Heme reactivity is uncoupled from quaternary structure in gel-encapsulated hemoglobin: a resonance Raman spectroscopic study

Encapsulation of hemoglobin (Hb) in silica gel preserves structure and function but greatly slows protein motion, thereby providing access to intermediates along the allosteric pathway that are inaccessible in solution. Resonance Raman (RR) spectroscopy with visible and ultraviolet laser excitation provides probes of heme reactivity and of key tertiary and quaternary contacts. These probes were monitored in gels after deoxygenation of oxyHb and after CO binding to deoxyHb, which initiate conformational change in the R-T and T-R directions, respectively. The spectra establish that quaternary structure change in the gel takes a week or more but that the evolution of heme reactivity, as monitored by the Fe-histidine stretching vibration, ν(FeHis), is completed within two days, and is therefore uncoupled from the quaternary structure. Within each quaternary structure, the evolving ν(FeHis) frequencies span the full range of values between those previously associated with the high- and low-affinity end states, R and T. This result supports the tertiary two-state (TTS) model, in which the Hb subunits can adopt high- and low-affinity tertiary structures, r and t, within each quaternary state. The spectra also reveal different tertiary pathways, involving the breaking and reformation of E and F interhelical contacts in the R-T direction but not the T-R direction. In the latter, tertiary motions are restricted by the T quaternary contacts.     

Measuring productivity growth under factor non-substitution: An application to US steam-electric power generation utilities

A theoretical framework is developed for decomposing partial factor productivity and measuring technical inefficiency when the underlying technology is characterized by factor non-substitution. With Farrell’s (1957) radial index of technical inefficiency being inappropriate in this case, Russell non-radial indices are adapted to measure technical inefficiency in a Leontief-type model. A system of factor demand equations with a regime specific technical inefficiency term is proposed and estimated allowing for dependence across inputs using a copula approach. Then the paper presents a complete decomposition of partial factor productivity changes using a dataset of US steam-power electric generation utilities.     

Microsecond melting of a folding intermediate in a coiled-coil peptide, monitored by T-jump/UV Raman spectroscopy

A truncated version of the GCN4 coiled-coil peptide has been studied by ultraviolet resonance Raman (UVRR) spectroscopy with 197 nm excitation, where amide modes are optimally enhanced. Although the CD melting curve could be satisfactorily described with a two-state transition having Tm = 30 degrees C, singular value decomposition of the UVRR data yielded three principal components, whose temperature dependence implicates an intermediate form between the folded and unfolded forms, with formation and melting temperatures of 10 and 40 degrees C. Two alpha-helical amide III bands, at 1340 and 1300 cm(-1), melted out selectively at 10 and 40 degrees C, respectively, and are assigned to hydrated and unhydrated helical regions. The hydrated regions are proposed to be melted in the intermediate form, while the unhydrated regions are intact. Time-resolved UVRR spectra following laser-induced temperature jumps revealed two relaxations, with time constants of 0.2 and 15 mus. These are suggested to reflect the melting times of hydrated and unhydrated helices. The unhydrated helical region may be associated with a 14-residue "trigger" sequence that has been identified in the C-terminal half of GCN4. Dehydration of helices may be a key step in the folding of coiled-coils.     

Some new Chebyshev spaces

In this note we see another circumstance where Chebyshev polynomials play a significant role. In particular, we present some new extended Chebyshev spaces that arise in the asymptotic stability of the zero solution of first order linear delay differential equations with m commensurate delays where a_j,j=0,…,m, are constants and τ>0 is constant.     

Drilling rate of five metals with picosecond laser pulses at 355, 532, and 1064 nm

Experimental results on picosecond laser processing of aluminum, nickel, stainless steel, molybdenum, and tungsten are described. Hole drilling is employed for comparative analysis of processing rates in an air environment. Drilling rates are measured over a wide range of laser fluences (0.05–20?J/cm²). Experiments with picosecond pulses at 355?nm are carried out for all five metals and in addition at 532?nm, and 1064?nm for nickel. A comparison of drilling rate with 6-ps and 6-ns pulses at 355?nm is performed. The dependence of drilling rate on laser fluence measured with picosecond pulses demonstrates two logarithmic regimes for all five metals. To determine the transition from one regime to another, a critical fluence is measured and correlated with the thermal properties of the metals. The logarithmic regime at high-fluence range with UV picosecond pulses is reported for the first time. The energy efficiency of material removal for the different regimes is evaluated. The results demonstrate that UV picosecond pulses can provide comparable quality and higher processing rate compared with literature data on ablation with near-IR femtosecond lasers. A significant contribution of two-photon absorption to the ablation process is suggested to explain high processing rate with powerful UV picosecond pulses.     

On Bessel distributions for quasi-split groups

We show that the Bessel distribution attached by Gelfand and Kazhdan and by Shalika to a generic representation of a quasi-split reductive group over a local field is given by a function when it is restricted to the open Bruhat cell. As in the case of the character distribution, this function is real analytic for archimedean fields and locally constant for non-archimidean fields.

     

Behaviour of an incrementally elastic thick walled sphere under internal and external pressure

The behaviour of a thick walled sphere underinternal and external pressure is considered. The material of the sphere is assumed to obey an incrementally elastic constitutive law. There is no restriction on the size of the deformation and a solution is given in terms of special functions associated with the non-linear differential equations of the problem.As a numerical example the behaviour of a spherical shell, subjected to internal pressure, is described. It is shown that at a certain critical pressure instability of the second kind (inflation) is obtained.