The structure and energetics of Cr(CO)6 and Cr(CO)5

The geometric structure of Cr(CO)6 is optimized at the modified coupled pair functional (MCPF), single and double excitation coupled-cluster (CCSD) and CCSD(T) levels of theory (including a perturbational estimate for connected triple excitations), and the force constants for the totally symmetric representation are determined. The geometry of Cr(CO)5 is partially optimized at the MCPF, CCSD, and CCSD(T) levels of theory. Comparison with experimental data shows that the CCSD(T) method gives the best results for the structures and force constants, and that remaining errors are probably due to deficiencies in the one-particle basis sets used for CO. The total binding energies of Cr(CO)6 and Cr(CO)5 are also determined at the MCPF, CCSD, and CCSD(T) levels of theory. The CCSD(T) method gives a much larger total binding energy than either the MCPF or CCSD methods. An analysis of the basis set superposition error (BSSE) at the MCPF level of treatment points out limitations in the one-particle basis used. Calculations using larger basis sets reduce the BSSE, but the total binding energy of Cr(CO)6 is still significantly smaller than the experimental value, although the first CO bond dissociation energy of Cr(CO)6 is well described. An investigation of 3s3p correlation reveals only a small effect. In the largest basis set, the total CO binding energy of Cr(CO)6 is estimated to be 140 kcal/mol at the CCSD(T) level of theory, or about 86 percent of the experimental value. The remaining discrepancy between the experimental and theoretical value is probably due to limitations in the one-particle basis, rather than limitations in the correlation treatment. In particular an additional d function and an f function on each C and O are needed to obtain quantitative results. This is underscored by the fact that even using a very large primitive set (1042 primitive functions contracted to 300 basis functions), the superposition error for the total binding energy of Cr(CO)6 is 22 kcal/mol at the MCPF level of treatment

Symmetry breaking in O4(+): An application of the Brueckner coupled-cluster method

A recent calculation of the antisymmetric stretch frequency for the rectangular structure of quartet O4(+) using the singles and doubles quadratic configuration interaction method with a perturbational estimate of connected triple excitations (QCISD(T)) method gave a value of 3710 cm(exp -1). This anomalous frequency is shown to be a consequence of symmetry breaking effects, which occur even though the QCISD(T) solution derived from a delocalized SCF reference function lies energetically well below the two localized (symmetry-broken) solutions at the equilibrium geometry. The symmetry breaking is almost eliminated at the CCSD level of theory, but the small remaining symmetry breaking effects are magnified at the CCSD(T) level of theory so that the antisymmetric stretch frequency is still significantly in error. The use of the Brueckner coupled cluster method, however, leads to a symmetrical solution which is free of symmetry breaking effects, with an antisymmetric stretch frequency of 1322 cm(exp -1), in good agreement with our earlier calculations using the complete active space self consistent field/complete active space state interaction (CASSCF/CASSI) method

Behavioural Effects of the Shelter Design on Male Guinea Pigs

To improve the welfare of group-housed male guinea pigs during the acclimatization period, which is when  social groups are formed, different designs of shelters were tested, one shelter having one entrance to a single  compartment – a Box for group hiding – and the other having individual entrances to a compartment  in the cage – a Garage for single hiding. Both were studied to evaluate whether they had any affect on the  behavioral levels. Behavioural and weight data were collected during five of the seven days of the acclimatization  period. Data were tested against the Mann-Whitney U and Variance Analysis test. Results demonstrated  that males in cages with the garage spent more time inside the shelter (P =0.0004), while males in  cages with the box spent more time resting (P =0.000), feeding (P =0.0043) and drinking (P =0.0022) on  the open floor, and yet there was no difference in individual weight between treatments at the end of the  study. Males in cages with garage experienced a more rapid establishment of the social hierarchy (P =  0.0024) by being involved with a lower number of social interactions. The conclusion from the present  study is considered to show that males in cages with the garage were able to avoid unnecessarily high levels  of stress and aggression caused by territorial defence while the hierarchy was established.

Prognos (R) in the diagnosis of amalgam hypersensitivity - A diagnostic case-control study

Objective: We aimed to investigate whether the Prognos (R) device might be a useful tool in the diagnosis of disorders suspected to be due to dental amalgam fillings. Participants and Methods: A diagnostic case-control study was performed in 27 patients who complained about health problems attributed to amalgam ( cases), 27 healthy volunteers with amalgam fillings ( controls I), and 27 healthy amalgam-free volunteers ( controls II). All participants were tested before and after application of 300 mg DMPS (2.3-dimercapto-1-propanesulfonic acid) with Prognos, a diagnostic device for the energetic measurement of Traditional Chinese Medicine meridians. In addition, mercury was measured in blood, urine, and saliva, and a lymphocyte transformation test (LTT) was performed. Results: Diagnoses derived from the first and second Prognos testing did not agree above chance (Cohen's Kappa = -0.11, 95% confidence interval -0.33 to 0.10; p = 0.30). Agreement for secondary outcome measures was poor, too. Prognos measurements did not differ between cases and controls. Correlations with measurements in urine, blood and saliva were low. Conclusion: In this study Prognos could not be shown to be a useful tool in the diagnosis of disorders suspected to be due to dental amalgam fillings

