Platinum Indolylphosphine Fluorido and Polyfluorido Complexes: An Interplay between Cyclometallation,Fluoride Migration,and Hydrogen Bonding

The reaction of [PtCl₂(COD)] (COD=1,5-cyclooctadiene) with diisopropyl-2-(3-methyl)indolylphosphine (iPr₂P(C₉H₈N)) led to the formation of the platinum(ii ) chlorido complexes, cis-[PtCl₂{iPr₂P(C₉H₈N)}₂] ( 1 ) and trans-[PtCl₂{iPr₂P(C₉H₈N)}₂] ( 2 ). The cis-complex 1 reacted with NEt₃ yielding the complex cis-[PtCl{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}] ( 3 ) bearing a cyclometalated κ²-(P,N)-phosphine ligand, while the isomer 2 with a trans-configuration did not show any reactivity towards NEt₃. Treatment of 1 or 3 with (CH₃)₄NF (TMAF) resulted in the formation of the twofold cyclometalated complex cis-[Pt{κ²-(P,N)-iPr₂P(C₉H₇N)}₂] ( 4 ). The molecular structures of the complexes 1–4 were determined by single-crystal X-ray diffraction. The fluorido complex cis-[PtF{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}] ⋅ (HF)₄ ( 5 ⋅ (HF)₄) was formed when complex 4 was treated with different hydrogen fluoride sources. The Pt(ii ) fluorido complex 5 ⋅ (HF)₄ exhibits intramolecular hydrogen bonding in its outer coordination sphere between the fluorido ligand and the NH group of the 3-methylindolyl moiety. In contrast to its chlorido analogue 3 , complex 5 ⋅ (HF)₄ reacted with CO or the ynamide 1-(2-phenylethynyl)-2-pyrrolidinone to yield the complexes trans-[Pt(CO){κ²-(P,C)-iPr₂P(C₉H₇NCO)}{iPr₂P(C₉H₈N)}][F(HF)₄] ( 7 ) and a complex, which we suggest to be cis-[Pt{C=C(Ph)OCN(C₃H₆)}{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}][F(HF)₄] ( 9 ), respectively. The structure of 9 was assigned on the basis of DFT calculations as well as NMR and IR data. Hydrogen bonding of HF and NH to fluoride was proven to be crucial for the existence of 7 and 9 .     

Chemical Probing of the Human Sirtuin 5 Active Site Reveals Its Substrate Acyl Specificity and Peptide‐Based Inhibitors

Sirtuins are NAD⁺‐dependent deacetylases acting as sensors in metabolic pathways and stress response. In mammals there are seven isoforms. The mitochondrial sirtuin 5 is a weak deacetylase but a very efficient demalonylase and desuccinylase; however, its substrate acyl specificity has not been systematically analyzed. Herein, we investigated a carbamoyl phosphate synthetase 1 derived peptide substrate and modified the lysine side chain systematically to determine the acyl specificity of Sirt5. From that point we designed six potent peptide‐based inhibitors that interact with the NAD⁺ binding pocket. To characterize the interaction details causing the different substrate and inhibition properties we report several X‐ray crystal structures of Sirt5 complexed with these peptides. Our results reveal the Sirt5 acyl selectivity and its molecular basis and enable the design of inhibitors for Sirt5.     

How to predict viscous fingering in three component flow

In a WAG process (Water Alternate Gas), water and a miscible solvent (gas) are injected into a reservoir containing water and oil. The solvent will finger through the oil, leading to early breakthrough and poor recovery. Compared with a miscible flood, when only solvent is injected, fingering is supressed by the simultaneous injection of water, since this reduces the apparent mobility contrast between the injected and displaced fluids. The fingering in a miscible flood, with only hydrocarbon flowing, can be modelled successfully using a Todd and Longstaff fractional flow. In this paper, we demonstrate how to modify the effective Todd and Longstaff mobility ratio self-consistently to account for fingering in three component systems. The resultant empirical equations of flow are solved exactly in one dimension and are in excellent agreement with the averaged saturation and concentration profiles computed using two dimensional high resolution simulation, for a variety of injected water saturations, in both secondary and tertiary displacements.     

A Fair Allocation of County Cricket Opponents

Each team in the English County Cricket Championship plays against some other teams twice a year, and others only once. This paper describes a case study whose aim was to overcome this inherent unfairness by producing a four-year schedule of opponents which was as fair as possible, and could be easily seen to be fair, while still allowing for traditional rivalries. The schedule also needed to be satisfactory in regard to several other constraints and objectives. Various simple heuristics were used; these are described in some detail. Of particular interest is the effectiveness of a ‘local non-worsening’ approach when the objective is to find any feasible solution. This is equivalent to simulated annealing at a constant temperature of absolute zero.     

