class, surgical difficulty, and anastomotic leakage may predict postoperative deterioration.

Central sleep apnea after acute coronary syndrome and association with ticagrelor use.

STUDY OBJECTIVES: By modifying the apneic threshold, the antiplatelet agent ticagrelor could promote central sleep apnea hypopnea syndrome (CSAHS). We aimed to assess the association between CSAHS and ticagrelor administration. METHODS: Patients were prospectively included within 1 year after acute coronary syndrome (ACS), if they had no heart failure (and left ventricular ejection fraction ≥ 45%) and no history of sleep apnea. After an overnight sleep study, patients were classified as "normal" with apnea hypopnea index (AHI) < 15, "CSAHS patients" with AHI ≥ 15 mostly with central sleep apneas, and "obstructive sleep apnea hypopnea syndrome (OSAHS) patients" with AHI ≥ 15 mostly with obstructive sleep apneas. RESULTS: We included 121 consecutive patients (mean age 56.8 ± 10.8, 88% men, mean body mass index 28.3 ± 4.4 kg/m2, left ventricular ejection fraction 56 ± 5%, at a mean of 67 ± 60 days (median 40 days, interquartile range: 30-80 days) after ACS. In total, 49 (45.3%) patients had AHI ≥ 15 (27 [22.3%] CSAHS %, 22 [18.2%] OSAHS). For 80 patients receiving ticagrelor, 24 (30%) had CSAHS with AHI ≥ 15, and for 41 patients not taking ticagrelor, only 3 (7.3%) had CSAHS with AHI ≥ 15 (chi-square = 8, p = 0.004). On multivariable analysis only age and ticagrelor administration were associated with the occurrence of CSAHS, (p = 0.0007 and p = 0.0006). CONCLUSION: CSA prevalence after ACS is high and seems promoted by ticagrelor administration. Results from monocentric study suggest a preliminary signal of safety. CLINICAL TRIALS. GOV ID: NCT03540459.

Long-term functional and clinical outcomes following transanal advancement flap for complex anal fistula repair: are there predictors of recurrence and incontinence?

AIM: Transanal flap is an attractive technique for complex fistulas. The aim of this study was to identify factors associated with poor outcome, recurrence and incontinence. METHOD: All patients who underwent an advancement flap for the treatment of a complex anal fistula between 1995 and 2019 were prospectively enrolled. The patient data obtained included age, sex, body mass index, comorbid conditions and smoking history. The fistula characteristics analysed included previous anal surgery, anatomy of the fistula according to Park's classification, horseshoe or supralevator extension and preoperative seton drainage. The postoperative data registered included complications, postoperative stay, recurrence and incontinence. Predictive factors for recurrence and incontinence were identified using univariate and multivariate analysis. RESULTS: One hundred and ninety patients were included; 134 (70.5%) were men and the mean patient age was 50 years. The median length of follow-up was 44.6 months. The fistula recurred in 14 patients (7.3%). Before surgery, 20 patients (10.5%) reported incontinence symptoms. In the continent patients a Wexner postoperative score of 0 was identified in 79.4%. Wexner scores between 1 and 3 were observed in 17% and scores of 4 or more in five patients (3%). Factors associated with recurrence included age < 50 years (OR = 4.8, P = 0.02, 95% CI 1.2-19), smoking (OR = 4.1, P = 0.03, 95% CI 1-16.5) and suprasphincteric fistula (OR = 0.5, P = 0.01, 95% CI 0.2-0.8) in multivariate log regression analysis. Major incontinence was influenced by female sex and previous anal surgery (OR = 7.5, P = 0.003, 95% CI 1.6-34 and OR = 0.1, P = 0.007, 95% CI 0.1-0.7, respectively). CONCLUSION: Full-thickness transanal advancement flap is a good treatment for complex anal fistula repair. This study provides relevant information on risk factors for failure of therapy and incontinence, which can help in advising patients before surgery and planning a good treatment strategy.

Impact of the number of stapler firings on anastomotic leakage in laparoscopic rectal surgery: a systematic review and meta-analysis.

