NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist

Tables of ^1H and ^(13)C NMR chemical shifts have been compiled for common organic compounds often used as reagents or found as products or contaminants in deuterated organic solvents. Building upon the work of Gottlieb, Kotlyar, and Nudelman in the Journal of Organic Chemistry, signals for common impurities are now reported in additional NMR solvents (tetrahydrofuran-d_8, toluene-d_8, dichloromethane-d_2, chlorobenzene-d_5, and 2,2,2-trifluoroethanol-d_3) which are frequently used in organometallic laboratories. Chemical shifts for other organics which are often used as reagents or internal standards or are found as products in organometallic chemistry are also reported for all the listed solvents

Where Are My Intelligent Assistant's Mistakes? A Systematic Testing Approach

Intelligent assistants are handling increasingly critical tasks, but until now, end users have had no way to systematically assess where their assistants make mistakes. For some intelligent assistants, this is a serious problem: if the assistant is doing work that is important, such as assisting with qualitative research or monitoring an elderly parent’s safety, the user may pay a high cost for unnoticed mistakes. This paper addresses the problem with WYSIWYT/ML (What You See Is What You Test for Machine Learning), a human/computer partnership that enables end users to systematically test intelligent assistants. Our empirical evaluation shows that WYSIWYT/ML helped end users find assistants’ mistakes significantly more effectively than ad hoc testing. Not only did it allow users to assess an assistant’s work on an average of 117 predictions in only 10 minutes, it also scaled to a much larger data set, assessing an assistant’s work on 623 out of 1,448 predictions using only the users’ original 10 minutes’ testing effort

Mass and Spin Renormalization in Lorentz Electrodynamics

A new, relativistically covariant, massive Lorentz Electrodynamics (LED) is presented in which the bare particle has a finite positive bare rest mass and moment of inertia. The particle's electromagnetic self-interaction renormalizes its mass and spin. Most crucially, the renormalized particle is a soliton: after any scattering process its rest mass and spin magnitude are dynamically restored to their pre-scattering values. This guarantees that ``an electron remains an electron,'' poetically speaking. A renormalization flow study of the limit of vanishing bare rest mass is conducted for this model. This limit yields a purely electromagnetic classical field theory with ultra-violet cutoff at about the electron's Compton wavelength! The renormalized limit model matches the empirical electron data as orderly as one can hope for at the level of Lorentz theory. In particular, no superluminal equatorial gyration speeds occur.Comment: LaTeX, 70 pages, 2 eps figures, submitted; a small computational blunder in Eq. (10.25)ff of earlier version has been correcte

Trial Protocol: Randomised controlled trial of the effects of very low calorie diet, modest dietary restriction, and sequential behavioural programme on hunger, urges to smoke, abstinence and weight gain in overweight smokers stopping smoking

Background\ud Weight gain accompanies smoking cessation, but dieting during quitting is controversial as hunger may increase urges to smoke. This is a feasibility trial for the investigation of a very low calorie diet (VLCD), individual modest energy restriction, and usual advice on hunger, ketosis, urges to smoke, abstinence and weight gain in overweight smokers trying to quit. \ud \ud Methods\ud This is a 3 armed, unblinded, randomized controlled trial in overweight (BMI > 25 kg/$m^2$), daily smokers (CO > 10 ppm); with at least 30 participants in each group. Each group receives identical behavioural support and NRT patches (25 mg(8 weeks),15 mg(2 weeks),10 mg(2 weeks)). The VLCD group receive a 429-559 kcal/day liquid formula beginning 1 week before quitting and continuing for 4 weeks afterwards. The modest energy restricted group (termed individual dietary and activity planning(IDAP)) engage in goal-setting and receive an energy prescription based on individual basal metabolic rate(BMR) aiming for daily reduction of 600 kcal. The control group receive usual dietary advice that accompanies smoking cessation i.e. avoiding feeling hungry but eating healthy snacks. After this, the VLCD participants receive IDAP to provide support for changing eating habits in the longer term; the IDAP group continues receiving this support. The control group receive IDAP 8 weeks after quitting. This allows us to compare IDAP following a successful quit attempt with dieting concurrently during quitting. It also aims to prevent attrition in the unblinded, control group by meeting their need for weight management. Follow-up occurs at 6 and 12 months. \ud \ud Outcome measures include participant acceptability, measured qualitatively by semi-structured interviewing and quantitatively by recruitment and attrition rates. Feasibility of running the trial within primary care is measured by interview and questionnaire of the treatment providers. Adherence to the VLCD is verified by the presence of urinary ketones measured weekly. Daily urges to smoke, hunger and withdrawal are measured using the Mood and Physical Symptoms Scale-Combined (MPSS-C) and a Hunger Craving Score (HCS). 24 hour, 7 day point prevalence and 4-week prolonged abstinence (Russell Standard) is confirmed by CO < 10 ppm. Weight, waist and hip circumference and percentage body fat are measured at each visit. \ud \ud Trial Registration\ud Current controlled trials ISRCTN83865809\ud \u

