Opening Enediyne Scissors Wider: pH‐Dependent DNA Photocleavage by meta‐Diyne Lysine Conjugates

Photochemical activation of meta‐diynes incapable of Bergman and C1–C5 cyclizations still leads to efficient double‐strand DNA cleavage. Spatial proximity of the two arylethynyl groups is not required for efficient DNA photocleavage by the enediyne‐lysine conjugates. Efficiency of the cleavage is a function of the external pH and DNA damage is strongly enhanced at pH < 7. The pH‐dependence of the DNA photocleavage activity stems from the protonation states of lysine amino groups, the internal electron donors responsible for intramolecular PET quenching and deactivation of the photoreactive excited states. DNA‐binding analysis suggests intercalative DNA binding for phenyl substituted conjugate and groove binding for TFP‐substituted conjugate. Additional insights in the possible mechanism for DNA damage from the ROS (Reactive Oxygen Species) scavenger experiments found that generation of singlet oxygen is partially involved in the DNA damage.     

A new method to determine viscosity of liquids using vibration principles

A new method for determining viscosity of liquids is examined. The method employs the principles of vibration and measures the viscous damping due to the motion of a liquid placed in a cylindrical tube. The apparatus and the test liquid are treated as a dynamic system and the measured mechanical impedances are used to calculate energy dissipation due to the viscous damping. The newly designed apparatus is able to generate shear deformations in the liquid without using moving solid surfaces. A harmonic varying force with a frequency close to the resonance frequency of the system is applied through a piston and the resulting velocities of the oscillations generated in the system are measured. Liquids with higher viscosities result in lower velocities due to the higher damping. Analytical equations are provided to relate the viscous damping of the dynamic system to the viscosity of the liquids. The viscosities obtained from the proposed method are in good agreement with the ones obtained from standard rotational viscometry using a cone and plate geometry.     

Catalyst Design by NH4OH Treatment of USY Zeolite

Hierarchical zeolites are a class of superior catalysts which couples the intrinsic zeolitic properties to enhanced accessibility and intracrystalline mass transport to and from the active sites. The design of hierarchical USY (Ultra‐Stable Y) catalysts is achieved using a sustainable postsynthetic room temperature treatment with mildly alkaline NH₄OH (0.02 m ) solutions. Starting from a commercial dealuminated USY zeolite (Si/Al = 47), a hierarchical material is obtained by selective and tuneable creation of interconnected and accessible small mesopores (2–6 nm). In addition, the treatment immediately yields the NH₄⁺ form without the need for additional ion exchange. After NH₄OH modification, the crystal morphology is retained, whereas the microporosity and relative crystallinity are decreased. The gradual formation of dense amorphous phases throughout the crystal without significant framework atom leaching rationalizes the very high material yields (>90%). The superior catalytic performance of the developed hierarchical zeolites is demonstrated in the acid‐catalyzed isomerization of α‐pinene and the metal‐catalyzed conjugation of safflower oil. Significant improvements in activity and selectivity are attained, as well as a lowered susceptibility to deactivation. The catalytic performance is intimately related to the introduced mesopores, hence enhanced mass transport capacity, and the retained intrinsic zeolitic properties.     

Theoretical study of substituent and solvent effects on the thermodynamics for <Emphasis Type="Italic">cis</Emphasis>/<Emphasis Type="Italic">trans</Emphasis> isomerization and intramolecular rearrangements of 2,2′-diphenoquinones

