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1.
In this paper the effects of surface roughness and annealing temperature (T) of latex coating films on adhesion are discussed for the different stages of the film formation process. The surface free energy of latex films was assessed in terms of practical work of adhesion (W) (or adherence) using a custom-built adhesion-testing device (ATD), atomic force microscopy (AFM), and contact angle measurements. For preannealed latex films surface roughness averages (Ra) were determined from AFM height images and were related to the values of W obtained from ATD measurements at room temperature. The results obtained using these tests exhibiting surface behavior on different length scales indicate a dependence of the measured adhesion on surface roughness and temperature, as well as on the length scale of the measurements.First preannealed samples were studied, which were obtained by heat treatment above the respective glass transition temperatures (Tg). Increasing the temperature of preannealing resulted in a decrease of the adherence observed in ATD experiments at room temperature. However, on the nanoscale, using AFM, no significant variation of the adherence was observed. This observation can be explained by roughness arguments. Preannealing decreases roughness which results in lower adherence values measured by ATD while for essentially single asperity AFM experiments roughness has an insignificant effect. Specimens were also annealed over a constant period of time (90 min) at different temperatures. At the end of the heat treatment, adhesion was measured at the treatment temperature by ATD. The amplified effect of temperature observed in this case on adherence is attributed to the combination of roughness decrease and increasing test temperature. In a third set of experiments completely annealed samples were studied by ATD as well as by AFM as a function of temperature. With increasing T values ATD showed a decrease in adherence, which is attributed to a decreasing surface free energy of the annealed films at elevated T values. AFM, on the other hand, showed an opposite trend which is assigned to increasing penetration of the tip into the tip/wetting polymer samples versus increasing temperature. Finally, annealing isotherms as a function of time were investigated by ATD in situ at different temperatures. This last set of experiments allowed us to optimize annealing time and temperature to achieve complete curing. 相似文献
2.
Abstract— Understanding of reaction mechanisms in photochemistry is advanced both by kinetic measurements to determine rates of reaction and by spectroscopic studies of the structures of precursors and photoproducts. When kinetics and spectroscopy are combined in a time-resolved, multiwavelength spectroscopic measurement on a reacting system, spectra and structures of intermediates can also be determined. In this paper, the application of multidimensional least-squares and factor analysis techniques for resolving overlapped spectra from intermediates in photochemical kinetics are discussed. The methods are employed specifically to resolve Raman spectra of intermediates in triplet-state photoreactions. By varying excitation intensity, spectra of excited-triplet states are resolved from ground states and solvent. By varying the concentration of a triplet quencher in the sample, the Raman spectrum of a sensitizer excited state (benzophe-none) can be resolved from those of acceptor-triplet states or radical photoproducts. Applications of these concepts in other areas of photochemical kinetics are addressed. 相似文献
3.
Balakumar A Lysenko AB Carcel C Malinovskii VL Gryko DT Schweikart KH Loewe RS Yasseri AA Liu Z Bocian DF Lindsey JS 《The Journal of organic chemistry》2004,69(5):1435-1443
A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols. 相似文献
4.
Žydrė Šaltienė Natalija Jatulienė Mudis Šalkauskas Daiva Brukštienė Asta Ruzgytė Aušra Tarasevičiūtė Julius Kalibatas 《Accreditation and quality assurance》2005,10(8):444-451
The estimation scheme of uncertainty of determination of 1-hydroxypyrene (1-OHP) in urine was developed analysing the main
stages of the analytical procedure: (1) preparation of 1-OHP standards, (2) creation of the calibration curve for the high
performance liquid chromatography (HPLC) analysis method with the evaluation of recovery, (3) measuring procedure of aliquot
of urine, (4) adjusting the pH of aliquot and hydrolysis with enzyme, (5) solid phase extraction, (6) concentration of the
extract, (7) injection of the extract to chromatograph and analysing by the HPLC method, (8) calculation of 1-OHP mass from
the calibration curve, (9) calculation of 1-OHP concentration in urine. The evaluation of the uncertainty is based on quantification
of individual components. Combined uncertainty was calculated using the law of propagation of uncertainties according to the
EURACHEM/CITAC guidelines. Level dependence of the uncertainty arises from the calibration curve.
The limits of detection and quantification were found to be equal to 0.03 and 0.1 ng/mL, respectively. The calculated expanded
level-dependent uncertainty covers 47–27–25% within the concentration range 0.03–0.1–0.4 ng/mL with the materials and equipment
used. These parameters could easily be recalculated according to the proposed scheme if there are some changes in the analysis
procedure. 相似文献
5.
