Microsolvation of phthalocyanines in superfluid helium droplets.

Experimental and theoretical investigations of the spectroscopy of molecules in superfluid helium droplets provide evidence for the key role of the first helium layer surrounding the dopant molecule in determining the molecule's spectroscopic features. Recent investigations of emission spectra of phthalocyanine in helium droplets revealed a doubling of all transitions. Herein, we present the emission spectra of Mg-phthalocyanine and of phthalocyanine-argon clusters in helium droplets, which confirm the splitting as a general effect of the helium environment. A scheme of levels is deduced from the emission spectra and attributed to quantized states of the first helium layer surrounding the dopant molecule.     

How to assess and report the performance of a stochastic algorithm on a benchmark problem: mean or best result on a number of runs?

Some authors claim that reporting the best result obtained by a stochastic algorithm in a number of runs is more meaningful than reporting some central statistic. In this short note, we analyze and refute the main argument brought in favor of this statement.     

Approximation bounds for quadratic maximization and max-cut problems with semidefinite programming relaxation

In this paper,we consider a class of quadratic maximization problems.For a subclass of the problems,we show that the SDP relaxation approach yields an approximation solution with the ratio is dependent on the data of the problem with α being a uniform lower bound.In light of this new bound,we show that the actual worst-case performance ratio of the SDP relaxation approach (with the triangle inequalities added) is at least α δd if every weight is strictly positive,where δd ＞ 0 is a constant depending on the problem dimension and data.     

Characterization of reduced iso‐α‐acids derived from hops (Humulus lupulus) by NMR

Reduced forms of iso‐α‐acids (isohumulones), used in modern beer brewing were separated and characterized by ¹H and ¹³C NMR spectroscopy. Components from mixtures of rho‐iso‐α‐acids, tetrahydro‐iso‐α‐acids, and hexahydro‐iso‐α‐acids were isolated using high‐performance liquid chromatography (HPLC) and analyzed by use of one‐ and two‐dimensional NMR experiments. The data presented assign the identities of the main peaks in the HPLC traces for the reduced iso‐α‐acids. Previous tentative assignments regarding the cis and trans configurations and the structures of the acyl residues of the reduced iso‐α‐acids were confirmed and extensive NMR assignments were made. Furthermore, the previously unknown stereochemistry in the C‐4 side‐chain of the rho‐ and hexahydro‐iso‐α‐acids was assigned. Copyright © 2003 John Wiley & Sons, Ltd.     

Time-resolved fluorescence study of the single tryptophan in thiocyanate and azide derivatives of horseradish peroxidase: Implication for a p H-induced conformational change in the heme cavity

Detailed pH-dependent steady state and picosecond time-resolved tryptophan fluorescence studies on thiocyanate and azide complexes of horseradish peroxidase have been carried out. The fluorescence decay of the single tryptophan in these species was fitted to a discrete three exponential model. Maximum entropy method analysis also gave three distinct regions of lifetime distributions. The fast subnanosecond lifetime component was found to have > 97% amplitude contribution while other two longer lifetime components have small contributions. Small contributions from the nanosecond lifetime components possibly arise from apoprotein impurity or some small amount of disordered heme conformer of the protein. pH dependence of the fast picosecond lifetime components was found to show a systematic behavior which has been interpreted in the light of obligatory conformation change associated with activation of the enzyme at low pH.     

闭排队网络中性能势与无穷小实现因子之间的关系

In this paper,the concept of the infinitesimal realization factor is extended to the parameter-dependent performance functions in closed queueing networks. Then the concepts of realization matrix (its elements are called realization factors) and performance potential are introduced,and the relations between infinitesimal realization factors and these two quantities are discussed. This provides a united framework for both IPA and non IPA approaches. Finally,another physical meaning of the service rate is given.     

Fluorescence line narrowed spectra of Zn and metal-free cytochrome c

Fluorescence line narrowing (FLN) spectroscopy was used to study the role of the polypeptide chain in influencing the spectrum of Zn-substituted cytochrome c (Zn cyt c) and metal-free cyt c (porphyrin cyt c). For both derivatives the spectra show characteristics of relaxed fluorescence from an inhomogeneously broadened sample. Zero phonon lines and phonon wings can be clearly distinguished, and vibrational frequencies of the ground and excited states were identified. The inhomogeneous distribution width for porphyrin cyt c is slightly wider than that of Zn cyt c and a second population of molecules was apparent in the porphyrin cyt c. The phonon coupling was greater for Zn cyt c than for porphyrin cyt c, which may be due to the extra coupling to the polypeptide chain by metal ligation.This work has been done in partial fulfillment of the requirements for the Doctor of Philosophy degree.     

Fluorescent humic substances–arsenic complex in well water in areas where blackfoot disease is endemic in Taiwan

The relationship between the four components, (1) fluorescence intensity, (2) arsenic concentration, (3) pH and (4) total dissolved solids, (TDS) measured in well waters from areas in Taiwan where blackfoot disease (BFD) is endemic was studied, as well as the relationships between the four degrees of BFD and each of the above four symptomatic components, in order to evaluate the etiological factors of BFD more progressively. The following 95% confidence intervals were obtained in well water samples (n = 1189): fluorescence intensity, 26.837–32.570; arsenic concentration, 0.103–0.127 mg dm^?3; pH, 7.466–7.519; and TDS 733.063–801.647 mg dm^?3. Fluorescence intensities of the four degrees of BFD were not all the same (F = 64.54, P < 0.001), and nor were arsenic concentrations (F = 72.03, P < 0.001), pH values (F = 7.30, P < 0.001), nor TDS values (F = 10.76, P < 0.001). In addition, multiple comparisons indicate that the higher the epidemical degree, the higher the fluorescence intensities, arsenic concentrations and pH values become; however, such a relationship is not found for TDS values. Moreover, the fluorescence intensities have positive linear correlations with arsenic concentrations (r = 0.49, P < 0.001), pH (r = 0.25, P < 0.001), and TDS (r = 0.18, P < 0.001), as do the arsenic concentrations with pH (r = 0.22, P < 0.001). Of the four epidemical degree groups, pairs are not significantly different from one another in correlation coefficients between fluorescence intensity and arsenic concentration, which implies a steady relationship between fluorescent compounds and arsenic. We conclude that fluorescent compounds in well water, as possible etiological factors of BFD, are closely related to arsenic along with pH and TDS values in the areas where BFD is endemic. In addition, we infer that a complex is formed by fluorescent compounds, arsenic and other metals.