Nursing assistants matters—An ethnographic study of knowledge sharing in interprofessional practice

© 2017 John Wiley & Sons Ltd Interprofessional collaboration involves some kind of knowledge sharing, which is essential and will be important in the future in regard to the opportunities and challenges in practices for delivering safe and effective health care. Nursing assistants are seldom mentioned as a group of health care workers that contribute to interprofessional collaboration in health care practice. The aim of this ethnographic study was to explore how the nursing assistants’ knowledge can be shared in a team on a spinal cord injury rehabilitation ward. Using a sociomaterial perspective on practice, we captured different aspects of interprofessional collaboration in health care. The findings reveal how knowledge was shared between professionals, depending on different kinds of practice architecture. These specific cultural–discursive, material–economic, and social–political arrangements enabled possibilities through which nursing assistants’ knowledge informed other practices, and others’ knowledge informed the practice of nursing assistants. By studying what health care professionals actually do and say in practice, we found that the nursing assistants could make a valuable contribution of knowledge to the team

Defining user perception of distributed multimedia quality

This article presents the results of a study that explored the human side of the multimedia experience. We propose a model that assesses quality variation from three distinct levels: the network, the media and the content levels; and from two views: the technical and the user perspective. By facilitating parameter variation at each of the quality levels and from each of the perspectives, we were able to examine their impact on user quality perception. Results show that a significant reduction in frame rate does not proportionally reduce the user's understanding of the presentation independent of technical parameters, that multimedia content type significantly impacts user information assimilation, user level of enjoyment, and user perception of quality, and that the device display type impacts user information assimilation and user perception of quality. Finally, to ensure the transfer of information, low-level abstraction (network-level) parameters, such as delay and jitter, should be adapted; to maintain the user's level of enjoyment, high-level abstraction quality parameters (content-level), such as the appropriate use of display screens, should be adapted

Dynamic Electron Correlation Effects On The Ground State Potential Energy Surface Of A Retinal Chromophore Model

The ground state potential energy surface of the retinal chromophore of visual pigments (e.g., bovine rhodopsin) features a low-lying conical intersection surrounded by regions with variable charge transfer and diradical electronic structures. This implies that dynamic electron correlation may have a large effect on the shape of the force fields driving its reactivity. To investigate this effect, we focus on mapping the potential energy for three paths located along the ground state CASSCF potential energy surface of the penta-2,4-dieniminium cation taken as a minimal model of the retinal chromophore. The first path spans the bond length alternation coordinate and intercepts a conical intersection point. The other two are minimum energy paths along two distinct but kinetically competitive thermal isomerization coordinates. We show that the effect of introducing the missing dynamic electron correlation variationally (with MRCISD) and perturbatively (with the CASPT2, NEVPT2, and XMCQDPT2 methods) leads, invariably, to a stabilization of the regions with charge transfer character and to a significant reshaping of the reference CASSCF potential energy surface and suggesting a change in the dominating isomerization mechanism. The possible impact of such a correction on the photoisomerization of the retinal chromophore is discussed

Utility of oropharyngeal real-time PCR for S. pneumoniae and H. influenzae for diagnosis of pneumonia in adults.

Efst á síðunni er hægt að nálgast greinina í heild sinni með því að smella á hlekkinn To access publisher's full text version of this article click on the hyperlink at the bottom of the pageor click on the hyperlink at the To access publisher's full text version of this article, please click on the hyperlink in Additional Links field top of the page marked FilesA lack of sensitive tests and difficulties obtaining representative samples contribute to the challenge in identifying etiology in pneumonia. Upper respiratory tract swabs can be easily collected and analyzed with real-time PCR (rtPCR). Common pathogens such as S. pneumoniae and H. influenzae can both colonize and infect the respiratory tract, complicating the interpretation of positive results. Oropharyngeal swabs were collected (n = 239) prospectively from adults admitted to hospital with pneumonia. Analysis with rtPCR targeting S. pneumoniae and H. influenzae was performed and results compared with sputum cultures, blood cultures, and urine antigen testing for S. pneumoniae. Different Ct cutoff values were applied to positive tests to discern colonization from infection. Comparing rtPCR with conventional testing for S. pneumoniae in patients with all tests available (n = 57) resulted in: sensitivity 87 %, specificity 79 %, PPV 59 % and NPV 94 %, and for H. influenzae (n = 67): sensitivity 75 %, specificity 80 %, PPV 45 % and NPV 94 %. When patients with prior antimicrobial exposure were excluded sensitivity improved: 92 % for S. pneumoniae and 80 % for H. influenzae. Receiver operating characteristic curve analysis demonstrated for S. pneumoniae: AUC = 0.65 (95 % CI 0.51-0.80) and for H. influenzae: AUC = 0.86 (95 % CI 0.72-1.00). Analysis of oropharyngeal swabs using rtPCR proved both reasonably sensitive and specific for diagnosing pneumonia caused by S. pneumoniae and H. influenzae. This method may be a useful diagnostic adjunct to other methods and of special value in patients unable to provide representative lower airway samples.Icelandic Center for Research Rannis Landspitali University Hospital Science Fund University of Iceland Research Fun