Results of density functional theory computations of infrared (IR) spectra of linear sandwich V(n)Bz(n+1), n = 1-6, complexes are presented. It is shown that the systematic changes in the spectra as a function of the complex size can be categorized and understood in terms of responses of the "parent" modes of the Bz molecule and the VBz complex. The analysis presented should be applicable to a broad class of linear sandwich systems. 相似文献
6.
Guibin Ma Andreas Fischer Julius Glaser 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m177-m178
The title compound, bis(dimethyl sulfoxide)triiodothallium(III), [TlI3(C2H6OS)2], was crystallized from equimolar amounts of TlII and I2 in a dimethyl sulfoxide (DMSO) solution. After the initial redox reaction, the thallium(III)–iodo complex forms and precipitates as a DMSO solvate. In the crystal structure, Tl is surrounded by three iodide ligands in the equatorial plane and two O‐coordinated DMSO molecules in the axial positions, forming a slightly distorted trigonal bipyramid. The complex lies on a twofold rotation axis, making the DMSO molecules and two of the I atoms crystallographically equivalent. 相似文献
7.
Rudzevich Y Vysotsky MO Bohmer V Brody MS Rebek Jr J Broda F Thondorf I 《Organic & biomolecular chemistry》2004,2(21):3080-3084
The dimerization of tetratolyl- and tetratosyl-urea derivatives 1 and 2, derived from a tetrapentoxy calix[4]arene in the cone conformation and of the corresponding tetra-urea derivatives 3 and 4, in which the cone conformation is rigidified by the two crown-3 tethers, have been studied. All six possible equimolar mixtures were examined by 1H NMR using CDCl3 and CD2Cl2 as solvents. While no heterodimers are found for the combinations 1/3 and 2/4 in either solvent, all remaining combinations lead to the (exclusive) formation of heterodimers in CD2Cl2. In CDCl3 heterodimers are only observed for the combinations of 3 with 2 or 4. These results are discussed in terms of entropic and enthalpic contributions and compared with MD-simulations in a box of chloroform solvent molecules. 相似文献
8.
Boumendjel A Roberts JC Hu E Pallai PV Rebek J 《The Journal of organic chemistry》1996,61(13):4434-4438
We describe the asymmetric synthesis of non-peptidic compounds that feature rigid backbone conformations and present various side-chain functions. The key step in the synthesis of these compounds is the C-acylation of an appropriate ketone with a suitably protected aspartic acid derivative. The resulting dipeptide modules may be connected to form tetrapeptide mimics. Specifically is described the mimicry of a four-residue segment of CD4, the cellular receptor of HIV-1. The design was based on molecular modeling and the X-ray crystal structures of CD4 and intended to present the most important side chains and backbone elements of the Phe43-Lys46 segment. 相似文献
9.
Julius Rebek Jr. 《Structural chemistry》1990,1(1):129-131
A structural refinement is proposed for the mechanistic details of the action of the serine proteases. The proposal involves ring flipping of the imidazole function of the histidine side chain as a vehicle for proton transfer. The geometric feasibility of this motion is established by molecular graphics analysis of the crystal structure of-chymotrypsin. It is suggested that the shape of histidine is as important as its pK
a for its function at the active sites of enzymes. 相似文献
10.
Crystal engineering of novel cocrystals of a triazole drug with 1,4-dicarboxylic acids 总被引:4,自引:0,他引:4
Remenar JF Morissette SL Peterson ML Moulton B MacPhee JM Guzmán HR Almarsson O 《Journal of the American Chemical Society》2003,125(28):8456-8457
Cocrystals of the poorly soluble antifungal drug cis-itraconazole (1) with 1,4-dicarboxylic acids have been prepared. The crystal structure of the succinic acid cocrystal with 1 was determined to be a trimer by single-crystal X-ray. The trimer is comprised of two molecules of 1 oriented in antiparallel fashion to form a pocket with a triazole at either end. The extended succinic acid molecule fills the pocket, bridging the triazole groups through hydrogen-bonding interactions rather than interacting with the more basic piperazine nitrogens. The solubility and dissolution rate of some of the cocrystals are approximately the same as those of the amorphous drug in the commercial formulation and are much higher than those for the crystalline free base. The results suggest that cocrystals of drug molecules have the possibility of achieving the higher oral bioavailability common for amorphous forms of water-insoluble drugs while maintaining the long-term chemical and physical stability that crystal forms provide. 相似文献