Amination with Pd-NHC complexes: rate and computational studies on the effects of the oxidative addition partner

Pd-PEPPSI-IPent, a recently-developed N-heterocyclic carbene (NHC) complex, has been evaluated in amination reactions with secondary amines and it has shown superb reactivity under the most mildly basic reaction conditions. Rate and computational studies were conducted to provide insight into the mechanism of the transformation. The IPent catalyst coordinates to the amine much more strongly than the IPr variant, thus favouring deprotonation with comparatively weak bases. Indeed the reaction is first order in base and only slightly more than zeroth order in amine.     

Multi‐asset barrier options and occupation time derivatives

A general framework is formulated to price various forms of European style multi‐asset barrier options and occupation time derivatives with one state variable having the barrier feature. Based on the lognormal assumption of asset price processes, the splitting direction technique is developed for deriving the joint density functions of multi‐variate terminal asset prices with provision for single or double barriers on one of the state variables. A systematic procedure is illustrated whereby multi‐asset option price formulas can be deduced in a systematic manner as extensions from those of their one‐asset counterparts. The formulation has been applied successfully to derive the analytic price formulas of multi‐asset options with external two‐sided barriers and sequential barriers, multi‐asset step options and delayed barrier options. The successful numerical implementation of these price formulas is demonstrated.     

Synthetic principles directing charge transport in low-band-gap dithienosilole-benzothiadiazole copolymers

Given the fundamental differences in carrier generation and device operation in organic thin-film transistors (OTFTs) and organic photovoltaic (OPV) devices, the material design principles to apply may be expected to differ. In this respect, designing organic semiconductors that perform effectively in multiple device configurations remains a challenge. Following "donor-acceptor" principles, we designed and synthesized an analogous series of solution-processable π-conjugated polymers that combine the electron-rich dithienosilole (DTS) moiety, unsubstituted thiophene spacers, and the electron-deficient core 2,1,3-benzothiadiazole (BTD). Insights into backbone geometry and wave function delocalization as a function of molecular structure are provided by density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) level. Using a combination of X-ray techniques (2D-WAXS and XRD) supported by solid-state NMR (SS-NMR) and atomic force microscopy (AFM), we demonstrate fundamental correlations between the polymer repeat-unit structure, molecular weight distribution, nature of the solubilizing side-chains appended to the backbones, and extent of structural order attainable in p-channel OTFTs. In particular, it is shown that the degree of microstructural order achievable in the self-assembled organic semiconductors increases largely with (i) increasing molecular weight and (ii) appropriate solubilizing-group substitution. The corresponding field-effect hole mobilities are enhanced by several orders of magnitude, reaching up to 0.1 cm(2) V(-1) s(-1) with the highest molecular weight fraction of the branched alkyl-substituted polymer derivative in this series. This trend is reflected in conventional bulk-heterojunction OPV devices using PC(71)BM, whereby the active layers exhibit space-charge-limited (SCL) hole mobilities approaching 10(-3) cm(2) V(-1) s(-1), and yield improved power conversion efficiencies on the order of 4.6% under AM1.5G solar illumination. Beyond structure-performance correlations, we observe a large dependence of the ionization potentials of the polymers estimated by electrochemical methods on polymer packing, and expect that these empirical results may have important consequences on future material study and device applications.     

Evidence for direct CP violation in B±→ηh± and observation of B0→ηK0

We report measurements of the branching fractions and CP asymmetries for B(±)→ηh(±) (h=K or π) and the observation of the decay B(0)→ηK(0) from the final data sample of 772×10(6) B ?B pairs collected with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. The measured branching fractions are B(B(±)→ηK(±))=(2.12±0.23±0.11)×10(-6), B(B(±)→ηπ(±))=(4.07±0.26±0.21)×10(-6), and B(B(0)→ηK(0))=(1.27(-0.29)(+0.33)±0.08)×10(-6), where the last decay is observed for the first time with a significance of 5.4 standard deviations (σ). We also find evidence for CP violation in the charged B modes, A(CP)(B(±)→ηK(±))=-0.38±0.11±0.01 and A(CP)(B(±)→ηπ(±))=-0.19±0.06±0.01 with significances of 3.8 σ and 3.0 σ, respectively. For all measurements, the first and second uncertainties are statistical and systematic, respectively.     

