Kinetics And Mechanisms Of The Aminolysis Of N-Hydroxysuccinimide Esters In Aqueous Buffers

Rate constants for the aminolysis of the N-hydroxysuccinimide (NHS) ester of ρ-methoxybenzoic acid, in aqueous buffer systems (20% dioxane), have been determined under pseudo-first-order conditions. For the amines studied (pKa = 7.60-11.1), the data fit the rate expression kobsd - KOH-⨯ [OH-] = k1[amine]free. This rate equation is in contrast to the two-term rate equation (kobsd = k1[amine] + k2[amine]2) obtained for this reaction in anhydrous dioxane (Cline, G. W.; Hanna, S. B. J. Am. Chem. Soc. 1987,109, 3087) and is suggestive of a disproportionate decrease in the catalyzed vs the uncatalyzed reaction path upon changing from a nonaqueous to an aqueous solvent system. The correlation of amine basicity with the nucleophilic rate constant, k1 yields a slope αnuc = 1.0. The magnitude of αnuc, in terms of a reaction mechanism where a tetrahedral intermediate is formed in a fast preequilibrium followed by rate-determining breakdown to products, reflects the sensitivity to changes in charge accumulation in the formation of the tetrahedral intermediate. The resultant increased rate constants, with increased basicity, are due to the effect of an increased concentration of the tetrahedral intermediate. A qualitative evaluation of the literature and current data concerning the leaving ability of N-hydroxy esters, in comparison to phenyl esters (equivalent acyl groups and nucleophiles), reveals that, with leaving groups of comparable basicity, the nucleophilic rate constants for N-hydroxy esters are about 2 orders of magnitude greater than that for phenyl esters. © 1988, American Chemical Society. All rights reserved

The Aminolysis Of N-Hydroxysuccinimide Esters. A Structure-Reactivity Study

Twelve amines, which vary substantially in basicity and in steric environment around N, have been allowed to compete—in anhydrous dioxane solution—in the aminolysis of the N-hydroxysuccinimide esters of unsubstituted, p-OCH3, p-N02, and 3,5-(N02)2 benzoic acids. The amines, which encompass a basicity range of 6.5 pk units, display a 10000-fold variation in reactivity in their reaction with the p-N02ester. for the sterically unhindered amines, a Bronsted-type plot of log kobsdvs. pKa has a slope of ~0.7. The data fit a model (Satterthwait, A. C.; Jencks, W. P. J. Am. Chem. Soc. 1974, 96, 7018–7044) in which reversible formation of a tetrahedral intermediate is followed by rate-determining breakdown to products. Appreciable sensitivity to steric factors, as evidenced from the depressed rates with a-methylbenzylamine and diethylamine, substantiates reversible formation of a crowded tetrahedral intermediate prior to the rate-determining step. The Hammett p values for the competitive acylation of aniline, a-methylbenzylamine, and benzylamine, by substituted N-succinimidyl benzoates, are 1.4,1.2, and 1.1, respectively. These values reflect the selectivity expected for these amines, and the substantial accumulation of charge density at the acyl C in the formation of the tetrahedral intermediate. Individual rate constants for the aminolysis of N-succinimidyl p-methoxybenzoate by n-butylamine and by piperidine, both show First-order and second-order terms in [amine]. The general-base catalysis term is suggestive of a path involving proton transfer in the rate-determining step. © 1987, American Chemical Society. All rights reserved

Facing alternative futures: prospects for and paths to food security in Africa

"Food security in Africa has substantially worsened since 1970. Although the proportion of malnourished individuals in Sub-Saharan Africa has remained in the range of 33–35 percent since around 1970, the absolute number of malnourished people in Africa has increased substantially with population growth, from around 88 million in 1970 to an estimate of over 200 million in 1999–2001. Yet this discouraging trend need not be a blueprint for the future. New research from IFPRI shows that the policy and investment choices of African policymakers and the international development community can make an enormous difference for Africa's future agricultural production and food security. By modeling the results of a number of different policy scenarios in Africa through the year 2025, we show that the number of malnourished children, one important indicator of food security, could rise as high as 41.9 million or fall as low as 9.4 million. These scenarios, therefore, shed light on the effectiveness of various policies and investments in assuring a food-secure future for Africa.' from TextFood insecurity, Forecasting, Agricultural productivity, Human capital, Malnutrition in children, Impact model,

Strange Quarks Nuggets in Space: Charges in Seven Settings

We have computed the charge that develops on an SQN in space as a result of balance between the rates of ionization by ambient gammas and capture of ambient electrons. We have also computed the times for achieving that equilibrium and binding energy of the least bound SQN electrons. We have done this for seven different settings. We sketch the calculations here and give their results in the Figure and Table II; details are in the Physical Review D.79.023513 (2009).Comment: Six pages, one figure. To appear in proceedings of the 2008 UCLA coference on dark matter and dark energ