BACKGROUND: Several univariate and multivariate studies have already identified the number of stapler firings for laparoscopic rectal transection for rectal cancer as an independent risk factor for anastomotic leakage. The aim of this study was to perform a systematic review and meta-analysis of the anastomotic leakage rate in laparoscopic rectal surgery according to the need of using one or two stapler firings for rectal transection. METHODS: PubMed, Ovid, the Cochrane Library database and ClinicalTrials.gov were searched. All of the statistical analyses were performed using Revman software. RESULTS: Five studies were included (1267 patients). The overall anastomotic leakage rate was 5.5% [0.7-8.4%]. Anastomotic leak occurred in 3.5% (17/491) of the cases where 1 stapler firing was used versus 6.7% (50/786) of the cases in which 2 firings were needed (50/786). Two stapler firings were significantly associated with an increased risk of anastomotic leakage (OR 2.44, 95% CI 1.34-4.42, p = 0.003, I2 = 1%). CONCLUSIONS: Our systematic review and meta-analysis suggest that two firings imply a higher rate of anastomotic leak than a single firing after laparoscopic rectal surgery with a double stapling technique. Coloproctologists should strive to reduce the number of linear stapler firings and try to transect the rectum with a single firing.

Electrospray ionization linear trap quadrupole Orbitrap in analysis of old tempera paintings: application to nineteenth-century Orthodox icons.

Proteomic approach in combination with mass spectrometry demonstrates a great potential for identification of proteinaceous materials in works of art. In this study we used a linear trap quadrupole Orbitrap (LTQ-Orbitrap), a state-of-the-art mass spectrometer for parts per million accuracy analyses of peptides behind tryptic hydrolysis. After the efficiency of the proteomic method was confirmed for reference and model samples, micro-samples from historical paintings were for the first time analysed using this technique. Superior performances of the liquid chromatography-mass spectrometry approach using a LTQ-Orbitrap mass spectrometer allowed identification of egg yolk peptides in two samples from nineteenth-century Orthodox icons, indicating egg tempera as the painting technique. Accurate precursor ion masses, in the range of ±2 ppm, and retention times of tryptic peptides strengthen protein identification. Additionally, in all historical samples the presence of animal glues suggested that the ground layer was likely bound using bovine collagen. Comparing to results acquired using matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry in our previous study, here we achieved higher ion scores and protein scores, better sequence coverage and more identified proteins. In fact, a combination of the two mass spectrometric techniques provided overlapping and complementary data, related to the detection of peptides with different physicochemical properties.

Colchicine for postoperative pericardial effusion: a multicentre, double-blind, randomised controlled trial.

OBJECTIVES: Pericardial effusion is common after cardiac surgery. Growing evidence suggests that colchicine may be useful for acute pericarditis, but its efficacy in reducing pericardial effusion volume postoperatively has not been assessed. METHODS: This randomised, double-blind, placebo-controlled study conducted in 10 centres in France included 197 patients at high risk of tamponade (ie, with moderate to large-sized persistent effusion (echocardiography grades 2, 3 or 4 on a scale of 0-4)) at 7-30 days after cardiac surgery. Patients were randomly assigned to receive colchicine, 1 mg daily (n=98), or a matching placebo (n=99). The main end point was change in pericardial effusion grade after 14-day treatment. Secondary end points included frequency of late cardiac tamponade. RESULTS: The placebo and the colchicine groups showed a similar mean baseline pericardial effusion grade (2.9±0.8 vs 3.0±0.8) and similar mean decrease from baseline after treatment (-1.1±1.3 vs -1.3±1.3 grades). The mean difference in grade decrease between groups was -0.19 (95% CI -0.55 to 0.16, p=0.23). In total, 13 cases of cardiac tamponade occurred during the 14-day treatment (7 and 6 in the placebo and colchicine groups, respectively; p=0.80). At 6-month follow-up, all patients were alive and had undergone a total of 22 (11%) drainages: 14 in the placebo group and 8 in the colchicine group (p=0.20). CONCLUSIONS: In patients with pericardial effusion after cardiac surgery, colchicine administration does not reduce the effusion volume or prevent late cardiac tamponade. CLINICAL TRIAL REG NO: NCT01266694.

Secondary metabolites of Seseli rigidum: Chemical composition plus antioxidant, antimicrobial and cholinesterase inhibition activity.

