Structurally Modelling the 2-His-1-Carboxylate Facial Triad with a Bulky N,N,O Phenolate Ligand

We present the synthesis and coordination chemistry of a bulky, tripodal N,N,O ligand, Im^Ph2NNO ^{t Bu} ( L ), designed to model the 2-His-1-carboxylate facial triad (2H1C) by means of two imidazole groups and an anionic 2,4-di-tert-butyl-subtituted phenolate. Reacting K-L with MCl₂ (M = Fe, Zn) affords the isostructural, tetrahedral non-heme complexes [Fe(L)(Cl)] ( 1 ) and [Zn(L)(Cl)] ( 2 ) in high yield. The tridentate N,N,O ligand coordination observed in their X-ray crystal structures remains intact and well-defined in MeCN and CH₂Cl₂ solution. Reacting 2 with NaSPh affords a tetrahedral zinc thiolate complex, [Zn(L)(SPh)] ( 4 ), that is relevant to isopenicillin N synthase (IPNS) biomimicry. Cyclic voltammetry studies demonstrate the ligand's redox non-innocence, where phenolate oxidation is the first electrochemical response observed in K-L , 2 and 4 . However, the first electrochemical oxidation in 1 is iron-centred, the assignment of which is supported by DFT calculations. Overall, Im^Ph2NNO ^{t Bu} provides access to well-defined mononuclear, monoligated, N,N,O-bound metal complexes, enabling more accurate structural modelling of the 2H1C to be achieved.     

Fracture data and stress-strain behavior of rocks in triaxial compression

Test results are reported for a recently completed experimental research program on rocks subjected to triaxial compression. Sandstone, marble, granite and shale specimens were tested at confining pressures as high as 90,000 psi corresponding to mean stresses of up to 143,000 psi. Recognizing that the largest potential experimental error in such tests results from making strain and load measurements external to the vessel, special load and strain-measuring devices were designed and fabricated for use inside the pressure vessel. The specimens were carefully machined cylinders with length-to-diameter ratios of two and with diameters ranging from 4/16 in. to 1 in. The confining pressure was held constant during each run, but varied from 0 to 90,000 psi over the tests. Results are reported in the form of:

1. Stress-strain curves for individual specimens
2. Maximum shear stress at fracture vs. mean-stress curves for each rock type tested
3. Tabulation of results for 59 specimens

A number of tests were run on granite specimens which had been previously fractured. Results from these tests showed good agreement with tests on intact granite, providing the confining pressure was above 30,000 psi.     

A sensitive and rapid bridge for the study of magnetic susceptibilities at frequencies from 200 to 106 Hz

Summary A new piece of equipment is described for measuring / ₀ and / ₀ as a function of field (0 to 4250 Oe), temperature (1.2°K to room temperature) and frequency (200 Hz to 1 MHz). It is about ten times more sensitive than the Hartshorn bridge used in Leiden²⁾ and it is more convenient to operate as the measuring procedure is automatic after initial adjustments have been made. The main component is a bridge circuit of four inductors, built as closely similar to each other as possible. The output from the bridge goes to two phase sensitive detectors which monitor the two outputs, one inphase, one /2 out of phase, of the bridge. A heterodyne system is used where the input signal to the bridge is obtained by mixing the output from a variable frequency oscillator with that from a 1.5 MHz oscillator and taking the difference frequency, which is phase locked to a master oscillator. The output from the bridge, after preamplification, is mixed with a second output from the variable oscillator and the difference taken again. This gives a 1.5 MHz signal modulated by the magnetic effects in the bridge which is used in the two phase-sensitive detectors. Their output is recorded on an x–y writer. The bridge needs only be balanced to an output of about 50 mV because the sample is moved between two coils and the difference voltage is measured. The use of the same equipment to measure relaxation times longer than 100 ms is also described.Communication No. 349a from The Kamerlingh Onnes Laboratorium, Leiden, The Netherlands     

Mechanism of Intramolecular Photostabilization in Self‐Healing Cyanine Fluorophores

Organic fluorophores, which are popular labels for microscopy applications, intrinsically suffer from transient and irreversible excursions to dark‐states. An alternative to adding photostabilizers at high concentrations to the imaging buffer relies on the direct linkage to the fluorophore. However, the working principles of this approach are not yet fully understood. In this contribution, we investigate the mechanism of intramolecular photostabilization in self‐healing cyanines, in which photodamage is automatically repaired. Experimental evidence is provided to demonstrate that a single photostabilizer, that is, the vitamin E derivative Trolox, efficiently heals the cyanine fluorophore Cy5 in the absence of any photostabilizers in solution. A plausible mechanism is that Trolox interacts with the fluorophore through intramolecular quenching of triplet‐related dark‐states, which is a mechanism that appears to be common for both triplet‐state quenchers (cyclooctatetraene) and redox‐active compounds (Trolox, ascorbic acid, methylviologen). Additionally, the influence of solution‐additives, such as cysteamine and procatechuic acid, on the self‐healing process are studied. The results suggest the potential applicability of self‐healing fluorophores in stochastic optical reconstruction microscopy (STORM) with optical super‐resolution. The presented data contributes to an improved understanding of the mechanism involved in intramolecular photostabilization and has high relevance for the future development of self‐healing fluorophores, including their applications in various research fields.     