Looking ahead: long-term prospects for Africa's agricultural development and food security

"Sub-Saharan Africa is the only developing region in the world where food insecurity has worsened instead of improved in recent decades. In this discussion paper, Mark W. Rosegrant, Sarah A. Cline, Weibo Li, Timothy B. Sulser, and Rowena A. Valmonte-Santos show that this discouraging trend need not be a blueprint for the future. The research contained in this discussion paper was conducted in preparation for the IFPRI 2020 Africa conference “Assuring Food and Nutrition Security in Africa by 2020: Prioritizing Actions, Strengthening Actors, and Facilitating Partnerships,” held in Kampala, Uganda, April 1–3, 2004. The authors examine the implications of several different policy scenarios based on IFPRI's International Model for Policy Analysis of Agricultural Commodities and Trade (IMPACT). This model, developed at IFPRI in the early 1990s, has been continually updated to incorporate more food sectors and geographic regions. In this paper, the authors use IMPACT to assess the consequences of a wide range of policy and investment choices for Africa, including a business as usual scenario (continuation of current policy and investment trends through 2025), a pessimistic scenario (declining trends in key investments and in agricultural productivity), and a vision scenario (improving trends in investments and hence in agricultural productivity and human capital), as well as scenarios for more effective use of rainfall in agriculture, reduced marketing margins, and three different scenarios for trade liberalization. The wide variation in results reveals how much these choices will matter. For example, the number of malnourished children under five years old in Sub-Saharan Africa in 2025 is projected to be 38.3 million under business as usual, 55.1 million under the pessimistic scenario, and 9.4 million under the vision scenario. It is our hope that this research will clarify the steps needed to help stimulate the actions contributing to approaching the vision scenario. " From Foreword by Joachim von BraunImpact model, Food insecurity, Forecasting, Agricultural productivity, Human capital, Malnutrition in children,

Simulations of snow distribution and hydrology in a mountain basin

We applied a version of the Regional Hydro‐Ecologic Simulation System (RHESSys) that implements snow redistribution, elevation partitioning, and wind‐driven sublimation to Loch Vale Watershed (LVWS), an alpine‐subalpine Rocky Mountain catchment where snow accumulation and ablation dominate the hydrologic cycle. We compared simulated discharge to measured discharge and the simulated snow distribution to photogrammetrically rectified aerial (remotely sensed) images. Snow redistribution was governed by a topographic similarity index. We subdivided each hillslope into elevation bands that had homogeneous climate extrapolated from observed climate. We created a distributed wind speed field that was used in conjunction with daily measured wind speeds to estimate sublimation. Modeling snow redistribution was critical to estimating the timing and magnitude of discharge. Incorporating elevation partitioning improved estimated timing of discharge but did not improve patterns of snow cover since wind was the dominant controller of areal snow patterns. Simulating wind‐driven sublimation was necessary to predict moisture losses

Protecting the Primordial Baryon Asymmetry From Erasure by Sphalerons

If the baryon asymmetry of the universe was created at the GUT scale, sphalerons together with exotic sources of $(B-L)$-violation could have erased it, unless the latter satisfy stringent bounds. We elaborate on how the small Yukawa coupling of the electron drastically weakens previous estimates of these bounds.Comment: 41 pp., 4 latex figures included and 3 uuencoded or postscript figures available by request, UMN-TH-1213-9

Can codimension-two branes solve the cosmological constant problem?

It has been suggested that codimension-two braneworlds might naturally explain the vanishing of the 4D effective cosmological constant, due to the automatic relation between the deficit angle and the brane tension. To investigate whether this cancellation happens dynamically, and within the context of a realistic cosmology, we study a codimension-two braneworld with spherical extra dimensions compactified by magnetic flux. Assuming Einstein gravity, we show that when the brane contains matter with an arbitrary equation of state, the 4D metric components are not regular at the brane, unless the brane has nonzero thickness. We construct explicit 6D solutions with thick branes, treating the brane matter as a perturbation, and find that the universe expands consistently with standard Friedmann-Robertson-Walker (FRW) cosmology. The relation between the brane tension and the bulk deficit angle becomes $\Delta=2\pi G_6(\rho-3 p)$ for a general equation of state. However, this relation does not imply a self-tuning of the effective 4D cosmological constant to zero; perturbations of the brane tension in a static solution lead to deSitter or anti-deSitter braneworlds. Our results thus confirm other recent work showing that codimension-two braneworlds in nonsupersymmetric Einstein gravity do not lead to a dynamical relaxation of the cosmological constant, but they leave open the possibility that supersymmetric versions can be compatible with self-tuning.Comment: Revtex4, 17 pages, references added, typos corrected, minor points clarified. Matches published versio