Library generation through successive substitution of trichlorotriazine

Summary The decreasing reactivity of tri-, di- and monochlorotriazine was utilized for the solid-phase construction of a combinatorial library with three randomized positions, using 20 amino acids and 50 amines as building blocks. The first chlorine atom was selectively substituted by coupling a large excess of trichlorotriazine to the support-bound amino acid, thus avoiding simultaneous substitution of the second chlorine. The second and third diversity positions were selectively introduced by coupling amines at different temperatures. Mixtures of model compounds were synthesized and analyzed, showing the correct representation of all expected components. A library composed of 12 000 compounds was generated using this method.     

Morphology and percolation conductivity of polymer blends containing carbon black

The structure of the polymers polypropylene (PP), polyethylene (PE), and poly-(oxymethylene) (POM) and the blends PE-PP and PE-POM containing carbon black (CB) were studied. It was found that spatial distribution of CB depends on the interface interactions between the components of composites. It is possible to obtain three cases of filler spatial distribution: Filler can be distributed randomly within the polymer matrix, can be contained in one of the polymer components, or can be localized on the polymer-polymer boundary. The conditions of various filler distribution in the heterogeneous polymer matrix are given. The correlation between morphology of the composites and their percolation conductivity was found.     

Testing the concept of a modulation filter bank: the audibility of component modulation and detection of phase change in three-component modulators

Two experiments were performed to test the concept that the auditory system contains a "modulation filter bank" (MFB). Experiment 1 examined the ability to "hear out" the modulation frequency of the central component of a three-component modulator applied to a 4-kHz sinusoidal carrier. On each trial, three modulated stimuli were presented. The modulator of the first stimulus contained three components. Within a run the frequencies of the outer two components were fixed and the frequency of the central ("target") component was drawn randomly from one of five values. The modulators of second and third stimuli contained one component. One had a frequency equal to that of the target and the other had a frequency randomly selected from one of the other possible values. Subjects indicated whether the target corresponded to the second or third stimulus. Scores were around 80% correct when the components in the three-component modulator were widely spaced and when the frequencies of the target and comparison differed sufficiently. Experiment 2 examined the ability to hear a change in the relative phase of the components in a three-component modulator with harmonically spaced components, using a 31FC task. The frequency of the central component, f(c), was either 50 or 100 Hz. Scores were 80%-90% correct when the component spacing was < or = 0.5 f(c), but decreased markedly for greater spacings. Performance was only slightly impaired by randomizing the overall modulation depth from one stimulus to the next. The results of both experiments are broadly consistent with what would be expected from a MFB with a Q value of 1 or slightly less.     

Segregation of concurrent sounds. I: Effects of frequency modulation coherence

Frequency modulation coherence was investigated as a possible cue for the perceptual segregation of concurrent sound sources. Synthesized chords of 2-s duration and comprising six permutations of three sung vowels (/a/, /i/, /o/) at three fundamental frequencies (130.8, 174.6, and 233.1 Hz) were constructed. In one condition, no vowels were modulated, and, in a second, all three were modulated coherently such that the ratio relations among all frequency components were maintained. In a third group of conditions, one vowel was modulated, while the other two remained steady. In a fourth group, one vowel was modulated independently of the two other vowels, which were modulated coherently with one another. Subjects were asked to judge the perceived prominence of each of the three vowels in each chord. Judged prominence increased significantly when the target vowel was modulated compared to when it was not, with the greatest increase being found for higher fundamental frequencies. The increase in prominence with modulation was unaffected by whether the target was modulated coherently or not with nontarget vowels. The modulation and pitch position of nontarget vowels had no effect on target vowel prominence. These results are discussed in terms of possible concurrent auditory grouping principles.     

