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`Ionic' size differences from bond-valence parameters and from ionic radii: Acta Crystallograph ica Section B: Structural Science, Vol. 62, No. 3. (June 2006), pp. 411-416.Keller , , Krämer,

Source: Acta Crystallographica Section B: Structural Science, Vol. 62, No. 3. (June 2006), pp. 411-416.
Experimental versus expected halide-ion size differences; structural changes in three series of isotypic bismuth chalcogenide halides: Acta Crystallograph ica Section B: Structural Science, Vol. 62, No. 3. (June 2006), pp. 417-423.Keller , , Krämer,

Source: Acta Crystallographica Section B: Structural Science, Vol. 62, No. 3. (June 2006), pp. 417-423.
Is foreign exchange intervention by central banks bad news for debt markets?: A case of Reserve Bank of Australia's interventions 1986-2003: Journal of International Financial Markets, Institutions and Money, Vol. 16, No. 5. (December 2006), pp. 446-467.We investigate the effects of the Reserve Bank of Australia's foreign exchange interventions on the USD/AUD market and 90-day and 10-year interest rate futures markets for the period July 1986-December 2003. Using recently released revised and updated intervention data, we investigate contemporaneou s and disaggregated intervention influences and find significant evidence for (i) intervention effectiveness in moderating the contemporaneou s exchange rate movements especially if interventions were cumulative and large, (ii) exchange rate volatility reducing effect with a day's lag, (iii) undesirable interest rate movements following interventions in some periods compromising monetary policy effectiveness, and (iv) a volatility reducing effect of cumulative interventions in the 90-day rate, and a volatility increasing effect of large interventions in both the 90-day and 10-year rate futures. These findings are a unique and significant contribution to the prevailing literature as they demonstrate that the RBA's interventions matter not only for the foreign exchange market but also for the debt markets.Suk-Jo ong Kim, Cyril Pham

Source: Journal of International Financial Markets, Institutions and Money, Vol. 16, No. 5. (December 2006), pp. 446-467.
Arbitrage and the Expectations Hypothesis: The Journal of Finance, Vol. 55, No. 2. (2000), pp. 989-994.This paper shows that all traditional forms of the expectations hypothesis can be consistent with the absence of arbitrage if markets are incomplete. A key implication is that the validity of the expectations hypothesis is purely an empirical issue; the expectations hypothesis cannot be ruled out on a priori theoretical grounds.Franci s Longstaff

Source: The Journal of Finance, Vol. 55, No. 2. (2000), pp. 989-994.
Dealer behavior in the specials market for US Treasury securities: Journal of Financial Intermediation , Vol. 16, No. 2. (April 2007), pp. 204-228.We assess dealer behavior in the specials market for US Treasury securities by comparing dealer participation in the Federal Reserve's securities loan auctions with prices in the private market. Dealer behavior is generally consistent with the law of one price and apparent violations can largely be explained by institutional differences between the private market and the Fed's program. However, for auctions that are effectively noncompetitive , dealers regularly pass up true arbitrage opportunities and frequently overpay to borrow securities. Dealers apparently do not realize that certain auctions are noncompetitive , even though the information needed to discern this fact is publicly available in advance.Michae l Fleming, Kenneth Garbade

Source: Journal of Financial Intermediation, Vol. 16, No. 2. (April 2007), pp. 204-228.
The U.S. Treasury yield curve: 1961 to the present: Journal of Monetary Economics, Vol. 54, No. 8. (November 2007), pp. 2291-2304.The discount function, which determines the value of all future nominal payments, is the most basic building block of finance and is usually inferred from the Treasury yield curve. It is therefore surprising that researchers and practitioners do not have available to them a long history of high-frequency yield curve estimates. This paper fills that void by making public the Treasury yield curve estimates of the Federal Reserve Board at a daily frequency from 1961 to the present. We use a well-known and simple smoothing method that is shown to fit the data very well. The resulting estimates can be used to compute yields or forward rates for any horizon. We hope that the data, which are posted on the website http://www.fed eralreserve.go v/pubs/feds/20 06 and which will be updated quarterly, will provide a benchmark yield curve that will be useful to applied economists.Ref et Gurkaynak, Brian Sack, Jonathan Wright

Source: Journal of Monetary Economics, Vol. 54, No. 8. (November 2007), pp. 2291-2304.
Theory of hydrogen bonded chains in bioenergetics: The Journal of Chemical Physics, Vol. 72, No. 7. (1980), pp. 3959-3971.JF Nagle, M Mille, HJ Morowitz

