Percolation phenomena in diffusion-controlled polymer matrix systems

The controlled release of two kinds of drugs,5-fluorouracil (5-FU) and hydrocortisonum (Hydro.) loaded in poly(ethylene-vinylalcohol) (EVAL) was dealt with,of which 5-FU/EVAL and Hydro /EVAL matrix systems are composed.The results were analyzed using the pseudo-steady-diffusion models coupled with the fundamental concepts of percolation theory.The percolation thresholds for the two systems were calculated,which could indicate the contributions of pore diffusion and matrix diffusion.     

Where is the sodium in self-assembled monolayers of single-stranded DNA?

Monolayers of single-stranded DNA (ssDNA) immobilized on surfaces form the basis of a number of important biotechnology applications, including DNA microarrays and biosensors. The organization of ssDNA as layer on a solid substrate allows one to investigate various properties of the DNA in a controlled manner and to use DNA for analytical applications as well as for exploring futuristic schemes for molecular electronics. It is commonly assumed that the adsorbed DNA layer contains some structural water and the cations. Here we show, based on XPS studies, that when monolayers of ssDNA are formed from sodium phosphate buffer and washed thoroughly, no Na+ signal is detected. A finite concentration of ions is observed when the DNA is made from a solution of Mg2+ ions, but it is still only a fifth of what it would be if all the phosphate ions were fully neutralized by the metal cations.     

TNF-α responsive DNA star trigon formation from four hairpin probes and the analytical application

Tumor necrosis factor-alpha(TNF-α) is a type of critical pro-inflammatory cytokines,which participates in numerous cellular signal pathways and is regarded as a critical protein biomarker for inflammatory based diseases.In this contribution,we have developed a strategy to fabricate multiple DNA star trigon structures with fluorescence signals from four hairpin probes which are detonated by a single molecule of TNF-α.This process causes significant enhancement of fluorescence and a sensitive and selective biosensor for TNF-α assay is constructed.This method is able to achieve the limit of detection(LOD) at 5 pg/mL(0.285 pM).Moreover,some other advantages such as fast response,high selectivity and convenient operation promise the potential use of this method for TNF-α measurement in point of care testing application.Upon further development,this strategy can also be converted to detect other analytes such as small molecules,nucleic acids and other proteins.     

Is Enantioselectivity Predictable in Asymmetric Catalysis?

S ee ing into the future : A range of computational methods have been applied to harmonize predicted ee values with experimental values. Novel ways of combining quantum mechanics and molecular mechanics feature prominently.

     

Is styrene planar in liquid phases?

The proton NMR spectra of two (13)C-labeled isotopomers of styrene dissolved in two liquid crystalline solvents have been obtained and analyzed to yield four sets each of 24 dipolar couplings. These couplings were then used to investigate the structure of the ring and the ene fragments of the molecule, and the position of the maximum, phi(0), in the ring-ene bond rotational probability distribution. To do this, the effect on the dipolar couplings of small-amplitude vibrational motion was taken into account using vibrational wave functions calculated by molecular orbital and density functional methods. It is concluded that the NMR data are consistent with the ring fragment, averaged over the ring-ene rotation, planar, while the ene fragment is not. The value of phi(0) is found to be 18.0 degrees +/-0.2 degrees for the two solutions, compared with a value of 27 degrees calculated by the molecular method MP2/6-31G(*).     

How can structural similarity analysis help in category formation?

Chemical category is a regulatory concept facilitating filling safety data gaps. Practically, all chemical management programs like the OECD HPV Program, EU REACH, or the Canadian DSL Categorization are planning to use or are already using categorization approaches to reduce resources including animal testing. The aim of the study was to discuss the feasibility to apply computational structural similarity methods to augment formation of a category. The article discusses also how this understanding can be translated into computer readable format, an ultimate need for practical, broad scope applications. We conclude that for the skin sensitization endpoint, used as a working example, mechanistic understanding expressed as chemical reactivity can be exploited by computational structural similarity methods to augment category formation process. We propose a novel method, atom environments ranking (AER), to assess similarity to a reference training set representing a common mechanism of action, as a potential method for grouping chemicals into reactivity domains.     

Is CO2 fixation promoted through the formation of DBU bicarbonate salt?