Utility of Raman Data in Studying Substituted Amines and Hydrazines

By utilizing the Raman spectra of gases, it is frequently possible m provide sufficient data to unequivocally assign the fundamental and several hot bands of the two torsional modes of two coupled methyl rotors which is illustrated by the Raman spectrum of gaseous dimethylamine. From these data V03 = V30, V33 and V‘33 terms have been obtained and their values are compared to those obtained from MP2/6 - 31G(d) ab initio calculations. Also if one of the conformers of an amine or hydrazine has a plane of symmetry and another one has no symmetry, it can be possible to determine the origin of the observed amino torsional mode with excited states from the Raman spectrum, i.e., ethylamine is an example. Since the NH stretches of substituted amines and hydrazines are frequently very weak in the infrared spectrum, the Raman spectra are necessary for the assignment of these fundamentals. Studies are in progress to use the “isolated” NH stretching frequencies to obtain the r0 distances for amines and hydrazinest     

Photoinduced Gas-Phase Electron Transfer Reactions

The electron transfer quenching process, when a reactive excited state is singlet or triplet, for gas-phase systems (benzophenone and anthraquinone with amines and pyridine as well as carbazole with halomethanes) was systematically investigated using time-resolved fluorescence. Bimolecular rate constants were obtained. Variable-temperature measurements were performed for eight donor-acceptor pairs. It was found that under solvent-free conditions various quenchers differing in photochemical reactivity led to change in quenching rates by almost three orders of magnitude. Positive and negative temperature dependences for the electron transfer rate constants were observed. The data were analyzed in terms of the Marcus-Jortner theory.     

On the role of the colloidal stability of mesoporous silica nanoparticles as gene delivery vectors

Mesoporous silica nanoparticles have been synthesized and functionalized with four different types of molecules containing amino groups, i.e., with primary amines only, with quaternary amines, with quaternized cyclic amines, or with polyethylenimine (PEI), which is formed by primary, secondary, and tertiary amines. These nanoparticles were then incubated with reporter plasmids and the ability of the resulting complexes to transfect human cells was studied. Only nanoparticles functionalized with PEI were efficient for transfection. The agglomeration behavior and the electrokinetic potential of the nanoparticle–plasmid complexes have been studied, as well as their cell internalization behavior using a fluorescent-labeled plasmid that allows its monitorization by confocal microscopy. The results indicate that the efficiency of PEI-functionalized nanoparticles for transfection resides to some extent in the different characteristics imparted to the nanoparticles regarding agglomeration and surface charge behavior.     

Thermodynamics of III–V solutions with n components

A method has been developed for the calculation of phase diagrams of III–V mixtures with more than three components. The equations for the chemical potentials, activity coefficients and the free energy of the mixture and for the liquidus- and iso-solidus-concentration lines are given. The parameters, needed for the calculation, are the temperature of fusion, heats of fusion, and the interaction parameters. The interaction parameters can be fitted to datas of the binary or quasi-binary phase diagrams, or can be calculated using the electronegativities, energies of sublimation and molar volumes of the constituent elements.Two approaches for a mixture with n components are given, which give in the ternary and binary case the known equations. The two possible cases of quaternary III–V solutions are discussed explicitly.     

Properties of the scalar mesons f_0(1370), f_0(1500) and f_0(1710)

In the three-state mixing framework, considering the possible glueball components of and , we investigate the hadronic decays of , and into two pseudoscalar mesons. The quarkonia–glueball content of the three states is determined from a fit to the new data presented by the WA102 Collaboration. We find that these data are insensitive to the possible glueball components of and . Furthermore, we discuss some properties of the mass matrix describing the mixing of the isoscalar scalar mesons. Received: 11 October 2000 / Revised version: 1 December 2000 / Published online: 23 March 2001     

Chemical role of amines in the colloidal synthesis of CdSe quantum dots and their luminescence properties

The role of organic amines in the colloidal synthesis of CdSe quantum dots (QDs) has been studied. CdSe QDs were synthesized from the source solutions containing 5 vol% of amines having various alkyl chain lengths, stereochemical sizes and electron donation abilities. The role of the additional amines was evaluated on the basis of the photoluminescence (PL) properties such as PL wavelength and intensity of the obtained CdSe QDs. The observed PL spectra were explained by the fact that the amines behaved as capping ligands on the surface of the QDs in the product colloidal solution and complex ligands for cadmium in the source solutions. It was shown that the particle size was controlled by the diffusion process depending on the mass and stereochemical shape of the amines, and the luminescence intensity increased with the increasing electron donation ability and capping density of the amines.     