Source: The Journal of Chemical Physics, Vol. 72, No. 7. (1980), pp. 3959-3971.
Use of Calculated Cation-? Binding Energies to Predict Relative Strengths of Nicotinic Acetylcholine Receptor Agonists: ACS Chemical Biology, Vol. 3, No. 11. (21 November 2008), pp. 693-702.doi: 10.1021/cb8001 89y Agonists and antagonists of the nicotinic acetylcholine receptor (nAChR) are used to treat nicotine addiction, neuromuscular disorders, and neurological diseases. In designing small molecule therapeutics with the nAChR as a target, it is useful to identify chemical parameters that correlate with ability to activate the receptor. Previous studies have shown that cation-? interactions at the transmitter binding sites of the nAChR are important for receptor activation by strong agonists such as acetylcholine. We hypothesized that a calculated estimate of cation-? binding ability could be used to predict the efficiency for channel opening (i.e., the gating efficiency) associated with activation of the acetylcholine receptor by a series of structurally related organic cations. We demonstrate that the calculated cation-? energy is strongly correlated with gating efficiency but only weakly correlated with closed-state binding affinity. Our results suggest that cation-? interactions contribute significantly to the open-state affinity of these cations and that the calculated cation-? energy will be a useful parameter for designing nAChR agonists and antagonists.Ma thew Tantama, Stuart Licht

Source: ACS Chemical Biology, Vol. 3, No. 11. (21 November 2008), pp. 693-702.
On the Cooperativity of Cation− π and Hydrogen Bonding Interactions: J. Phys. Chem. B (3 July 2008)Abstract: Quantum chemical calculations are performed to gauge the effect of cationŔ and hydrogen bonding interactions on each other. Mphenolaccepto r (M = Li+ and Mg2+; acceptor = H2O, HCOOH, HCN, CH3OH, HCONH2 and NH3) is taken as a model ternary system that exhibits the cationŔ and hydrogen bonding interactions. Cooperativity is quantified and the computed positive cooperativity between cationŔ and hydrogen bonding interactions is rationalized through reduced variational space (RVS) and charge analyses.Dolly Vijay, Hendrik Zipse, Narahari Sastry

Source: J. Phys. Chem. B (3 July 2008)
Predicting Hydrogen-Bond Strengths from Acid−Ba se Molecular Properties. The pKa Slide Rule: Toward the Solution of a Long-Lasting Problem: Acc. Chem. Res. (16 October 2008)Abstract: Unlike normal chemical bonds, hydrogen bonds (H-bonds) characteristic ally feature binding energies and contact distances that do not simply depend on the donor (D) and acceptor (:A) nature. Instead, their chemical context can lead to large variations even for a same donoracceptor couple. As a striking example, the weak HOH···OH2 bond in neutral water changes, in acidic or basic medium, to the 6-fold stronger and 15% shorter [H2O···H···OH2 ]+ or [HO···H···OH] bonds. This surprising behavior, sometimes called the H-bond puzzle, practically prevents prediction of H-bond strengths from the properties of the interacting molecules. Explaining this puzzle has been the main research interest of our laboratory in the last 20 years. Our first contribution was the proposal of RAHB (resonance-ass isted H-bond), a new type of strong H-bond where donor and acceptor are linked by a short Ŕ-conjugated fragment. The RAHB discovery prompted new studies on strong H-bonds, finally leading to a general H-bond classification in six classes, called the six chemical leitmotifs, four of which include all known types of strong bonds. These studies attested to the covalent nature of the strong H-bond showing, by a formal valence-bond treatment, that weak H-bonds are basically electrostatic while stronger ones are mixtures of electrostatic and covalent contributions. The covalent component gradually increases as the difference of donoracceptor proton affinities, PA, or acidic constants, pKa, approaches zero. At this limit, the strong and symmetrical D···H···A bonds formed can be viewed as true three-center-f our-electron covalent bonds. These results emphasize the role PA/pKa equalization plays in strengthening the H-bond, a hypothesis often invoked in the past but never fully verified. In this Account, this hypothesis is reconsidered by using a new instrument, the pKa slide rule, a bar chart that reports in separate scales the pKas of the DH proton donors and :A proton acceptors most frequently involved in DH···:A bond formation. Allowing the two scales to shift so to bring selected donor and acceptor molecules into coincidence, the ruler permits graphical evaluation of pKa and then empirical appreciation of the DH···:A bond strength according to the pKa equalization principle. Reliability of pKa slide rule predictions has been verified by extensive comparison with two classical sources of H-bond strengths: (i) the gas-phase dissociation enthalpies of charged [X···H···X] and [X···H···X]+ bonds derived from the thermodynamic NIST Database and (ii) the geometries of more than 9500 H-bonds retrieved from the Cambridge Structural Database. The results attest that the pKa slide rule provides a reliable solution for the long-standing problem of H-bond-strengt h prediction and represents an efficient and practical tool for making such predictions directly accessible to all scientists.Pao la Gilli, Loretta Pretto, Valerio Bertolasi, Gastone Gilli

Source: Acc. Chem. Res. (16 October 2008)

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