Alkyne-functionalized ruthenium nanoparticles: ruthenium-vinylidene bonds at the metal-ligand interface

Stable ruthenium nanoparticles were prepared by the self-assembly of 1-dodecyne onto the "bare" Ru colloid surface. The formation of a Ru-vinylidene (Ru═C═CH-R) interfacial bonding linkage was confirmed by the specific reactivity of the nanoparticles with imine derivatives to form a heterocyclic complex at the metal-ligand interface, as manifested in (1)H and (13)C NMR, photoluminescence, and electrochemical measurements in which a ferrocenyl imine was used as the labeling probe. Notably, the resulting nanoparticles could also undergo olefin metathesis reactions with vinyl-terminated molecules, as exemplified by the functionalization of the nanoparticles with 1-vinylpyrene. In sharp contrast, no reactvity was observed with 1-dodecynide-stabilized ruthenium nanoparticles with either imine or vinyl derivatives, indicating that these (deprotonated) nanoparticles were stabilized instead by the formation of a Ru-C≡ dπ bond at the metal-ligand interface.     

Commutative quantum operator algebras

A key notion bridging the gap between quantum operator algebras [26] and vertex operator algebras [4, 9] is the definition of the commutativity of a pair of quantum operators (see Section 2). This is not commutativity in any ordinary sense, but it is clearly the correct generalization to the quantum context. In [26] we give a definition of a commutative quantum operator algebra. We show in [26] that a vertex operator algebra gives rise to a special case of a CQOA. The main purpose of the current paper is to further develop the foundations for a complete mathematical theory of CQOAs. We give proofs of most of the relevant results announced in [26], and we carry out some calculations with sufficient detail to enable the interested reader to become proficient with the algebra of commuting quantum operators.     

Intraparticle charge delocalization of carbene-functionalized ruthenium nanoparticles manipulated by selective ion binding

Olefin metathesis reactions of carbene-stabilized ruthenium nanoparticles were exploited for the incorporation of multiple functional moieties onto the nanoparticle surface. When the nanoparticles were cofunctionalized with 4-vinylbenzo-18-crown-6 and 1-vinylpyrene, the resulting particles exhibited fluorescence characteristics that were consistent with dimeric pyrene with a conjugated chemical bridge, with three peaks observed in the emission spectra at 391, 410, and 485 nm. The behaviors were ascribed to intraparticle charge delocalization between the pyrene moieties afforded by the conjugated Ru═carbene interfacial linkages. Notably, upon the binding of metal ions in the crown ether cavity, the emission intensity of the nanoparticle fluorescence was found to diminish at 485 nm and concurrently increase at 391 and 410 nm rather markedly, with the most significant effects observed with K(+). This was accounted for by the selective binding of 18-crown-6 to potassium ions, where the positively charged ions led to the polarization of the nanoparticle core electrons that was facililated by the conjugated linkage to the metal surface and hence impeded intraparticle charge delocalization. Control experiments with a pyrene-crown ether conjugate (2) and with ruthenium nanoparticles cofunctionalized with 4-vinylbenzo-18-crown-6 and 1-allylpyrene suggested that the through-bond pathway played a predominant role in the manipulation of intraparticle electronic communication whereas the contributions from simple electrostatic interactions (i.e., through-space pathway) were minimal.     

A Construction of Generalized Harish-Chandra Modules for Locally Reductive Lie Algebras

We study cohomological induction for a pair $ {\left( {\mathfrak{g},\mathfrak{k}} \right)} $ , $ \mathfrak{g} $ being an infinitedimensional locally reductive Lie algebra and $ \mathfrak{k} \subset \mathfrak{g} $ being of the form $ \mathfrak{k}_{0} \subset C_{\mathfrak{g}} {\left( {\mathfrak{k}_{0} } \right)} $ , where $ \mathfrak{k}_{0} \subset \mathfrak{g} $ is a finite-dimensional reductive in $ \mathfrak{g} $ subalgebra and $ C_{\mathfrak{g}} {\left( {\mathfrak{k}_{0} } \right)} $ is the centralizer of $ \mathfrak{k}_{0} $ in $ \mathfrak{g} $ . We prove a general nonvanishing and $ \mathfrak{k} $ -finiteness theorem for the output. This yields, in particular, simple $ {\left( {\mathfrak{g},\mathfrak{k}} \right)} $ -modules of finite type over k which are analogs of the fundamental series of generalized Harish-Chandra modules constructed in [PZ1] and [PZ2]. We study explicit versions of the construction when $ \mathfrak{g} $ is a root-reductive or diagonal locally simple Lie algebra.     