Flagellar sensilla of Quadraspidiotus perniciosus Comstock (Rhynchota: Diaspididae) male

The flagellar sensory structures of Quadraspidiotus perniciosus Comstock (Rhynchota: Diaspididae) male have been investigated, using scanning and transmission electron microscopy. Five categories of sensilla have been identified: three types of sensilla trichodea, a sensillum coeloconicum and a sensillum basiconicum. The possible function of sensilla is discussed, considering their location, morphology and ultrastructure. No gustatory sensilla have been detected. All the setae (sensilla trichodea) present on the flagellomeres, except for the three 'knobbed' ones that are mechanosensilla, are cuticular components of olfactory structures. These olfactory sensilla are of two distinct types, having fluted or smooth hairs; furthermore, the fluted ones present different typologies for a varied number of dendrites. They are conceivably used for perceiving female sexual pheromone. It might be that each of the different components of the female sexual pheromone is perceived by a specific sensillum. Two types of supposed thermo-hygroreceptors have been found, one sensillum coeloconicum and two sensilla basiconica.     

Solid phase synthesis of combinatorial libraries using anhydrides as templates

A simple and general approach to the synthesis of chemical libraries based on a universal anhydride template allows the preparation of large number of compounds. Various cyclic/acyclic amines, primary/secondary amines, differentially protected bifunctional amines were used as nucleophiles to react with anhydrides. The free carboxylic acid generated was then coupled with solid-bound amines. The facile and rapid generation of compounds through this multi-component assembly can be accomplished in a combinatorial parallel synthesis. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fluorescence of organic dyes in lipid membranes: Site of solubilization and effects of viscosity and refractive index on lifetimes

The fluorescence decay of several organic dye molecules intercalated in egg phosphatidylcholine lipid membrane vesicles is consistent with the existence of two or three prominent lifetime components rather than a single continuous distribution of lifetimes. The major lifetime components are identified with different sites of solubilization in the membrane. The variation of the lifetime of the membrane-bound dye was studied as a function of the sucrose concentration, which varied the viscosity and refractive index of the aqueous solution. The combined effect of viscosity and refractive index on the lifetime of the dye was used to identify the site of solubilization of the dye in the membrane. The study was useful to identify dye molecules on the surface which are exposed to the aqueous phase, for which the fluorescence lifetime increased systematically with sucrose (viscosity effect). More importantly, it was possible in a few cases to identify the dye molecules which are oriented in the membrane phase, and the fluorescence lifetime decreased systematically with sucrose (refractive index effect). Anomalous values of order parameters determined from the refractive index effect are explained in terms of an orientational distribution of the linear dye molecule weighted in favor of mutually orthogonal orientations.     

分子印迹材料选择性截留卷烟烟气中芳胺的研究

采用分子印迹技术合成了一种对1-萘胺有高度选择性的分子印迹聚合物材料。应用固相萃取吸附试验研究了该聚合物对1-萘胺及其结构类似物的选择特性,表明印迹聚合物材料对4种芳胺类物质表现出良好的选择性结合能力。将所制备的印迹聚合物按不同剂量添加到卷烟嘴棒中,考察其对卷烟烟气中芳胺的截留效果。结果显示,该分子印迹材料能选择性截留卷烟烟气中的1-萘胺、2-萘胺、3-氨基联苯和4-氨基联苯等烟气有害成分;当印迹聚合物添加量为50mg时,卷烟烟气中芳胺的降低率达到30%。     

Coherent description of D*± production in e + e - and low-Q 2 ep collisions

A real photon has a complicated nature, whereby it may remain unresolved or fluctuate into a vector meson or a perturbative qq? pair. In γγ events, this gives three by three combinations of the nature of the two incoming photons, and thus six distinct event classes. The properties of these classes are partly constrained by the choices already made in our related γp model. It is therefore possible to predict the energy-dependence of the cross section for each of the six components separately. The total cross section gives support to the idea that a simple factorized ansatz with a pomeron and a reggeon term can be a good approximation. Event properties undergo a stepwise evolution from pp to γp to γγ events, with larger charged multiplicity, more transverse energy flow and a higher jet rate in the latter process.     

