Mechanism of azole antifungal activity as determined by liquid chromatographic/mass spectrometric monitoring of ergosterol biosynthesis

A liquid chromatography/mass spectrometry (LC/MS) method for separation and characterization of ergosterol biosynthetic precursors was developed to study the effect of Posaconazole on sterol biosynthesis in fungi. Ergosterol biosynthetic precursors were characterized from their electron ionization mass spectra acquired by a normal-phase chromatography, particle beam LC/MS method. Fragment ions resulting from cleavage across the D-ring and an abundant M - 15 fragment ion were diagnostic for methyl substitution at C-4 and C-14. Comparison of the sterol profile in control and treated Candida albicans incubations showed depletion of ergosterol and accumulation of C-4 and C-14 methyl-substituted sterols following treatment with Posaconazole. These C-4 and C-14 methyl sterols are known to be incapable of sustaining cell growth. The results demonstrate that Posaconazole exerts its antifungal activity by inhibition of ergosterol biosynthesis. Furthermore, Posaconazole appears to disrupt ergosterol biosynthesis by inhibition of lanosterol 14alpha-demethylase.     

Chemical Sensors for Electronic Nose Systems

Chemical sensors have been widely used for the analysis of volatile organic compounds. Employing chemical sensors in an array format with pattern recognition provides a higher degree of selectivity and reversibility leading to an extensive range of applications. When such systems are used for odour analysis they are termed electronic noses. Application of electronic noses ranges from the food industry, medical industry to environmental monitoring and process control. Many types of different gas sensors have been employed in the array. These include conducting polymers, metal oxide semiconductors, piezoelectric, optical fluorescence and amperometric gas sensors The transducer principle of these sensors is varied and is discussed in detail within this review. Examples of the current trends in sensor array technology as well as the applications to which the sensor-based noses have been applied are also discussed.     

Standard enthalpy of solution and formation of cesium chromate. Derived thermodynamic properties of the aqueous chromate,bichromate, and dichromate ions,alkali metal and alkaline earth chromates,and lead chromate

Calorimetric measurements of the enthalpy of solution of cesium chromate gave ΔH_soln = (7622 ± 24) cal_th mol^?1 for a dilution of Cs₂CrO₄·21128H₂O. This result, along with the enthalpy of dilution gave the standard enthalpy of solution, ΔH_soln^o = (7512 ± 31) cal_th mol^?1, whence the standard enthalpy of formation, ΔH_f⁰(Cs₂CrO₄, c, 298.15 K), was calculated to be ?(341.78 ± 0.46) kcal_th mol^?1. Recomputed thermodynamic data for the formation of the other alkali metal chromates have been tabulated. From their solubilities and enthalpies of solution, the standard entropies, S⁰(298 K), of BaCrO₄ and PbCrO₄ were estimated to be (38.9 ± 0.9) and (43.7 ± 1.2) cal_th K^?1 mol^?1, respectively. There is evidence that ΔH_f⁰(SrCrO₄, c, 298.15 K) may be in error. Thermochemical, solubility, and equilibrium data, have been combined to update the thermodynamic properties of the aqueous chromate (CrO₄^2?), bichromate (HCrO₄^?), and dichromate (Cr₂O₇^2?) ions. The new values at 298.15 K are as follows:

     

4.

Ultrafast excited-state dynamics of adenine and monomethylated adenines in solution: implications for the nonradiative decay mechanism     

Cohen B  Hare PM  Kohler B 《Journal of the American Chemical Society》2003,125(44):13594-13601