Evanescent-wave photoacoustic spectroscopy with optical micro/nano fibers

We demonstrate gas detection based on evanescent-wave photoacoustic (PA) spectroscopy with tapered optical fibers. Evanescent-field instead of open-path absorption is exploited for PA generation, and a quartz tuning fork is used for PA detection. A tapered optical fiber with a diameter down to the wavelength scale demonstrates detection sensitivity similar to an open-path system but with the advantages of easier optical alignment, smaller insertion loss, and multiplexing capability.     

High-sensitivity fiber-tip pressure sensor with graphene diaphragm

A miniature fiber-tip pressure sensor was built by using an extremely thin graphene film as the diaphragm. The graphene also acts as a light reflector, which, in conjunction with the reflection at the fiber end-air interface, forms a low finesse Fabry-Perot interferometer. The graphene based sensor demonstrated pressure sensitivity over 39.4 nm/kPa with a diaphragm diameter of 25 μm. The use of graphene as diaphragm material would allow highly sensitive and compact fiber-tip sensors.     

Option pricing with mean reversion and stochastic volatility

Many underlying assets of option contracts, such as currencies, commodities, energy, temperature and even some stocks, exhibit both mean reversion and stochastic volatility. This paper investigates the valuation of options when the underlying asset follows a mean-reverting lognormal process with stochastic volatility. A closed-form solution is derived for European options by means of Fourier transform. The proposed model allows the option pricing formula to capture both the term structure of futures prices and the market implied volatility smile within a unified framework. A bivariate trinomial lattice approach is introduced to value path-dependent options with the proposed model. Numerical examples using European options, American options and barrier options demonstrate the use of the model and the quality of the numerical scheme.     

Electron‐Deficient Alkynes as Cleavable Reagents for the Modification of Cysteine‐Containing Peptides in Aqueous Medium

Enriched cleavage : An efficient chemoselective cysteine modification of unprotected peptides and proteins has been developed by using electron‐deficient alkynes in aqueous media. Interestingly, terminal alkynone‐modified peptides could be converted back into the unmodified peptides by cleavage by adding thiols under mild conditions (see scheme).

     

Propagation of near-limit gaseous detonations in small diameter tubes

In this study, detonation limits in very small diameter tubes are investigated to further the understanding of the near-limit detonation phenomenon. Three small diameter circular tubes of 1.8, 6.3, and 9.5 mm inner diameters, of 3 m length, were used to permit the near-limit detonations to be observed over long distances of 300 to 1500 tube diameters. Mixtures with high argon dilution (stable) and without dilution (unstable) are used for the experiments. For stable mixtures highly diluted with argon for which instabilities are not important and where failure is due to losses only, the limit obtained experimentally appears well to be in good agreement in comparison to that computed by the quasi-steady ZND theory with flow divergence or curvature term modeling the boundary layer effects. For unstable detonations it is suggested that suppression of the instabilities of the cellular detonation due to boundary conditions is responsible for the failure of the detonation wave. Different near-limit propagation regimes are also observed, including the spinning and galloping mode. Based on the present experimental results, an attempt is made to study an operational criterion for the propagation limits of stable and unstable detonations.     

Synthesis,Structure, and Spectroscopic and Electrochemical Properties of Heteroleptic Bis(phthalocyaninato) Rare Earth Complexes with a C4 Symmetry

A series of eleven heteroleptic bis(phthalocyaninato) rare earth double‐deckers [M^III(pc){pc(α‐OC₅H₁₁)₄}] 1 – 11 (M=Y, Sm? Lu; pc=phthalocyaninato; pc(α‐OC₅H₁₁)₄=1,8,15,22‐tetrakis(1‐ethylpropoxy)phthalocyaninato) were prepared as racemic mixtures by [M^III(pc)(acac)]‐induced (acac=acetylacetonato) cyclic tetramerization of 3‐(1‐ethylpropoxy)phthalonitrile in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in refluxing pentanol. These compounds could also be prepared by treating [M^III(pc)(acac)] with the metal‐free phthalocyanine H₂{pc(α‐OC₅H₁₁)₄} in refluxing octanol. The whole series of double‐decker complexes 1 – 11 were characterized by elemental analysis and various spectroscopic methods. The molecular structures of the Sm, Eu, and Er complexes 1, 2 , and 8 , respectively, were also determined by single‐crystal X‐ray diffraction analysis. The effects of the rare earth ion size on the reaction yield, molecular structure, and spectroscopic and electrochemical properties of these complexes were systematically examined.