Geometry of interpolation sets in derivative free optimization

We consider derivative free methods based on sampling approaches for nonlinear optimization problems where derivatives of the objective function are not available and cannot be directly approximated. We show how the bounds on the error between an interpolating polynomial and the true function can be used in the convergence theory of derivative free sampling methods. These bounds involve a constant that reflects the quality of the interpolation set. The main task of such a derivative free algorithm is to maintain an interpolation sampling set so that this constant remains small, and at least uniformly bounded. This constant is often described through the basis of Lagrange polynomials associated with the interpolation set. We provide an alternative, more intuitive, definition for this concept and show how this constant is related to the condition number of a certain matrix. This relation enables us to provide a range of algorithms whilst maintaining the interpolation set so that this condition number or the geometry constant remain uniformly bounded. We also derive bounds on the error between the model and the function and between their derivatives, directly in terms of this condition number and of this geometry constant.     

A note on using alternative second-order models for the subproblems arising in barrier function methods for minimization

Summary. Inequality constrained minimization problems are often solved by considering a sequence of parameterized barrier functions. Each barrier function is approximately minimized and the relevant parameters subsequently adjusted. It is common for the estimated solution to one barrier function problem to be used as a starting estimate for the next. However, this has unfortunate repercussions for the standard Newton-like methods applied to the barrier subproblem. In this note, we consider a class of alternative Newton methods which attempt to avoid such difficulties. Such schemes have already proved of use in the Harwell Subroutine Library quadratic programming codes {\tt VE14} and {\tt VE19}. Received May 2, 1993/Revised form received February 12, 1994     

Room temperature peierls distortion in small diameter nanotubes

By means of ab initio simulations, we investigate the phonon band structure and electron-phonon coupling in small 4-A diameter nanotubes. We show that both the C(5,0) and C(3,3) tubes undergo above room temperature a Peierls transition mediated by an acoustical long wavelength and an optical q=2k(F) phonon, respectively. In the armchair geometry, we verify that the electron-phonon coupling parameter lambda originates mainly from phonons at q=2k(F) and is strongly enhanced when the diameter decreases. These results question the origin of superconductivity in small diameter nanotubes.     

Monitoring manufacturing process yields,purity and stability of structural variants of PEGylated staphylokinase mutant SY161 by quantitative reverse-phase chromatography

Staphylokinase variant SY161 is a recombinant mutant of the Staphylococcus aureus polypeptide staphylokinase (Sak), and is currently in human clinical trials as a thrombolytic agent. The 15 kDa single chain SY161 protein is expressed as a soluble cytoplasmic product in E. coli with a single cysteine inserted near the N-terminus. The protein as extracted from E. coli is a mixture of both monomeric and intermolecularly disulfide crosslinked species. To improve protein purification yields SY161 is sulfitolyzed during the early stages of production, preventing disulfide formation. The protein is later modified during manufacturing to incorporate a single 5 kDa polyethylene glycol group on the single sulfhydryl sidechain. We have developed and qualified a reverse-phase chromatographic method to quantitate SY161 during product manufacturing. We discuss the use of the assay during manufacturing development to monitor fermentation yields, the SY161 PEGylation reaction, and as an in-process manufacturing control assay. The assay has been applied as a product purity and identity release assay and is suitable for use in assessing product structural integrity during stability testing. The assay has a linear range of quantitation for SY161 from at least 0.15 to 16 micro g, and is-in addition capable of detecting and quantitating protein de-PEGylation events and host cell-derived protein contaminants.     

A projection method for the uncapacitated facility location problem

Several algorithms already exist for solving the uncapacitated facility location problem. The most efficient are based upon the solution of the strong linear programming relaxation. The dual of this relaxation has a condensed form which consists of minimizing a certain piecewise linear convex function. This paper presents a new method for solving the uncapacitated facility location problem based upon the exact solution of the condensed dual via orthogonal projections. The amount of work per iteration is of the same order as that of a simplex iteration for a linear program inm variables and constraints, wherem is the number of clients. For comparison, the underlying linear programming dual hasmn + m + n variables andmn +n constraints, wheren is the number of potential locations for the facilities. The method is flexible as it can handle side constraints. In particular, when there is a duality gap, the linear programming formulation can be strengthened by adding cuts. Numerical results for some classical test problems are included.     

A progressive barrier derivative-free trust-region algorithm for constrained optimization

We study derivative-free constrained optimization problems and propose a trust-region method that builds linear or quadratic models around the best feasible and around the best infeasible solutions found so far. These models are optimized within a trust region, and the progressive barrier methodology handles the constraints by progressively pushing the infeasible solutions toward the feasible domain. Computational experiments on 40 smooth constrained problems indicate that the proposed method is competitive with COBYLA, and experiments on two nonsmooth multidisciplinary optimization problems from mechanical engineering show that it can be competitive with the NOMAD software.     

A pressure-jump time-resolved X-ray diffraction study of cubic-cubic transition kinetics in monoolein

In the past two decades, the geometric pathways involved in the transformations between inverse bicontinuous cubic phases in amphiphilic systems have been extensively theoretically modeled. However, little experimental data exists on the cubic-cubic transformation in pure lipid systems. We have used pressure-jump time-resolved X-ray diffraction to investigate the transition between the gyroid QGII and double-diamond QDII phases in mixtures of 1-monoolein in 30 wt % water. We find for this system that the cubic-cubic transition occurs without any detectable intermediate structures. In addition, we have determined the kinetics of the transition, in both the forward and reverse directions, as a function of pressure-jump amplitude, temperature, and water content. A recently developed model allows (at least in principle) the calculation of the activation energy for lipid phase transitions from such data. The analysis is applicable only if kinetic reproducibility is achieved, at least within one sample, and achievement of such kinetic reproducibility is shown here, by carrying out prolonged pressure-cycling. The rate of transformation shows clear and consistent trends with pressure-jump amplitude, temperature, and water content, all of which are shown to be in agreement with the effect of the shift in the position of the cubic-cubic phase boundary following a change in the thermodynamic parameters.