The DNA base adenine and four monomethylated adenines were studied in solution at room temperature by femtosecond pump-probe spectroscopy. Transient absorption at visible probe wavelengths was used to directly observe relaxation of the lowest excited singlet state (S(1) state) populated by a UV pump pulse. In H(2)O, transient absorption signals from adenine decay biexponentially with lifetimes of 0.18 +/- 0.03 ps and 8.8 +/- 1.2 ps. In contrast, signals from monomethylated adenines decay monoexponentially. The S(1) lifetimes of 1-, 3-, and 9-methyladenine are similar to one another and are all below 300 fs, while 7-methyladenine has a significantly longer lifetime (tau = 4.23 +/- 0.13 ps). On this basis, the biexponential signal of adenine is assigned to an equilibrium mixture of the 7H- and 9H-amino tautomers. Excited-state absorption (ESA) by 9-methyladenine is 50% stronger than by 7-methyladenine. Assuming that ESA by the corresponding tautomers of adenine is unchanged, we estimate the population of 7H-adenine in H(2)O at room temperature to be 22 +/- 4% (estimated standard deviation). To understand how the environment affects nonradiative decay, we performed the first solvent-dependent study of nucleobase dynamics on the ultrafast time scale. In acetonitrile, both lowest energy tautomers of adenine are present in roughly similar proportions as in water. The lifetimes of the 9-substituted adenines depend somewhat more sensitively on the solvent than those of the 7-substituted adenines. Transient signals for adenine in H(2)O and D(2)O are identical. These solvent effects strongly suggest that excited-state tautomerization is not an important nonradiative decay pathway. Instead, the data are most consistent with electronic energy relaxation due to state crossings between the optically prepared (1)pipi* state and one or more (1)npi* states and the electronic ground state. The pattern of lifetimes measured for the monomethylated adenines suggests a special role for the (1)npi* state associated with the N7 electron lone pair.     

5.

Some computations on the spectra of Pisot and Salem numbers     

Peter Borwein  Kevin G. Hare. 《Mathematics of Computation》2002,71(238):767-780

Properties of Pisot numbers have long been of interest. One line of questioning, initiated by Erdos, Joó and Komornik in 1990, is the determination of for Pisot numbers , where

Although the quantity is known for some Pisot numbers , there has been no general method for computing . This paper gives such an algorithm. With this algorithm, some properties of and its generalizations are investigated.

A related question concerns the analogy of , denoted , where the coefficients are restricted to ; in particular, for which non-Pisot numbers is nonzero? This paper finds an infinite class of Salem numbers where .

     

6.

Photon channelling in foams     

Schmiedeberg M  Miri MF  Stark H 《The European physical journal. E, Soft matter》2005,18(1):123-131

Experiments by Gittings, Bandyopadhyay and Durian (Europhys. Lett. 65, 414 (2004)) demonstrate that light possesses a higher probability to propagate in the liquid phase of a foam due to total reflection. The authors term this observation photon channelling which we investigate in this article theoretically. We first derive a central relation in the work of Gitting et al. without any free parameters. It links the photon's path-length fraction f in the liquid phase to the liquid fraction ɛ. We then construct two-dimensional Voronoi foams, replace the cell edges by channels to represent the liquid films and simulate photon paths according to the laws of ray optics using transmission and reflection coefficients from Fresnel's formulas. In an exact honeycomb foam, the photons show superdiffusive behavior. It becomes diffusive as soon as disorder is introduced into the foams. The dependence of the diffusion constant on channel width and refractive index is explained by a one-dimensional random-walk model. It contains a photon channelling state that is crucial for the understanding of the numerical results. At the end, we shortly comment on the observation that photon channelling only occurs in a finite range of ɛ.     

7.

Multipliers of spherical harmonics and energy of measures on the sphere     

Kathryn E. Hare  Maria Roginskaya 《Arkiv f?r Matematik》2003,41(2):281-294

We consider the operator,f(Δ) for Δ the Laplacian, on spaces of measures on the sphere inR ^d , show how to determine a family of approximating kernels for this operator assuming that certain technical conditions are satisfied, and give estimates for theL²-norm off(Δ)μ in terms of the energy of the measure μ. We derive a formula, analogous to the classical formula relating the energy of a measure onR ^d with its Fourier transform, comparing the energy of a measure on the sphere with the size of its spherical harmonics. An application is given to pluriharmonic measures.     

8.

A Fourier series formula for energy of measures with applications to Riesz products     

Kathryn E. Hare  Maria Roginskaya 《Proceedings of the American Mathematical Society》2003,131(1):165-174

In this paper we derive a formula relating the energy and the Fourier transform of a finite measure on the -dimensional torus which is similar to the well-known formula for measures on .