Alkene Isomerisation Catalysed by a Ruthenium PNN Pincer Complex

The [Ru(CO)H(PNN)] pincer complex based on a dearomatised PNN ligand (PNN: 2‐di‐tert‐butylphosphinomethyl‐6‐diethylaminomethylpyridine) was examined for its ability to isomerise alkenes. The isomerisation reaction proceeded under mild conditions after activation of the complex with alcohols. Variable‐temperature (VT) NMR experiments to investigate the role of the alcohol in the mechanism lend credence to the hypothesis that the first step involves the formation of a rearomatised alkoxide complex. In this complex, the hemilabile diethylamino side‐arm can dissociate, allowing alkene binding cis to the hydride, enabling insertion of the alkene into the metal–hydride bond, whereas in the parent complex only trans binding is possible. During this study, a new uncommon Ru⁰ coordination complex was also characterised. The scope of the alkene isomerisation reaction was examined.     

Synthesis, crystal structure and magnetic characterization of metal(II) coordination polymers based on 2-carboxyethylphosphonic acid and 1,10-phenanthroline (metal=Cu, Co, Cd)

Three non-isostructural metal(II) coordination polymers (metal=copper, cobalt, cadmium) were synthesized under the same mild hydrothermal conditions (T=408 K) by mixture of the corresponding metal acetate with 2-carboxyethylphosphonic acid and 1,10-phenanthroline (1:1:1 M ratio) and their structures were determined by single-crystal X-ray diffraction. Cu₂(HO₃PCH₂CH₂COO)₂(C₁₂H₈N₂)₂(H₂O)₂ and Cd₂(HO₃PCH₂CH₂COO)₂(C₁₂H₈N₂)₂ are triclinic (space group P-1) with a=7.908(5) Å, b=10.373(5) Å, c=11.515(5) Å, α=111.683(5)°, β=95.801(5)°, γ=110.212(5)° (T=120 K), and a=8.162(5) Å, b=9.500(5) Å, c=11.148(5) Å, α=102.623(5)°, β=98.607(5)°, γ=113.004(5)° (T=293 K), respectively. In contrast, [Co₂(HO₃PCH₂CH₂COO)₂(C₁₂H₈N₂)₂(μ-OH₂)](H₂O) is orthorhombic (space group Pbcn) with a=21.1057(2) Å, b=9.8231(1) Å, c=15.4251(1) Å (T=120 K). For these three compounds, structural features, including H-bond network and the π-π stacking interactions, and thermal stability are reported and discussed. None of the materials present a long-range magnetic order in the range of temperatures investigated from 300 K down to 1.8 K.     

EC–SPE–stripline-NMR analysis of reactive products: a feasibility study

Flow-through electrochemical conversion (EC) of drug-like molecules was hyphenated to miniaturized nuclear magnetic resonance spectroscopy (NMR) via on-line solid-phase extraction (SPE). After EC of the prominent p38α mitogen-activated protein kinase inhibitor BIRB796 into its reactive products, the SPE step provided preconcentration of the EC products and solvent exchange for NMR analysis. The acquisition of NMR spectra of the mass-limited samples was achieved in a stripline probe with a detection volume of 150 nL offering superior mass sensitivity. This hyphenated EC–SPE–stripline-NMR setup enabled the detection of the reactive products using only minute amounts of substrate. Furthermore, the integration of conversion and detection into one flow setup counteracts incorrect assessments caused by the degradation of reactive products. However, apparent interferences of the NMR magnetic field with the EC, leading to a low product yield, so far demanded relatively long signal averaging. A critical assessment of what is and what is not (yet) possible with this approach is presented, for example in terms of structure elucidation and the estimation of concentrations. Additionally, promising routes for further improvement of EC–SPE–stripline-NMR are discussed.     

The expected payoff to Internet auctions

In an Internet auction, the expected payoff acts as a benchmark of the reasonableness of the price that is paid for the purchased item. Since the number of potential bidders is not observable, the expected payoff is difficult to estimate accurately. We approach this problem by considering the bids as a record and 2-record sequence of the potential bidder’s valuation and using the Extreme Value Theory models to model the tail distribution of the bidder’s valuation and study the expected payoff. Along the discussions for three different cases regarding the extreme value index γ, we show that the observed payoff does not act as an accurate estimation of the expected payoff in all the cases except a subclass of the case γ = 0. Within this subclass and under a second order condition, the observed payoff consistently converges to the expected payoff and the corresponding asymptotic normality holds.