Fragmentation chemistry of [M + Cu]+ peptide ions containing an N-terminal arginine

[M + Cu]+ peptide ions formed by matrix-assisted laser desorption/ionization from direct desorption off a copper sample stage have sufficient internal energy to undergo metastable ion dissociation in a time-of-flight mass spectrometer. On the basis of fragmentation chemistry of peptides containing an N-terminal arginine, we propose the primary Cu+ ion binding site is the N-terminal arginine with Cu+ binding to the guanidine group of arginine and the N-terminal amine. The principal decay products of [M + Cu]+ peptide ions containing an N-terminal arginine are [a(n) + Cu - H]+ and [b(n) + Cu - H]+ fragments. We show evidence to suggest that [a(n) + Cu - H]+ fragment ions are formed by elimination of CO from [b(n) + Cu - H]+ ions and by direct backbone cleavage. We conclude that Cu+ ionizes the peptide by attaching to the N-terminal arginine residue; however, fragmentation occurs remote from the Cu+ ion attachment site involving metal ion promoted deprotonation to generate a new site of protonation. That is, the fragmentation reactions of [M + Cu]+ ions can be described in terms of a "mobile proton" model. Furthermore, proline residues that are adjacent to the N-terminal arginine do not inhibit formation of [b(n) + Cu - H]+ ion, whereas proline residues that are distant to the charge carrying arginine inhibit formation of [b(n) + Cu - H]+ ions. An unusual fragment ion, [c(n) + Cu + H]+, is also observed for peptides containing lysine, glutamine, or asparagine in close proximity to the Cu+ carrying N-terminal arginine. Mechanisms for formation of this fragment ion are also proposed.     

Percy W. Bridgman's second century

Percy Williams Bridgman's impact on science began in 1909 with his first three experimental papers. These publications on high pressure calibration, techniques, and compressibility, together with the many articles that followed, established his influence on the course of modern high pressure research. Grounded in classical thermodynamics and practical mechanics, his developments showed how the variable of pressure leads to myriad transformations in materials. Studies carried out under a broader range of conditions now provide unprecedented insights into chemical and physical properties at multimegabar pressures and temperatures from millikelvins to thousands of degrees, where novel electronic, magnetic, and superconducting phases are now being discovered. With careful attention to experimental techniques and material performance, Bridgman extended the available pressure range that could be achieved in the laboratory with the development of new devices. We are now witness to continued refinement of static and dynamic compression methods and in situ measurement techniques, including the marriage of high pressure methods with large facilities such as synchrotron, neutron, and laser sources. Bridgman showed the broad range of implications of this work; the modern field of high pressure research now spans physics and chemistry, geosciences and planetary science, materials science and technology, and biology. Selected examples illustrate Bridgman's impact and legacy in this, his second century. For dense hydrogen, new insights have been obtained from high P–T measurements as well as studies of alloys and compounds of hydrogen, leading to the creation of new metallic and superconducting phases. Studies of other hydrogen-rich systems provide both tests of fundamental theory and potentially useful materials for hydrogen storage. High pressure studies of oxides have led to new ferroelectric and multiferroic materials and phases with remarkable properties that guide the design and fabrication of new devices. With the discovery of super-Earths outside our solar system, the high pressure properties of silicates, oxides, volatiles, and the full complement of planetary materials are now problems of cosmic importance well beyond the conditions found on and within the Earth. Developments in high pressure biology are addressing the question of the depth of the biosphere, the processes and reservoirs of carbon in our planet, and new insights into the origins of life as we know it, as well as the possibility of extraterrestrial life. Improved materials that can withstand high P–T conditions and other extreme environments include new forms of diamond, which are advancing experimental methods and finding numerous applications in advanced technology. These developments dovetail with synergetic advances in a broad spectrum of radiation techniques including coherent X-ray, intense neutron, and ultrabright laser sources.     

No Evidence is False

If evidence is propositional, is one’s evidence limited to true propositions or might false propositions constitute evidence? In this paper, I consider three recent attempts to show that there can be ‘false evidence,’ and argue that each of these attempts fails. The evidence for the thesis that evidence consists of truths is much stronger than the evidence offered in support of the theoretical assumptions that people have relied on to argue against this thesis. While I shall not defend the view that evidence is propositional, I shall defend the view that any propositional evidence must be true.     

Projective Character Degree Patterns of p-Groups for p Odd

In this article, we classify up to isomorphism the character tables of 2-generator p-groups of class two.     

Optical soliton perturbation in non-Kerr law media: Traveling wave solution

This paper analyses the dynamics of soliton propagation through optical fibers with non-Kerr law nonlinearities. The governing nonlinear Schrödinger equation is integrated in the presence of perturbation terms. The traveling wave hypothesis is used to carry out the integration. Domain restrictions on the soliton parameters are identified in the process. The five forms of nonlinearity that are studied are Kerr-law, power-law, parabolic-law, dual-power law and the log-law nonlinearity. Numerical simulations are presented for each of these nonlinear media.     

Influence of timing jitter on nonlinear dynamics of a photonic crystal fiber ring cavity

We demonstrate that timing jitter has a strong influence on supercontinua generated in a photonic crystal fiber ring cavity synchronously pumped by 140?fs pulses. The global dynamics with respect to cavity detuning is analyzed both numerically and experimentally by tracking the cavity pulse energy. The results show that low-frequency timing jitter, induced by both the pump oscillator and the external cavity, masks the fine underlying bifurcation structure of the system. Numerical simulations in the absence of timing jitter reveal that the system dynamics fall into four qualitatively different regimes. The existence of these regimes is experimentally observed in first-return diagrams.     

A Hybrid Differential Dynamic Programming Algorithm for Constrained Optimal Control Problems. Part 2: Application

In the first part of this paper series, a new solver, called HDDP, was presented for solving constrained, nonlinear optimal control problems. In the present paper, the algorithm is extended to include practical safeguards to enhance robustness, and four illustrative examples are used to evaluate the main algorithm and some variants. The experiments involve both academic and applied problems to show that HDDP is capable of solving a wide class of constrained, nonlinear optimization problems. First, the algorithm is verified to converge in a single iteration on a simple multi-phase quadratic problem with trivial dynamics. Successively, more complicated constrained optimal control problems are then solved demonstrating robust solutions to problems with as many as 7 states, 25 phases, 258 stages, 458 constraints, and 924 total control variables. The competitiveness of HDDP, with respect to general-purpose, state-of-the-art NLP solvers, is also demonstrated.