We apply the formula to obtain estimates on the Hausdorff dimension of Riesz product measures. These give improvements on the earlier, classical results which were based on completely different techniques.

     

9.

Maximal functions with polynomial densities in lacunary directions     

Kathryn Hare  Fulvio Ricci 《Transactions of the American Mathematical Society》2003,355(3):1135-1144

Given a real polynomial in one variable such that , we consider the maximal operator in ,

0\,,\,i,j\in \mathbb{Z}}\frac{1... ...t f\big (x_{1}-2^{i}p(t),x_{2}-2^{j}p(t)\big )\big \vert\,dt . \end{displaymath}">

We prove that is bounded on for 1$"> with bounds that only depend on the degree of .

     

10.

Frequency tuning of the whispering-gallery modes of silica microspheres for cavity quantum electrodynamics and spectroscopy     

von Klitzing W  Long R  Ilchenko VS  Hare J  Lefèvre-Seguin V 《Optics letters》2001,26(3):166-168

We have tuned the whispering-gallery modes of a fused-silica microresonator over nearly 1 nm at 800 nm, i.e., over half a free spectral range, or 10(6) linewidths of the resonator. This result has been achieved by use of a new method based on the stretching of a two-stem microsphere. We describe devices that will permit new cavity QED experiments with this high- Q optical resonator when it is desirable to optimize its coupling to emitters with given transition frequencies. The demonstrated tuning capability is compatible with both UHV and low-temperature operation, which should be useful for future experiments with laser-cooled atoms or single quantum dots.     

1 [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] 下一页 » 末  页»

	$\text{S}{}^0\text{/}\text{cal}{}_{\mathrm{th}}\text{K}{}^{\mathrm{?1}}\text{mol}{}^{\mathrm{?1}}$	$\text{ΔH}{}_{\mathrm{f}}{}^0\text{/kcal}{}_{\mathrm{th}}\text{mol}{}^{\mathrm{?1}}$	$\text{ΔG}{}_{\mathrm{f}}{}^0\text{/kcal}{}_{\mathrm{th}}\text{mol}{}^{\mathrm{?1}}$
CrO42?(aq)	(13.8 ± 0.5)	?(210.93 ± 0.45)	?(174.8 ± 0.5)
HCrO4?(aq)	(46.6 ± 1.8)	?(210.0 ± 0.7)	?(183.7 ± 0.5)
Cr2O72?(aq)	(67.4 ± 3.9)	?(356.5 ± 1.5)	?(312.8 ± 1.0)

Ultrafast excited-state dynamics of adenine and monomethylated adenines in solution: implications for the nonradiative decay mechanism

The DNA base adenine and four monomethylated adenines were studied in solution at room temperature by femtosecond pump-probe spectroscopy. Transient absorption at visible probe wavelengths was used to directly observe relaxation of the lowest excited singlet state (S(1) state) populated by a UV pump pulse. In H(2)O, transient absorption signals from adenine decay biexponentially with lifetimes of 0.18 +/- 0.03 ps and 8.8 +/- 1.2 ps. In contrast, signals from monomethylated adenines decay monoexponentially. The S(1) lifetimes of 1-, 3-, and 9-methyladenine are similar to one another and are all below 300 fs, while 7-methyladenine has a significantly longer lifetime (tau = 4.23 +/- 0.13 ps). On this basis, the biexponential signal of adenine is assigned to an equilibrium mixture of the 7H- and 9H-amino tautomers. Excited-state absorption (ESA) by 9-methyladenine is 50% stronger than by 7-methyladenine. Assuming that ESA by the corresponding tautomers of adenine is unchanged, we estimate the population of 7H-adenine in H(2)O at room temperature to be 22 +/- 4% (estimated standard deviation). To understand how the environment affects nonradiative decay, we performed the first solvent-dependent study of nucleobase dynamics on the ultrafast time scale. In acetonitrile, both lowest energy tautomers of adenine are present in roughly similar proportions as in water. The lifetimes of the 9-substituted adenines depend somewhat more sensitively on the solvent than those of the 7-substituted adenines. Transient signals for adenine in H(2)O and D(2)O are identical. These solvent effects strongly suggest that excited-state tautomerization is not an important nonradiative decay pathway. Instead, the data are most consistent with electronic energy relaxation due to state crossings between the optically prepared (1)pipi* state and one or more (1)npi* states and the electronic ground state. The pattern of lifetimes measured for the monomethylated adenines suggests a special role for the (1)npi* state associated with the N7 electron lone pair.     