Enthalpies (Δ_isom H _(g)^o), Gibbs free energies (Δ_isom G _(g)^o), and equilibrium constants (log K _isom) for the trans → cis isomerization of various 3,3′-, 4,4′-, and 5,5′- disubstituted 2,2′-diphenoquinones with a range of electron withdrawing and releasing moieties (methyl, fluoro, chloro, bromo, trifluoromethyl, and amino) were calculated in the gas phase and in the solvent phase (n-hexane, benzene, n-octanol, acetonitrile, and water). In the gas phase, the trans isomer of the parent and all substituted 2,2′-diphenoquinones is predicted to be more thermodynamically stable than the cis configuration, with log K _isom ranging from −2.8 to −7.0. For all compounds, increasing solvent polarity/proticity progressively favors shifting the cis/trans equilibrium towards greater contributions of the cis configuration and substantially increases the log K _isom by up to 5.1 units relative to the gas phase. In polar protic and polar aprotic solvents, the estimated log K _isom ranges as low as −0.4, indicating significant populations of the cis isomers should be present. The findings support the polar solvent phase mechanistic predictions for a cis configuration of 2,2′-diphenoquinones participating in the thermal transformation of trans-2,2′-diphenoquinones to oxepino[2,3-b]benzofurans. With limited exceptions for some amino derivatives, the cis-2,2′-diphenoquinone to oxepino[2,3-b]benzofuran isomerization is expected to be thermodynamically favorable for all substituents/phases under consideration. The cis-2,2′-diphenoquinone to oxepino[2,3-b]benzofuran rearrangement is predicted to become less thermodynamically favored with increasing solvent polarity/proticity.     

Comparison of certain value-at-risk estimation methods for the two-parameter Weibull loss distribution

The Weibull distribution is one of the most important distributions that is utilized as a probability model for loss amounts in connection with actuarial and financial risk management problems. This paper considers the Weibull distribution and its quantiles in the context of estimation of a risk measure called Value-at-Risk (VaR). VaR is simply the maximum loss in a specified period with a pre-assigned probability level. We attempt to present certain estimation methods for VaR as a quantile of a distribution and compare these methods with respect to their deficiency (Def) values. Along this line, the results of some Monte Carlo simulations, that we have conducted for detailed investigations on the efficiency of the estimators as compared to MLE, are provided.     

Comparison of epithelial and fibroblastic cell behavior on nano/micro-topographic PCL membranes produced by crystallinity control

In this study, the relationship between the cellular morphology and the material surface topography was investigated. Poly(ε-caprolactone) (PCL) membranes were prepared in a wide range of surface wettabilities by means of crystallinity-controlled solvent casting process. Membrane surfaces were characterized by atomic force microscope (AFM), scanning electron microscope (SEM), and static/dynamic water contact angle measurements. It was found that solvent evaporation and non-solvent (methanol) addition to the solvent (THF) are the most decisive parameters to change the surface topography. The non-solvent addition and the decrease in solvent evaporation temperature from room temperature to -20 °C caused increased polymeric chain mobility and crystallization time. Such changes in crystallization parameters led to the formation of micro/nano-sized features on the membrane. Cell culture studies indicated that in contrast to Madin Darby kidney (MDBK) epithelial cells, L929 mouse fibroblast preferred rough and porous surfaces.     

Optimal residuals and the Dahlquist test problem

Numerical Algorithms - We show how to compute the optimal relative backward error for the numerical solution of the Dahlquist test problem by one-step methods. This is an example of a general...     

Periodic variation method for blind symbol rate estimation

In order to obtain unknown symbol rate of incoming signal at a receiver, in this paper, cyclostationary features of linear digitally modulated signals are exploited by proposed periodic variation method. A low complexity but highly accurate symbol rate estimation technique is obtained. The proposed method is based on a superposed epoch analysis over autocorrelations obtained blindly in different sampling frequencies. The obtained autocorrelations are analyzed in the frequency domain, and it is seen that there are large oscillations when the autocorrelation is obtained around the symbol rate. Then, a superposed epoch analysis is developed in order to estimate symbol rate based of the periodic variations on the frequency responses of autocorrelations. The proposed algorithm is quite accurate in the noisy environment because the noise is having no frequency component after taking Fourier transform of autocorrelations in all sampling rates, and this feature is also valid for the offset frequency that the purposed estimation is not affected by offset frequency. Thus, a successful blind symbol rate estimation algorithm is obtained, and it performs much better error performance than those using the well‐known cyclic correlation based symbol rate estimations, as it is proven by the obtained performances presented in the paper. Copyright © 2013 John Wiley & Sons, Ltd.     

SVL fluorescence and duschinskii effect in the S1 state of pyridine

SVL fluorescence spectra from principal bands in the S₁ state of pyridine h₅ and -d₅ were measured. A large displacement of the normal coordinate origin of v_6a and the Duschinskii rotation of v_10a and v_16a were established.