Kinetics of the aza-Michael Reaction at Room Temperature

The rates of the aza-Michael reaction at room temperature were measured for some amines and alkenes. When the reaction mixture was diluted with methanol, the reaction was accelerated. The acceleration with methanol was especially strong for acrylonitrile. In the latter case, the reaction rate constant can increase by almost three decimal orders. The bulky substituent in the alpha position of methacrylates had little effect on the reaction rate, while the bulky substituent in the ester group significantly slowed the aza-Michael reaction.     

Synergy and Redundancy in a Signaling Cascade with Different Feedback Mechanisms

Feedback plays an important role in various biological signal transmission systems. In this paper, a signaling cascade system (including three layers:input (S), intermediate (V), output (X) components) is employed to study the fluctuations and net synergy in information transmission, in which the V component is regulated by itself or the X component, and each feedback on V is either positive or negative. The Fano factor, the net synergy, and the signalto-noise ratio (SNR) of signaling cascade with the four possible feedback types are theoretically derived by using linear noise approximation of the master equation, and the ability of information transmission through the signaling cascade is characterized by using the partial information decomposition of information theory. It is found that the signaling cascade exhibits different responses to the four feedback mechanisms, which depend on the relationships between degradation rates of components. Our results not only clarify the dependence of the Fano factor, net synergy, and SNR on the feedback regulations with the varying of degradation rates of components, but also imply that living cells could utilize different feedback mechanisms to adapt to the external fluctuating environments.     

钴卟啉对三种胺的固定用于SO2的脱除

利用紫外-可见光谱和荧光光谱手段研究了四苯基卟啉钴(CoTPP)对苯胺、乙二胺和二乙胺的超分子固定用于脱除SO₂. 紫外-可见光谱表明CoTPP与三种胺作用后生成CoTPP-胺配合物,Soret吸收带发生红移. 当通入SO₂后,SO₂与胺的作用强于CoTPP与胺的作用,CoTPP-胺配合物释放出CoTPP,CoTPP 在胺法脱硫过程中起到胺固定作用. 荧光光谱表明CoTPP与三种胺作用形成1:1的分子配合物,且为熵驱动反应. CoTPP与苯胺和二乙胺作用为吸热反应,CoTPP与乙二胺作用为放热反应.     

Scaffold-directed and traceless synthesis of tricyclic quinoxalinone imidazoles under microwave irradiation

Traceless synthesis of 2-aminoimidazoquinoxalinones has been performed on soluble polymer support under open-vessel microwave dielectric heating. The reaction progression is monitored directly by the conventional proton NMR which indicated no release of the substrate from the support. Fmoc-deprotected amino acid polymer conjugates react with 1,5-difluoro-2,4-dinitro benzene to yield polymer bound dinitro fluoro amines, which are further substituted by various primary amines to yield PEG-immobilized dinitrodiamines. Simultaneous reduction of aromatic meta-dinitro group leads to the traceless release of 2-quinoxalinones, followed by N-hetero cyclization with various isothiocyanates in the presence of mercury(II)chloride to furnish 2-aminoimidazoquinolinone rings with three points of diversity at rapid pace.     

Wall shear stress from single almost spherical and long Taylor bubbles in laminar upward tube flow

An experimental electrodiffusional technique with eight double probes is used to detect perturbation of the wall shear stress by a single bubble in laminar upward tube flow. Small almost spherical and long Taylor bubbles are tested. The wall shear stress perturbations by bubbles have a complex structure. It is possible to define three components of perturbation caused by a small bubble. The perturbation by Taylor bubble contains only two components due to the main flow symmetry around the bubble. An unexpectedly long shear stress pulsations zone is registered behind the Taylor bubbles.