Extracts of different polarity obtained from various plant parts (root, leaf, flower and fruit) of Seseli rigidum were studied by different antioxidant assays: DPPH and ABTS radical scavenging activity, by total reducing power method as well as via total content of flavonoids and polyphenols. Essential oils of all plant parts showed weak antioxidant characteristics. The inhibitory concentration range of the tested extracts, against bacteria Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus cereus, and fungi Candida albicans and Aspergillus niger was 0.01-1.50 mg/mL and of a microbicidal 0.02-3.00 mg/mL. In the interaction with cholinesterase, all essential oils proved effective as inhibitors. The highest percentage of inhibition versus human and horse cholinesterase was shown by root essential oil (38.20% and 48.30%, respectively) among oils, and root hexane extract (40.56% and 50.65% respectively). Essential oils and volatile components of all plant parts were identified by GC, GC-MS and headspace/GC-MS. Statistical analysis of the ensemble of results showed that the root essential oil composition differed significantly from essential oils of other parts of the plant. Taking into account all of the studied activities, the root hexane extract showed the best overall properties. By means of high performance liquid chromatography coupled to high resolution mass spectrometry, the 30 most abundant constituents were identified in extracts of different polarity. The presence of identified constituents was linked to observed specific biological activities, thus designating compounds potentially responsible for each exhibited activity.

HPV Prevalence and Prognostic Value in a Prospective Cohort of 255 Patients with Locally Advanced HNSCC: A Single-Centre Experience.

Background. HPV is a positive prognostic factor in HNSCC. We studied the prevalence and prognostic impact of HPV on survival parameters and treatment toxicity in patients with locally advanced HNSCC treated with concomitant chemoradiation therapy. Methods. Data on efficacy and toxicity were available for 560 patients. HPV was detected by PCR. Analysis was performed using Kaplan-Meier survival curves, Fisher's test for categorical data, and log-rank statistics for failure times. Results. Median follow-up was 4.7 years. DNA extraction was successful in 255 cases. HPV prevalence was 68.6%, and 53.3% for HPV 16. For HPV+ and HPV-, median LRC was 8.9 and 2.2 years (P = 0.0002), median DFS was 8.9 and 2.1 years (P = 0.0014), and median OS was 8.9 and 3.1 years (P = 0.0002). Survival was different based on HPV genotype, stage, treatment period, and chemotherapy regimen. COX adjusted analysis for T, N, age, and treatment remained significant (P = 0.004). Conclusions. Oropharyngeal cancer is increasingly linked to HPV. This study confirms that HPV status is associated with improved prognosis among H&N cancer patients receiving CRT and should be a stratification factor for clinical trials including H&N cases. Toxicity of CRT is not modified for the HPV population.

Identification of protein binders in artworks by MALDI-TOF/TOF tandem mass spectrometry.

Aim of this work is to propose an analytical protocol for proteinaceous binder identification in paintings using tryptic peptide analysis and MALDI-TOF mass spectrometry strengthened with MALDI-TOF/TOF tandem mass spectrometry (LIFT method). Proteinaceous binders are enzymatically digested with trypsin. From each individual protein frequently occurring in binders, a specific set of peptides is releasing during enzymatic digestion giving a peptide mass fingerprint (PMF) of that particular protein. The most intensive peptide peaks in PMF were determined and annotated with their corresponding amino acid sequence by MALDI-TOF/TOF analysis and subsequent database search. Before analyzing historical painting samples, procedure was tested and optimized on several painting model samples for a reliable and efficient identification of proteinaceous materials. The method is avoiding sample manipulation as much as possible in order to reduce sample loss. Since the applied procedures led to protein identification of binding media in model samples, MALDI-TOF/TOF was for the first time applied for analysis of proteinaceous binders in old painting samples.

Fourier transform mass spectrometry for metabolome analysis.

The metabolome is characterized by a large number of molecules exhibiting a high diversity of chemical structures and abundances, requiring complementary analytical platforms for extensive coverage. Of these analytical platforms, atmospheric pressure ionization Fourier transform mass spectrometry (FT/MS) instruments are popular because they provide accurate mass measurements with ppm and even sub-ppm errors, and also high and ultra-high resolving power. In this article, we evaluate the improvements provided for metabolomics by different types of FT/MS instruments, together with the ability of these platforms to cover the various analytical requirements: global metabolite profiling, absolute quantification and also structural characterization, of metabolomics. The specificities of FT/MS in terms of data pre-processing and the input of accurate mass measurements for biological interpretation and for highlighting metabolic networks are also addressed.

