Carbon dioxide activation by a uranium(III) complex derived from a chelating bis(aryloxide) ligand

The new dianionic ligand, C6H4{p-C(CH3)2C6H2Me2O−}2 (= p-Me2bp), featuring two aryloxide donors and a central arene ring, has been synthesized, and used to prepare the mixed-ligand U(III) compound, [U(Cp*)(p-Me2bp)] which exhibits an η6-interaction with the uranium center. Reductive activation of CO2 was investigated using [U(Cp*)(p-Me2bp)] in supercritical CO2, which gave a dinuclear uranium carbonate complex,{U(Cp*)(p-Me2bp)}2(μ-η1:η2-CO3), cleanly and selectively. Reactivity studies in conventional solvents using lower pressures of CO2 showed the formation of a rare U(IV) oxalate complex, {U(Cp*)(p-Me2bp)}2(μ-η2:η2-C2O2), alongside {U(Cp*)(p-Me2bp)}2(μ-η1:η2-CO3). The relative ratio of the latter two products is temperature dependent: at low temperatures (-78 ˚C) oxalate formation is favored, whilst at room temperature the carbonate is the dominant product. The U(IV) iodide, [U(Cp*)(p-Me2bp)I], was also synthesized and used as part of an electrochemical study, the results of which showed that [U(Cp*)(p-Me2bp)] has a UIV/UIII redox couple of −2.18 V vs FeCp2+/0 as well as an possible electrochemically accessible UIII/UII reduction process at −2.56 V vs FeCp2+/0

A Variational Expansion for the Free Energy of a Bosonic System

In this paper, a variational perturbation scheme for nonrelativistic many-Fermion systems is generalized to a Bosonic system. By calculating the free energy of an anharmonic oscillator model, we investigated this variational expansion scheme for its efficiency. Using the modified Feynman rules for the diagrams, we obtained the analytical expression of the free energy up to the fourth order. Our numerical results at various orders are compared with the exact and other relevant results.Comment: 9 pages, 3 EPS figures. With a few typo errors corrected. to appear in J. Phys.

Levinson's theorem and scattering phase shift contributions to the partition function of interacting gases in two dimensions

We consider scattering state contributions to the partition function of a two-dimensional (2D) plasma in addition to the bound-state sum. A partition function continuity requirement is used to provide a statistical mechanical heuristic proof of Levinson's theorem in two dimensions. We show that a proper account of scattering eliminates singularities in thermodynamic properties of the nonideal 2D gas caused by the emergence of additional bound states as the strength of an attractive potential is increased. The bound-state contribution to the partition function of the 2D gas, with a weak short-range attraction between its particles, is found to vanish logarithmically as the binding energy decreases. A consistent treatment of bound and scattering states in a screened Coulomb potential allowed us to calculate the quantum-mechanical second virial coefficient of the dilute 2D electron-hole plasma and to establish the difference between the nearly ideal electron-hole gas in GaAs and the strongly correlated exciton/free-carrier plasma in wide-gap semiconductors such as ZnSe or GaN.Comment: 10 pages, 3 figures; new version corrects some minor typo

The NIDDK Central Repository at 8 years—Ambition, Revision, Use and Impact

The National Institute of Diabetes and Digestive and Kidney Diseases (NIDDK) Central Repository makes data and biospecimens from NIDDK-funded research available to the broader scientific community. It thereby facilitates: the testing of new hypotheses without new data or biospecimen collection; pooling data across several studies to increase statistical power; and informative genetic analyses using the Repository’s well-curated phenotypic data. This article describes the initial database plan for the Repository and its revision using a simpler model. Among the lessons learned were the trade-offs between the complexity of a database design and the costs in time and money of implementation; the importance of integrating consent documents into the basic design; the crucial need for linkage files that associate biospecimen IDs with the masked subject IDs used in deposited data sets; and the importance of standardized procedures to test the integrity data sets prior to distribution. The Repository is currently tracking 111 ongoing NIDDK-funded studies many of which include genotype data, and it houses over 5 million biospecimens of more than 25 types including serum, plasma, stool, urine, DNA, red blood cells, buffy coat and tissue. Repository resources have supported a range of biochemical, clinical, statistical and genetic research (188 external requests for clinical data and 31 for biospecimens have been approved or are pending). Genetic research has included GWAS, validation studies, development of methods to improve statistical power of GWAS and testing of new statistical methods for genetic research. We anticipate that the future impact of the Repository’s resources on biomedical research will be enhanced by (i) cross-listing of Repository biospecimens in additional searchable databases and biobank catalogs; (ii) ongoing deployment of new applications for querying the contents of the Repository; and (iii) increased harmonization of procedures, data collection strategies, questionnaires etc. across both research studies and within the vocabularies used by different repositories

The reductive activation of CO2 across a Ti═Ti double bond: synthetic, structural, and mechanistic studies

[Image: see text] The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti(2)Pn(†)(2) (1) (Pn(†) = 1,4-{Si(i)Pr(3)}(2)C(8)H(4)) with CO(2) is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO(2) reaction is performed at −78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO(2) molecule bound symmetrically to the two Ti centers in a μ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO(2) is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti–Ti bond has been cleaved and one pentalene ligand binds in an η(8) fashion to each of the formally Ti(III) centers. The molecular structure of 7 shows a “side-on” bound carbonyl ligand. Bonding of the double-sandwich species Ti(2)Pn(2) (Pn = C(8)H(6)) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO(2) reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-Ti(III) species to yield di-Ti(II) and di-Ti(IV) products. 1 forms a structurally characterized, thermally stable CS(2) adduct 8 that shows symmetrical binding to the Ti(2) unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph(3)PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti–Ti bond has been cleaved