The bicyclic amidines, 1,8‐diazabicyclo [5.4.0]undec‐7‐ene (DBU) and 1,5‐diazabicyclo[4.3.0] non‐5‐ene (DBN), were used for the chemical fixation of carbon dioxide. The promotion for CO₂ fixation is often reported through the formation of a thermally unstable DBU or DBN bicarbonate salt. To examine the effects of the DBU or DBN bicarbonate salt, reactions of 2‐aminobenzonitrile with the DBU salt or DBN salt in dimethylformamide (DMF) were performed at 20°C for 24 h in argon or carbon dioxide (0.1 MPa). However, in all the cases, 1H‐quinazoline‐2,4‐dione was not obtained completely. In contrast with room temperature reactions, 2‐aminobenzonitriles and DBU bicarbonate salt in DMF reacted for 4 h under high temperature (80°C) and CO₂ atmosphere (0.1 MPa) gave 1H‐quinazoline‐2,4‐diones in good to excellent yields. At high‐temperature conditions, DBU bicarbonate salt is decomposed to DBU and carbon dioxide. Also, the carbonylation of 2‐aminobenzonitrile using DBU and carbon dioxide afforded 1H‐quinazoline‐2,4‐dione in good yields under similar reaction conditions. These results suggest that the combination of DBU or DBN as a strong base and carbon dioxide is much more important than the in situ formation of DBU or DBN bicarbonate salt for the acceleration of CO₂ fixation. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:276–280, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21014     

Is charge reduction in ESI really necessary?

The technique of charge reduction electrospray mass spectrometry (CREMS), which can reduce the charge state complexity produced in electrospray ionization (ESI), is discussed.     

Which surfactants reduce surface tension faster? A scaling argument for diffusion-controlled adsorption

Consider the example of surfactant adsorbing from an infinite solution to a freshly formed planar interface. There is an implicit length scale in this problem, the adsorption depth h, which is the depth depleted to supply the interface with the absorbed surfactant. From a mass balance, h can be shown to be the ratio of the equilibrium surface concentration gamma eq to the bulk concentration C infinity. The characteristic time scale for diffusion to the interface is tau D = h2/D, where D is the diffusivity of the surfactant in solution. The significance of this time scale is demonstrated by numerically integrating the equations governing diffusion-controlled adsorption to a planar interface. The surface tension equilibrates within 1-10 times tau D regardless of bulk concentration, even for surfactants with strong interactions. Dynamic surface tension data obtained by pendant bubble method are rescaled using tau D to scale time. For high enough bulk concentrations, the re-normalized surface tension evolutions nearly superpose, demonstrating that tau D is indeed the relevant time scale for this process. Surface tension evolutions for a variety of surfactants are compared. Those with the smallest values for tau D equilibrate fastest. Since diffusion coefficients vary only weakly for surfactants of similar size, the differences in the equilibration times for various surfactant solutions can be attributed to their differing adsorption depths. These depth are determined by the equilibrium adsorption isotherms, allowing tau D to be calculated a priori from equilibrium surface tension data, and surfactant solutions to be sorted in terms of which will reduce the surface tension more rapidly. Finally, trends predicted by tau D to gauge what surfactant properties are required for rapid surface tension reduction are discussed. These trends are shown to be in agreement with guiding principles that have been suggested from prior structure-property studies.     

Limits of delocalization in through-conjugated dinitrenes: aromatization or bond formation?

[reaction: see text] Dinitrenes 4 and 5 both can form quinonoidal structures by conjugative bond formation. However, ESR spectroscopy detects a thermally populated, excited-state, triplet quinonoidal structure only for 4, with a zero-field splitting of |D/hc| = 0.0822 cm(-)(1), |E/hc| congruent with 0.0 cm(-)(1). The tendency to maintain aromaticity in the additional ring of 5 favors a dinitrene structure (with one less formal pi-bond) over a quinonoidal structure. The thermally populated quintet state of 5 has a zero-field splitting of |D/hc| = 0.287 cm(-)(1), |E/hc| 相似文献   

Concerning the question of covalent bonding in hypericin-chromoproteins: Schiff base formation?

Summary Depending on the reaction conditions,peri-hydroxy substituted anthraquinones like 1,8-dihydroxyanthraquinone and 1,4-dihydroxyanthraquinone could be derivatized with ammonia, propylamine, isopropylamine, and a lysine derivative to yield a variety of imino and amino substitution and addition products. However, hypericin resisted such derivatization under a variety of reaction conditions. Therefore, the hypothesis that hypericin is bound to its apoprotein in photopigmentsvia a Schiff base to the -amino group of a lysine residue or a terminal amino group seems to be rather unlikely.

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Zur Frage der kovalenten Bindung in Hypericin-Chromoproteiden: Schiff-Basenbildung?