Accuracy of a portable international normalized ratio monitor for patients receiving a low molecular weight heparin as a bridge pending full oral anticoagulant efficacy.

BACKGROUND: Point of care (POC) devices measuring the international normalized ratio (INR) are accurate for patients with stable disease, but their efficiency has not been prospectively assessed during the "bridging period" when patients are receiving a low molecular weight heparin (LMWH) on top of a vitamin K antagonist (VKA) until the target INR is reached. METHODS: 188 dual INR measurement using the POC (INR(POC)) and the laboratory (INR(lab)) at the same time were consecutively determined : 69 in patients receiving LMWH+VKA (bridging group) and 119 in patients receiving only a VKA (control group). INRpoc was compared to INR(lab). RESULTS: Test strip failure rate was higher in the bridging group than in the control group (29% vs 4%; p<0,001). In successful tests, POC accuracy was not modified by LMWH administration: the correlation coefficients between POC and lab INR values for the bridging group and the control group were 0,81 and 0,87 respectively, and the relative measure of divergence (RMD=INR(lab) - INR(poc)/INR(lab)) was lower in the bridging group than in the control group (4+/-7% vs 10+/-14%; p=0,02). Finally, clinically relevant agreement between POC and laboratory was of 90% in the bridging group and 92.1% in the control group (p=0.6). CONCLUSION: With the POC used (INRatio), in patients receiving LMWH when the POC gives a result, it is as accurate as in patients not receiving a LMWH.

Photochemical activation of an azido manganese-monosubstituted keggin polyoxometalate: on the road to a Mn(V)-nitrido derivative.

The manganese(V)-nitrido polyoxometalate derivative [PW(11)O(39){Mn(V)N}](5-) has been synthesized by photochemical activation of the parent manganese(III)-azido derivative [PW(11)O(39)Mn(III)N(3)](5-). It was characterized by mass spectrometry, (31)P NMR, UV-vis, and IR spectroscopies. An electrochemistry study indicated that only the Mn(V) state was stable. The photoactivation of the manganese(III)-azido derivative proceeds through two competitive routes, yielding to the targeted product of photooxidation {Mn(V)N} or the undesirable product of photoreduction {Mn(II)L} (L = H(2)O, N(3)), depending on the photolysis conditions. A simplified photolysis mechanism involving two different excited states was proposed to account for the temperature and wavelength dependence.

Identification of new odorous compounds in Swedish water: mixed haloanisoles and phenolic precursors.

Mixed chlorobromoanisoles have recently been recognized as new potential odorous compounds in tap water. The odour threshold concentrations (OTCs) of these compounds are close to the sub ng/L (ppt) and associated descriptors are "earthy, musty, rubber". During a "swampy, musty" episode in water of the Norrtälje district (Sweden), 2,4,6-mixed chlorobromoanisoles and their phenolic precursors were identified. These compounds were synthesised in order to quantify them in different types of waters, Samplings were performed during two different seasons. Results show that whatever the season, mixed haloanisoles and their precursors were present. Chlorination, biofilm activity and residence time in the distribution system seem to be critical factors for the appearance of such compounds.

Direct analysis and MALDI imaging of formalin-fixed, paraffin-embedded tissue sections.

Formalin fixation, generally followed by paraffin embedding, is the standard and well-established processing method employed by pathologist. This treatment conserves and stabilizes biopsy samples for years. Analysis of FFPE tissues from biopsy libraries has been, so far, a challenge for proteomics biomarker studies. Herein, we present two methods for the direct analysis of formalin-fixed, paraffin-embedded (FFPE) tissues by MALDI-MS. The first is based on the use of a reactive matrix, 2,4-dinitrophenylhydrazine, useful for FFPE tissues stored less than 1 year. The second approach is applicable for all FFPE tissues regardless of conservation time. The strategy is based on in situ enzymatic digestion of the tissue section after paraffin removal. In situ digestion can be performed on a specific area of the tissue as well as on a very small area (microdigestion). Combining automated microdigestion of a predefined tissue array with either in situ extraction prior to classical nanoLC/MS-MS analysis or automated microspotting of MALDI matrix according to the same array allows the identification of both proteins by nanoLC-nanoESI and MALDI imaging. When adjacent tissue sections are used, it is, thus, possible to correlate protein identification and molecular imaging. These combined approaches, along with FFPE tissue analysis provide access to massive amounts of archived samples in the clinical pathology setting.