Justifications-on-demand as a device to promote shifts of attention associated with relational thinking in elementary arithmetic

Student responses to arithmetical questions that can be solved by using arithmetical structure can serve to reveal the extent and nature of relational, as opposed to computational thinking. Here, student responses to probes which require them to justify-on-demand are analysed using a conceptual framework which highlights distinctions between different forms of attention. We analyse a number of actions observed in students in terms of forms of attention and shifts between them: in the short-term (in the moment), medium-term (over several tasks), and long-term (over a year). The main factors conditioning students´ attention and its movement are identified and some didactical consequences are proposed

Safeguarding children in dentistry: 1. Child protection training, experience and practice of dental professionals with an interest in paediatric dentistry

* Few dental professionals with child protection training have experience of making referrals. * There is a wide gap in practice between recognising signs of child abuse and neglect and responding effectively. * This may indicate missed opportunities to save children from continuing abuse. * There is a need for improved child protection information, support and training for dental professionals. Abstract Following several highly publicised inquiries into the deaths of children from abuse and neglect, there has been much recent interest in the role and responsibility of all health professionals to protect children at risk of maltreatment. The findings of a postal questionnaire, sent in March 2005 to 789 dentists and dental care professionals with an interest in paediatric dentistry working in varied settings in the UK, are presented in a two-part report and discussed in the context of current multi-agency good practice in safeguarding and promoting the welfare of children. This first part explores reported child protection training, experience and practice. There was a significant gap between recognising signs of abuse and responding effectively: 67% of respondents had suspected abuse or neglect of a child patient at some time in their career but only 29% had ever made a child protection referral. The dental profession is alerted to the need to ensure necessary appropriate action to safeguard children is always taken when child abuse or neglect are suspected

Impact of Glycemic and Blood Pressure Variability on Surrogate Measures of Cardiovascular Outcomes in Type 2 Diabetic Patients

OBJECTIVE—The effect of glycemic variability (GV) on cardiovascular risk has not been fully clarified in type 2 diabetes. We evaluated the effect of GV, blood pressure (BP), and oxidative stress on intima-media thickness (IMT), left ventricular mass index (LVMI), flow-mediated dilation (FMD), and sympathovagal balance (low frequency [LF]/high frequency [HF] ratio) in 26 type 2 diabetic patients (diabetes duration 4.41 6 4.81 years; HbA1c 6.70 6 1.25%) receiving diet and/or metformin treatment, with no hypotensive treatment or complications. RESEARCH DESIGN AND METHODS—Continuous glucose monitoring (CGM) data were used to calculate mean amplitude of glycemic excursion (MAGE), continuous overall net glycemic action (CONGA)-2, mean blood glucose (MBG), mean postprandial glucose excursion (MPPGE), and incremental area under the curve (IAUC). Blood pressure (BP), circadian rhythm, and urinary 15-F2t-isoprostane (8-iso-prostaglandin F2a [PGF2a]) were also evaluated. Subjects were divided into dipper (D) and nondipper (ND) groups according to DBP. RESULTS—IMT and LVMIwere increased inNDversusD(0.7760.08 vs. 0.6860.13 [P=0.04] and 67 6 14 vs. 55 6 11 [P = 0.03], respectively). MBG, MAGE, and IAUC were significantly associated with LF/HF ratio at night (r = 0.50, P = 0.01; r = 0.40, P = 0.04; r = 0.41, P = 0.04, respectively), MPPGE was negatively associated with FMD (r =20.45, P = 0.02), andCONGA-2was positively associatedwith LVMI (r=0.55, P=0.006).TheDsystolic BP was negatively associated with IMT (r =20.43, P = 0.03) andwith LVMI (r =20.52, P = 0.01). Urinary 8-iso-PGF2a was positively associated with LVMI (r = 0.68 P , 0.001). CONCLUSIONS—An impaired GV and BP variability is associated with endothelial and cardiovascular damage in short-term diabetic patients with optimal metabolic control. Oxidative stress is the only independent predictor of increased LV mass and correlates with glucose and BP variability

The racist bodily imaginary: the image of the body-in-pieces in (post)apartheid culture

This paper outlines a reoccurring motif within the racist imaginary of (post)apartheid culture: the black body-in-pieces. This disturbing visual idiom is approached from three conceptual perspectives. By linking ideas prevalent in Frantz Fanon’s description of colonial racism with psychoanalytic concepts such as Lacan’s notion of the corps morcelé, the paper offers, firstly, an account of the black body-in-pieces as fantasmatic preoccupation of the (post)apartheid imaginary. The role of such images is approached, secondly, through the lens of affect theory which eschews a representational ‘reading’ of such images in favour of attention to their asignifying intensities and the role they play in effectively constituting such bodies. Lastly, Judith Butler’s discussion of war photography and the conditions of grievability introduces an ethical dimension to the discussion and helps draw attention to the unsavory relations of enjoyment occasioned by such images