Pulsed fourier transform NMR of substituted aryltrimethyltin derivatives : II. (119Sn-13C) coupling constants and 13C chemical shifts of meta- and para-derivatives

Carbon-13 NMR data are reported for thirteen para- and meta-substituted phenyltrimethyltin compounds, RC₆H₄Sn(CH₃)₃, where R = para-N(CH₃)₂, para-OCH₃, para-OC₂H₅, para-CH₃, meta-CH₃, -H, para-F, meta-OCH₃, para-Cl, para-Br, meta-F, meta-Cl and para-Sn(CH₃)₃. In the para-derivatives, correlation coefficients with Hammet σ-constants of greater than ca. 0.9 are obtained with the tin-carbon couplings to methyl, C₁ and C₄ carbons, and with the carbon-13 chemical shifts δ(C(1)). In the meta-derivatives, the couplings |J(Sn-CH₃)|:, |:J(Sn-C(1))|:, |:J(Sn-C(3))|: and |:J(Sn-C(6))|:, and the shifts δ(C(1)) and δ(C(5)) correlate well with Hammett σ. In the para-derivatives, sensitivity to change in substituent falls off C(4) > C(3, 5) > C(1) > C(2, 6) > CH₃ as registered by the δ(C), while in the meta-derivatives δ(C) changes decrease C(3) > C(2), C(4) > C(1) > C(5), C(6) > CH₃. The magnitudes of the tin coupling constants decrease C(1) > CH₃ > C(3, 5) > C(2, 6) > C(4) in the para-derivatives, while in the meta-series the order is C(1) > CH₃ > C(3), C(5) > C(2) > C(6) > C(4). The two sets of one-bond |:J(Sn-CH₃)|: and |:J(Sn-C(1)|: values correspond closely to the 0.25/0.33 ratio of coefficients in the LCAO approach, and are interpreted in terms of s-electron redistributions at the tin atom with change in substituent.     

Principles and performance of an electron spin echo spectrometer using far infrared lasers as excitation sources

We have built an electron spin echo spectrometer operating at 604 GHz, extending the frequency limit of existing spectrometers by more than a factor of 4. In order to handle this high frequency we have used optical techniques, i.e., molecular gas lasers for the excitation pulses and far infrared techniques for the heterodyne detection system. The different components of the spectrometer are described in detail and first experimental results are given.     

N-Stage output procedure of a finite dam

Summary We examine the problem of optimizing operation of a reservoir with a finite capacity, described by the following model: The input of water into the reservoir is a Wiener process with positive drift. Water may be released at one ofR possible rates. At any time the output rate may be increased with costK per unit increase or it may be decreased to zero with zero cost. There is a reward ofA monetary units for each unit of output. The problem is to control the output in such a way as to maximize the long run average profit per unit time.

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Zusammenfassung In diesem Beitrag geht es um eine optimale Steuerung eines Wasserspeichers mit endlicher Kapazität: Der Zufluß wird durch einen Wiener Prozeß mit positivem Drift beschrieben. Der Abfluß erfolgt in einer von mehreren vorgegebenen Geschwindigkeitsstufen, die jedoch in jedem Zeitpunkt geändert werden kann. Eine Erhöhung der Abflußgeschwindigkeit ist im Gegensatz zu einer Verminderung mit Kosten verbunden. Die Abflußmengen führen zu pro Mengeneinheit konstanten Erlösen. Das Entscheidungsproblem besteht darin, eine Steuerung des Abflusses zu finden, die den durchschnittlichen Gewinn pro Zeiteinheit maximiert.

     

Annealed importance sampling of peptides

Annealed importance sampling assigns equilibrium weights to a nonequilibrium sample that was generated by a simulated annealing protocol [R. M. Neal, Stat. Comput. 11, 125 (2001)]. The weights may then be used to calculate equilibrium averages, and also serve as an "adiabatic signature" of the chosen cooling schedule. In this paper we demonstrate the method on the 50-atom dileucine peptide and an alanine 5-mer, showing that equilibrium distributions are attained for manageable cooling schedules. For dileucine, as naively implemented here, the method is modestly more efficient than constant temperature simulation. The alanine application demonstrates the success of the method when there is little overlap between the high (unfolded) and low (folded) temperature distributions. The method is worth considering whenever any simulated heating or cooling is performed (as is often done at the beginning of a simulation project or during a NMR structure calculation), as it is simple to implement and requires minimal additional computational expense. Furthermore, the naive implementation presented here can be improved.