Detection of functional ricin by immunoaffinity and liquid chromatography-tandem mass spectrometry.

The toxin ricin is a biological weapon that may be used for bioterrorist purposes. As a member of the group of ribosome-inactivating proteins (RIPs), ricin has an A-chain possessing N-glycosidase activity which irreversibly inhibits protein synthesis. In this paper, we demonstrate that provided appropriate sample preparation is used, this enzymatic activity can be exploited for functional ricin detection with sensitivity similar to the best ELISA and specificity allowing application to environmental samples. Ricin is first captured by a monoclonal antibody directed against the B chain and immobilized on magnetic beads. Detection is then realized by determination of the adenine released by the A chain from an RNA template using liquid chromatography coupled to tandem mass spectrometry. The immunoaffinity step combined with the enzymatic activity detection leads to a specific assay for the entire functional ricin with a lower limit of detection of 0.1 ng/mL (1.56 pM) after concentration of the toxin from a 500 microL sample size. The variability of the assay was 10%. Finally, the method was applied successfully to milk and tap or bottled water samples.

[BNP and echocardiography can predict the occurrence of acute cardiac decompensation during titration of bisoprolol in chronic systolic heart failure]. / Le BNP et l'échocardiographie prédisent la survenue de décompensation cardiaque aigue au cours de la titration du bisoprolol dans l'insuffisance cardiaque chronique systolique.

OBJECTIVES: Based on the fact that NYHA class, plasma BNP level, and echocardiographic indices of left ventricular filling pressures are prognostic factors in chronic systolic heart failure, we evaluated their predictive value for acute decompensation following initiation and titration of bisoprolol in this illness. METHODS AND RESULTS: Bisoprolol was initiated and/or increased according to the ESC/ACC/AHA recommendations in 50 patients with stable chronic systolic heart failure (age: 60+/-2 years, males: 88%) in NYHA class? 2 with a left ventricular ejection fraction (LVEF)<40% and a plasma creatinine<250 micromol/l. The clinical parameters, plasma BNP levels and echocardiographic indices were measured blind on the same day, on admission and then once a week for three weeks. On admission, the NYHA was 2.9+/-0.1, mean plasma creatinine 99+/-3 micromol/l, plasma BNP 503+/-57 pg/ml, LVEF 29+/-1%, E/A ratio 1.9+/-0.2, E/Ea ratio 8.8+/-0.3, E wave deceleration time 155+/-9 ms, systolic pulmonary artery pressure 40+/-2 mmHg and the diameter of the inferior vena cava was 16+/-1 mm. Over the course of follow up, an episode of acute decompensation occurred in 16% of the patients (8/50). Using univariate analysis, age and initial (admission) values for NYHA class, blood pressure, plasma BNP level, E/A ratio, E wave deceleration time, E/Ea ratio and the systolic pulmonary arterial pressure allowed prediction of the occurrence of acute decompensation following initiation and titration of bisoprolol. The use of the initial value of NYHA class alone allowed prediction of the occurrence of acute decompensation in just 56% of the patients, and the absence of an occurrence of acute decompensation in 93% of them. Normal results for the echocardiographic indices (systolic pulmonary arterial pressure<40 mmHg or E/A ratio<1.4 or E wave deceleration time>145 ms) as recorded on admission were associated with the absence of an occurrence of acute decompensation is 100% of cases. The combined use of NYHA class>3 and either a BNP>398 pg/ml or echocardiographic indices in favour of an elevation in left ventricular filling pressures (systolic pulmonary arterial pressure>40 mmHg, E/A ratio>1.4 or E wave deceleration time<145 ms) allowed prediction of the occurrence of acute heart failure in 100% of cases CONCLUSION: The combined use of NYHA class, BNP level and echocardiographic indices for measuring left ventricular filling pressures is more pertinent than the isolated use of clinical parameters for predicting tolerance to bisoprolol in chronic heart failure with a LVEF<40%.