Some computations on the spectra of Pisot and Salem numbers

Properties of Pisot numbers have long been of interest. One line of questioning, initiated by Erdos, Joó and Komornik in 1990, is the determination of for Pisot numbers , where

Although the quantity is known for some Pisot numbers , there has been no general method for computing . This paper gives such an algorithm. With this algorithm, some properties of and its generalizations are investigated.

A related question concerns the analogy of , denoted , where the coefficients are restricted to ; in particular, for which non-Pisot numbers is nonzero? This paper finds an infinite class of Salem numbers where .

     

Photon channelling in foams

Experiments by Gittings, Bandyopadhyay and Durian (Europhys. Lett. 65, 414 (2004)) demonstrate that light possesses a higher probability to propagate in the liquid phase of a foam due to total reflection. The authors term this observation photon channelling which we investigate in this article theoretically. We first derive a central relation in the work of Gitting et al. without any free parameters. It links the photon's path-length fraction f in the liquid phase to the liquid fraction ɛ. We then construct two-dimensional Voronoi foams, replace the cell edges by channels to represent the liquid films and simulate photon paths according to the laws of ray optics using transmission and reflection coefficients from Fresnel's formulas. In an exact honeycomb foam, the photons show superdiffusive behavior. It becomes diffusive as soon as disorder is introduced into the foams. The dependence of the diffusion constant on channel width and refractive index is explained by a one-dimensional random-walk model. It contains a photon channelling state that is crucial for the understanding of the numerical results. At the end, we shortly comment on the observation that photon channelling only occurs in a finite range of ɛ.     

Multipliers of spherical harmonics and energy of measures on the sphere

We consider the operator,f(Δ) for Δ the Laplacian, on spaces of measures on the sphere inR ^d , show how to determine a family of approximating kernels for this operator assuming that certain technical conditions are satisfied, and give estimates for theL²-norm off(Δ)μ in terms of the energy of the measure μ. We derive a formula, analogous to the classical formula relating the energy of a measure onR ^d with its Fourier transform, comparing the energy of a measure on the sphere with the size of its spherical harmonics. An application is given to pluriharmonic measures.     

A Fourier series formula for energy of measures with applications to Riesz products

In this paper we derive a formula relating the energy and the Fourier transform of a finite measure on the -dimensional torus which is similar to the well-known formula for measures on .

We apply the formula to obtain estimates on the Hausdorff dimension of Riesz product measures. These give improvements on the earlier, classical results which were based on completely different techniques.

     

Maximal functions with polynomial densities in lacunary directions

Given a real polynomial in one variable such that , we consider the maximal operator in ,

0\,,\,i,j\in \mathbb{Z}}\frac{1... ...t f\big (x_{1}-2^{i}p(t),x_{2}-2^{j}p(t)\big )\big \vert\,dt . \end{displaymath}">

We prove that is bounded on for 1$"> with bounds that only depend on the degree of .

     

Frequency tuning of the whispering-gallery modes of silica microspheres for cavity quantum electrodynamics and spectroscopy

We have tuned the whispering-gallery modes of a fused-silica microresonator over nearly 1 nm at 800 nm, i.e., over half a free spectral range, or 10(6) linewidths of the resonator. This result has been achieved by use of a new method based on the stretching of a two-stem microsphere. We describe devices that will permit new cavity QED experiments with this high- Q optical resonator when it is desirable to optimize its coupling to emitters with given transition frequencies. The demonstrated tuning capability is compatible with both UHV and low-temperature operation, which should be useful for future experiments with laser-cooled atoms or single quantum dots.