On scattering of solitons for the Klein-Gordon equation coupled to a particle

We establish the long time soliton asymptotics for the translation invariant nonlinear system consisting of the Klein-Gordon equation coupled to a charged relativistic particle. The coupled system has a six dimensional invariant manifold of the soliton solutions. We show that in the large time approximation any finite energy solution, with the initial state close to the solitary manifold, is a sum of a soliton and a dispersive wave which is a solution of the free Klein-Gordon equation. It is assumed that the charge density satisfies the Wiener condition which is a version of the ``Fermi Golden Rule''. The proof is based on an extension of the general strategy introduced by Soffer and Weinstein, Buslaev and Perelman, and others: symplectic projection in Hilbert space onto the solitary manifold, modulation equations for the parameters of the projection, and decay of the transversal component.Comment: 47 pages, 2 figure

Dynamics of a Massive Black Hole at the Center of a Dense Stellar System

We develop a simple physical model to describe the dynamics of a massive point-like object, such as a black hole, near the center of a dense stellar system. It is shown that the total force on this body can be separated into two independent parts, one of which is the slowly varying influence of the aggregate stellar system, and the other being the rapidly fluctuating stochastic force due to discrete encounters with individual stars. For the particular example of a stellar system distributed according to a Plummer model, it is shown that the motion of the black hole is then similar to that of a Brownian particle in a harmonic potential, and we analyze its dynamics using an approach akin to Langevin's solution of the Brownian motion problem. The equations are solved to obtain the average values, time-autocorrelation functions, and probability distributions of the black hole's position and velocity. By comparing these results to N-body simulations, we demonstrate that this model provides a very good statistical description of the actual black hole dynamics. As an application of our model, we use our results to derive a lower limit on the mass of the black hole Sgr A* in the Galactic center.Comment: 27 pages, 4 figures. ApJ, in press (2002). New section with application to SgrA

State based model of long-term potentiation and synaptic tagging and capture

Recent data indicate that plasticity protocols have not only synapse-specific but also more widespread effects. In particular, in synaptic tagging and capture (STC), tagged synapses can capture plasticity-related proteins, synthesized in response to strong stimulation of other synapses. This leads to long-lasting modification of only weakly stimulated synapses. Here we present a biophysical model of synaptic plasticity in the hippocampus that incorporates several key results from experiments on STC. The model specifies a set of physical states in which a synapse can exist, together with transition rates that are affected by high- and low-frequency stimulation protocols. In contrast to most standard plasticity models, the model exhibits both early- and late-phase LTP/D, de-potentiation, and STC. As such, it provides a useful starting point for further theoretical work on the role of STC in learning and memory

Wigner's Dynamical Transition State Theory in Phase Space: Classical and Quantum

A quantum version of transition state theory based on a quantum normal form (QNF) expansion about a saddle-centre-...-centre equilibrium point is presented. A general algorithm is provided which allows one to explictly compute QNF to any desired order. This leads to an efficient procedure to compute quantum reaction rates and the associated Gamov-Siegert resonances. In the classical limit the QNF reduces to the classical normal form which leads to the recently developed phase space realisation of Wigner's transition state theory. It is shown that the phase space structures that govern the classical reaction d ynamicsform a skeleton for the quantum scattering and resonance wavefunctions which can also be computed from the QNF. Several examples are worked out explicitly to illustrate the efficiency of the procedure presented.Comment: 132 pages, 31 figures, corrected version, Nonlinearity, 21 (2008) R1-R11

The BL Lac objects OQ 530 and S5 0716+714. Simultaneous observations in the X-rays, radio, optical and TeV bands

We present the results of the BeppoSAX observations of two BL Lacs, OQ 530 and S5 0716+714, as part of a ToO program for the simultaneous observation at radio, optical, X-ray and TeV energies. Both sources are detected in the LECS and MECS, with S5 0716+714 visible also in the PDS band, up to about 60 keV. The X-ray spectra of both sources are better fitted by a double power-law model, with a steep soft X-ray component flattening at harder energies, with breaks at 0.3 and 1.5 keV, respectively. The concave shape of the spectra in both objects is consistent with soft X-rays being produced by the synchrotron and harder X-rays by the inverse Compton processes. Also the X-ray variability properties confirm this scenario, in particular for S5 0716+714 our observation shows variations by about a factor 3 over one hour below 3 keV and no variability above. Their simultaneous broad band energy spectral distributions can be successfully interpreted within the frame of a homogeneous synchrotron and inverse Compton model, including a possible contribution from an external source of seed photons with the different spectral states of S5 0716+714 being reproduced by changing the injected power. The resulting parameters are fully consistent with the two sources being intermediate objects within the "sequence" scenario proposed for blazars.Comment: 10 pages, 8 figures, accepted by A&