Mapping The Excited State Potential Energy Surface Of A Retinal Chromophore Model With Multireference And Equation-of-motion Coupled-cluster Methods

The photoisomerization of the retinal chromophore of visual pigments proceeds along a complex reaction coordinate on a multidimensional surface that comprises a hydrogen-out-of-plane (HOOP) coordinate, a bond length alternation (BLA) coordinate, a single bond torsion and, finally, the reactive double bond torsion. These degrees of freedom are coupled with changes in the electronic structure of the chromophore and, therefore, the computational investigation of the photochemistry of such systems requires the use of a methodology capable of describing electronic structure changes along all those coordinates. Here, we employ the penta-2,4-dieniminium (PSB3) cation as a minimal model of the retinal chromophore of visual pigments and compare its excited state isomerization paths at the CASSCF and CASPT2 levels of theory. These paths connect the cis isomer and the trans isomer of PSB3 with two structurally and energetically distinct conical intersections (CIs) that belong to the same intersection space. MRCISD+Q energy profiles along these paths provide benchmark values against which other ab initio methods are validated. Accordingly, we compare the energy profiles of MRPT2 methods (CASPT2, QD-NEVPT2, and XMCQDPT2) and EOM-SF-CC methods (EOM-SF-CCSD and EOM-SF-CCSD(dT)) to the MRCISD+Q reference profiles. We find that the paths produced with CASSCF and CASPT2 are topologically and energetically different, partially due to the existence of a locally excited region on the CASPT2 excited state near the Franck-Condon point that is absent in CASSCF and that involves a single bond, rather than double bond, torsion. We also find that MRPT2 methods as well as EOM-SF-CCSD(dT) are capable of quantitatively describing the processes involved in the photoisomerization of systems like PSB3

Administration of aromatase inhibitor MPV-2213ad to blue fox vixens (Vulpes lagopus) as a model for contraception in female dogs

The interest in non-surgical approaches to contraception and fertility control in female dogs has increased in recent years. In this study the effect of an aromatase inhibitor (finrozole) was evaluated in fur production animals, farmed blue fox vixens, as a model for contraception in bitches. A total of 80 vixens were divided into 4 groups, receiving orally placebo (A) or finrozole 0.5 mg/kg (B), 3.5 mg/kg (C) or 24.5 mg/kg (D) for 21 consecutive days beginning in the pre-ovulatory period of heat. Monitoring of the vixens included clinical signs of heat, measurement of vaginal electrical resistance (VER) as well as oestradiol and progesterone concentrations in plasma. The approximate relation of the start of treatment to ovulation varied from 11 days before to one day after ovulation provided that the LH peak occurred 0.5 -2 days before the VER peak and ovulation was then estimated to occur 2 days after the LH peak. Seventy vixens were artificially inseminated within 8 h after a 50 Omega decline in vaginal electrical resistance was detected. Ten vixens were not inseminated. Pregnancy was confirmed by transabdominal ultrasound examination and birth of cubs was recorded. The pregnancy rates in the groups were 89.5% (A), 81.3% (B), 55.6% (C) and 52.9% (D). The average number of live born pups in the four groups was 9.4 (A), 7.0 (B), 5.8 (C), and 3.8 (D), respectively. No deleterious effects (for instance malformations) of finrozole on pups could be verified. The administration of finrozole did not have a significant effect on oestradiol parameters and VER values in vixens. Progesterone values were significantly higher in treatment groups compared with the placebo group. The results indicate that pregnancy could be avoided by finrozole provided that doses of >= 3.5 mg/kg were used and the treatment was initiated at least four days before the day of artificial insemination. This corresponds with two to six days before ovulation provided that the LH peak occurred 0.5-2 days before the VER peak and that ovulation then occurred in average 2 days after the LH peak. (C) 2020 The Authors. Published by Elsevier Inc.Peer reviewe