Zusammenfassung Abhängig von den Reaktionsbedingungen gabenperi-hydroxylsubstituierte Anthrachinone, wie 1,8-Dihydroxyanthrachinon oder 1,4-Dihydroxyanthrachinon, mit Propylamin, Isopropylamin und einem Lysinderivat eine Reihe von Imino- und Amino-Substitutionsprodukten oder Addukten. Allerdings widerstand Hypericin unter Variation der Reaktionsbedingungen einer solchen Derivatisierung. Deshalb ist die Hypothese, daß Hypericin in seinen Photopigmenten über eine Schiffsche Base mit der -Aminogruppe eines Lysinrestes oder mit einer terminalen Aminogruppe verknüpft ist, eher unwahrscheinlich.

     

Is the HCCS radical linear in the excited state?

The A (2)Pi-X (2)Pi 415 nm band system of the linear HCCS radical has been known since 1978, but the vibronic structure in this complex spectrum, which has both spin-orbit and Renner-Teller complications, has never been satisfactorily assigned, despite serious experimental and theoretical efforts. In a further attempt to understand the spectrum, we have studied the laser-induced fluorescence spectra of jet-cooled HCCS and DCCS, produced from thiophene precursors using the discharge jet technique. The 0(0) (0) bands of HCCS and DCCS have been rotationally analyzed, providing precise ground and excited state spin-orbit splittings. The energy levels of the v(')=0 (2)Pi(3/2) component of DCCS are found to be perturbed by a very low-lying (2)Sigma vibronic level, indicating that the HCC bending mode Renner-Teller effect is much larger than predicted by ab initio calculations with a linear excited state geometry. With this observation, the vibronic bands in the spectra of both isotopomers have been consistently assigned for the first time. Model calculations show that the large Renner-Teller effect and substantially different HCCS and DCCS excited state zero-point spin-orbit splittings can be explained with the assumption of a quasilinear excited state geometry.     

Is a major breakthrough in the oxygen electrocatalysis possible?

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Is catenation beneficial for hydrogen storage in metal-organic frameworks?

Grand canonical Monte Carlo (GCMC) simulations demonstrate that catenation can be beneficial for improving hydrogen storage in metal-organic frameworks at cryogenic temperatures and low pressures but not necessarily at room temperature.     

The formation of beta-beta structures in lignin biosynthesis--are there two different pathways?

Based on results from 2D NMR studies, both pinoresinol and secoisolariciresinol structures were found to be present in native lignin from spruce wood as well as in spruce kraft lignin and residual kraft pulp lignin. These two structures constitute the major types of beta-beta inter-unit linkages present in spruce lignin, but their formation in the lignin polymer may follow different pathways leading to their different bonding patterns with the rest of the lignin polymer. The mechanisms involved are discussed.     

Translocation of single-stranded DNA through the α-hemolysin protein nanopore in acidic solutions

The effect of acidic pH on the translocation of single-stranded DNA through the α-hemolysin pore is investigated. Two significantly different types of events, i.e. deep blockades and shallow blockades, are observed at low pH. The residence times of the shallow blockades are not significantly different from those of the DNA translocation events obtained at or near physiological pH, whereas the deep blockades have much larger residence times and blockage amplitudes. With a decrease in the pH of the electrolyte solution, the percentage of the deep blockades in the total events increases. Furthermore, the mean residence time of these long-lived events is dependent on the length of DNA, and also varies with the nucleotide base, suggesting that they are appropriate for use in DNA analysis. In addition to being used as an effective approach to affect DNA translocation in the nanopore, manipulation of the pH of the electrolyte solution provides a potential means to greatly enhance the sensitivity of nanopore stochastic sensing.     

Interfacial enzyme activation, non-lamellar phase formation and membrane fusion. Is there a conducting thread?

Previous studies from this laboratory have shown that the enzymic generation of diacylglycerol in bilayers by phospholipase C may lead to membrane fusion through the formation of transient non-lamellar lipidic intermediates. The present paper intends to explore the correlations existing among the three main processes involved, namely (a) the induction (or inhibition) of lamellar-to-non-lamellar phase transitions in lipid mixtures through the addition of small (< 5 mol%) proportions of other lipids, (b) the promotion, by the latter lipids, of fusion in otherwise stable phospholipid vesicles (large unilamellar liposomes) under conditions leading to inverted hexagonal/inverted cubic phase formation in bulk lipid systems, and (c) the modulation, by the same small proportions of lipids, of phospholipase C hydrolysis of phosphatidylcholine in liposome bilayers. It is concluded that phospholipase C may give rise to non-lamellar lipidic structures that in turn permit liposomal fusion to occur, but neither enzyme activity is directly modulated by non-lamellar phase formation, nor will whatever kind of enzyme-induced non-lamellar structure give rise to fusion. Moreover, only under certain kinetic conditions will the enzyme give rise to the organization of non-lamellar structures that are conducive to the fusion event.