Profiling of generic anti-phosphopeptide antibodies and kinases with peptide microarrays using radioactive and fluorescence-based assays

Kinases represent one of the largest enzyme families and key regulatory proteins in the cell. Only a small subset of these enzymes has been characterised so far. We have prepared different types of phosphopeptide and peptide microarrays displaying peptides deduced from annotated human phosphorylation sites and cytoplasmic domains of all annotated human membrane proteins. This approach was enabled by fully-automated high throughput micro-scale synthesis of peptides by the SPOT technology combined with chemo-selective immobilisation on modified glass slides. The phosphopeptide microarrays displaying 2923 peptides in total have been used for the characterisation of commercially available generic anti-phosphopeptide antibodies. This enabled us to detect Abl kinase activity on a microarray with anti-phosphotyrosine antibodies yielding results comparable to those obtained from a radioactive assay. More than 13 000 peptides deposited on six glass slides were used to profile casein kinase 2 (CK2) using a radioactive assay, since no generic antibody for the reliable detection of serine or threonine phosphorylation could be identified. All previously identified substrates were detected in the microarray experiment. In order to confirm whether substrates on the microarray are substrates in solution phase assays, more than 700 peptides were synthesised and tested with CK2 in a solution phase assay. All substrates identified in the solution phase assay were also detected on the microarray.     

Direct angle resolved photoemission spectroscopy and superconductivity of strained high-T c films

Since 1997 we systematically perform direct angle resolved photoemission spectroscopy (ARPES) on in-situ grown thin (<30 nm) cuprate films. Specifically, we probe low-energy electronic structure and properties of high-T _c superconductors (HTSC) under different degrees of epitaxial (compressive vs. tensile) strain. In overdoped and underdoped in-plane compressed (the strain is induced by the choice of substrate) ≈15 nm thin La_{2 − x} Sr _x CuO₄ (LSCO) films we almost double T _c to 40 K, from 20 K and 24 K, respectively. Yet the Fermi surface (FS) remains essentially two-dimensional. In contrast, ARPES data under tensile strain exhibit the dispersion that is three-dimensional, yet T _c drastically decreases. It seems that the in-plane compressive strain tends to push the apical oxygen far away from the CuO₂ plane, enhances the two-dimensional character of the dispersion and increases T _c, while the tensile strain acts in the opposite direction and the resulting dispersion is three-dimensional. We have established the shape of the FS for both cases, and all our data are consistent with other ongoing studies, like EXAFS. As the actual lattice of cuprates is like a ‘Napoleon-cake’, i.e. rigid CuO₂ planes alternating with softer ‘reservoir’, that distort differently under strain, our data rule out all oversimplified two-dimensional (rigid lattice) mean field models. The work is still in progress on optimized La-doped Bi-2201 films with enhanced T _c.      

Electrochemical characteristics of the dynamic progression of erosion-corrosion under different flow conditions and their effects on corrosion rate calculation

Journal of Solid State Electrochemistry - The erosion-corrosion performance of X65 carbon steel at different flow conditions was electrochemically studied. Results show that the anodic polarization...     

Crossover mitigation strategies for redox-flow batteries

Redox-flow batteries can, in principle, use a wide range of active materials. However, a number of simultaneous requirements must be met to make a chemistry attractive. One of the most challenging requirements is minimizing transport of active species through the membrane separating the positive and negative electrodes, and the ensuing inefficiency and capacity loss. Developing technologies to mitigate crossover, and strategies for recovering from its consequences, will enable development of successful systems with new active materials. The rate and impact of crossover depend on the nature of the active materials and their fate after they transport across the separator. Accordingly, electrolyte solutions can be classified by what happens to the active species at the opposing electrolyte. This behavior also dictates what recovery strategies may be employed, and at what frequency. This review describes desirable attributes for active materials and separators that help diminish crossover, and strategies that can be used to recover from its effects for each of the different classes of electrolytes.     

Bounds on absorption times of directionally biased random sequences

A sequence of random variables X₀,X₁, … with values in {0, 1, …, n} representing a general finite-state stochastic process with absorbing state 0 is said to be directionally biased towards 0, if, for all j > 0, ϵ_j: = inf_k>0 {j − E[X_k | X_k−1 = j]} > 0. For such sequences, let t be the expected value of the time to absorption at 0. For a fixed set of biases, the least upper bound for this time can be computed with an algorithm requiring O(n²) steps. Simple upper bounds are described. In particular, t ≤ E[b_x0], where b_i = Σ_j≤i 1/¯ϵ_j and ¯ϵ_j = min_l≥j {ϵ_l}. If all ϵ_j ≤ ϵ_{j + 1} (so ¯ϵ_j = ϵ_j) and ϵ_n < 1, this bound for t is the best possible. For certain finite stochastic processes which we term conditionally independent of X₀ = i, b(i) bounds the expected time given X₀ = i. Similar results are given for lower bounds. The results of this paper were designed to be a useful tool for determining rates of convergence of stochastic optimization algorithms. © 1996 John Wiley & Sons, Inc.     

Multivariate dynamic modeling for Bayesian forecasting of business revenue

Forecasting enterprise-wide revenue is critical to many companies and presents several challenges and opportunities for significant business impact. This case study is based on model developments to address these challenges for forecasting in a large-scale retail company. Focused on multivariate revenue forecasting across collections of supermarkets and product categories, hierarchical dynamic models are natural: these are able to couple revenue streams in an integrated forecasting model, while allowing conditional decoupling to enable relevant and sensitive analysis together with scalable computation. Structured models exploit multi-scale modeling to cascade information on price and promotion activities as predictors relevant across categories and groups of stores. With a context-relevant focus on forecasting revenue 12 weeks ahead, the study highlights product categories that benefit from multi-scale information, defines insights into when, how, and why multivariate models improve forecast accuracy, and shows how cross-category dependencies can relate to promotion decisions in one category impacting others. Bayesian modeling developments underlying the case study are accessible in custom code for interested readers.