The kinetics of base hydrolysis of [Co(trien)(amine)Cl]2+ complexes (amine=imidazole,pyridine,n-butylamine and 2,2-dimethoxyethylamine)

Summary The complexescis--[Co(trien)(ImH)Cl]²⁺ (ImH=imidazole, trien=1,8-diamino-3,6-diazaoctane),cis--[Co(trien)(Buⁿ-NH₂)Cl^–]²⁺,cis--[Co(trien)(NH₂CH₂-CH(OMe)₂)Cl^–]²⁺ andcis-₂-[Co(trien)(py)Cl]²⁺ (py=pyridine) have been characterised and their kinetics of base hydrolysis studied. Thecis--isomers which have afac-fac arrangement of the trien ligand have values of k _OH ²⁵ in the 73 to 253 dm³ mol^–1 s^–1 range at I=0.1 mol dm^–3. Extremely rapid base hydrolysis is observed withcis-₂-[Co(trien)(py)Cl]²⁺ where k _OH ²⁵ is 6.65×10⁶ mol³ mol^–1 s^–1 at I=0.1 mol dm^–3. This complex has amer-fac arrangement of the trien ligand with flatsec-NH donor leading to rapid base hydrolysis due to good -overlap between the conjugate base and cobalt(III). The pyridine ligand causes aca. 30 fold rate increase compared with the hydrolysis ofcis-₂-[Co(trien)(NH₃)Cl]²⁺.     

Generation of accurate on-chip time constants and stabletransconductances

A method for generating accurately known on-chip time constants and less accurate but stable transistor transconductances over process, power-supply, and temperature variations is presented. The technique uses a constant-g_m bias circuit, which has a resistor that is tuned with a fully integrated CMOS phase-locked loop (PLL) locked to an external frequency reference (normally present in most systems). Other on-chip analog circuits biased using the same constant-g_m bias circuit are also stabilized. The PLL uses a charge-pump structure with three control loops (two digital and one analog) having overlapping ranges with hysteresis to minimize tuning glitches in the steady state. The PLL has a lock range of 135 to 300 MHz, and displays an RMS jitter of 15.6 ps. The transconductances generated from the circuit display a 2.2% variation for a 60°C change in temperature, and a 1.3% variation for a 10% variation in power-supply voltage. The design has been fabricated in a 0.35-μm CMOS process, using an active area of 1200×1200 μm² and draws 5.8 mA from a 3.3-V supply     

Preserving energy resp. dissipation in numerical PDEs using the “Average Vector Field” method

We give a systematic method for discretizing Hamiltonian partial differential equations (PDEs) with constant symplectic structure, while preserving their energy exactly. The same method, applied to PDEs with constant dissipative structure, also preserves the correct monotonic decrease of energy. The method is illustrated by many examples. In the Hamiltonian case these include: the sine–Gordon, Korteweg–de Vries, nonlinear Schrödinger, (linear) time-dependent Schrödinger, and Maxwell equations. In the dissipative case the examples are: the Allen–Cahn, Cahn–Hilliard, Ginzburg–Landau, and heat equations.     

Editing strategies in television news documentaries

This study describes the editing techniques used in four renowned television news documentaries that aired between 1954 and 1982. It is informed by Peirce's theories of signs, and realist and symbolic film theory, as well as some of the understandings common to broadcast journalists. The analysis attempts to bridge subdisciplinary boundaries to advance an accessible vocabulary for discussing journalistic representational strategies. The prevalence of continuity and thematic editing styles, special transitional effects, audio track synchronization, and differing cutting rates was quantitatively analyzed and linked to classic film realism and montage strategies. The quantitative findings and a comparative case study analysis of the structural nuances of each documentary illustrate the variety of representational strategies used by network journalists. These findings are discussed in light of analysts' assertions that televised reports have become increasingly journalist centered.     

Bragg-wave scattering and the narrow-vee wake

A coherent radar on a cliff overlooking the ocean was used to illuminate the ocean surface at a grazing angle of 10° during and after the passage of a ship through the beam. Simultaneous L-band and X-band data were collected. The display of surface reflectivity (power) showed a prominent narrow-vee feature at L-band, as was observed in earlier L-band satellite observations. A corresponding narrow-vee structure was observed in X-band, but was not as strong as other components of the wake signature. On the other hand, the Doppler-velocity displays at both radar frequencies yielded the same distinctive signature, i.e., a pair of compact features traveling outward from the centerline, each exhibiting a Doppler velocity that was the Bragg phase velocity corresponding to that radar frequency. The location of the velocity signature coincided at L-band with that of the power signature. Further, the L-band wake was persistent enough to verify that the feature was propagating at the Bragg group velocity, roughly the same as that for X-band. This result confirms an earlier hypothesis that the mechanism underlying the narrow-vee signature is the outward propagation of Bragg waves created by the ship's passage     

High‐Throughput Bioassays using “Dip‐and‐Go” Multiplexed Electrospray Mass Spectrometry

A multiplexed system based on inductive nanoelectrospray mass spectrometry (nESI‐MS) has been developed for high‐throughput screening (HTS) bioassays. This system combines inductive nESI and field amplification micro‐electrophoresis to achieve a “dip‐and‐go” sample loading and purification strategy that enables nESI‐MS based HTS assays in 96‐well microtiter plates. The combination of inductive nESI and micro‐electrophoresis makes it possible to perform efficient in situ separations and clean‐up of biological samples. The sensitivity of the system is such that quantitative analysis of peptides from 1–10 000 nm can be performed in a biological matrix. A prototype of the automation system has been developed to handle 12 samples (one row of a microtiter plate) at a time. The sample loading and electrophoretic clean‐up of biosamples can be done in parallel within 20 s followed by MS analysis at a rate of 1.3 to 3.5 s per sample. The system was used successfully for the quantitative analysis of BACE1‐catalyzed peptide hydrolysis, a prototypical HTS assay of relevance to drug discovery. IC₅₀ values for this system were in agreement with LC‐MS but recorded in times more than an order of magnitude shorter.     

Photochemistry of formic acid monomer at 222 nm

The yields of CO₂ and CO formed from the gas-phase photolysis at 222 nm of very low pressures of formic acid where the monomer predominates have been determined using FTIR spectroscopy. The observed ratio of CO₂/CO approaches unity as the formic acid pressure approaches zero. Previous studies have shown that the quantum yield for HCOOH + hv → OH + HCO (or H + CO) is 0.70 at 298 K. The present experimental results indicate that the ratio of the quantum yields of the possible molecular photolysis channels forming H₂ + CO₂ (?_1b) and H₂O + CO (?_1c) is ca. 1. Including this result in an analysis of previously reported quantum yields of CO and CO₂ determined at higher pressures of formic acid, where both monomer and dimer contribute significantly to the products, indicates that ?_1b = ?_1c = 0. © 1994 John Wiley & Sons, Inc.