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141.
甘氨酸在SiO2表面的吸附及热缩合反应 总被引:2,自引:0,他引:2
考察了甘氨酸水溶液平衡浓度和pH值对其在SiO2表面吸附行为的影响,采用DTG,XRD和FT-IR等手段对甘氨酸在SiO2表面的吸附量及晶相结构等进行了表征. 结果表明,甘氨酸在SiO2上的吸附不符合Langmuir吸附模型,当甘氨酸水溶液平衡浓度小于0.073 mol/L时,主要为特定位置吸附,此时SiO2对甘氨酸的吸附源于其表面≡Si-O-基团与甘氨酸离子的-NH+3 端的相互作用; 当平衡浓度大于0.073 mol/L时,呈多层吸附,形成α和β两种晶型的甘氨酸. 用TPD-MS对甘氨酸的热缩合行为进行了考察,结合FT-IR结果表明,产物为环状二聚体哌嗪二酮(DKP),没有检测到线式二聚体以及表面硅酯类物种形成. SiO2对表面吸附的甘氨酸分子产生了诱导活化,使其热缩合温度与体相α甘氨酸相比降低了50 ℃左右. 相似文献
142.
Marcus L. Young Suzanne Schnepp Francesca Casadio Andrew Lins Melissa Meighan Joseph B. Lambert David C. Dunand 《Analytical and bioanalytical chemistry》2009,395(1):171-184
Inductively coupled plasma-optical emission spectroscopy (ICP-OES) was used to determine the bulk metal elemental composition
of 62 modern bronze sculptures cast in Paris in the first half of the twentieth century from the collections of The Art Institute
of Chicago and the Philadelphia Museum of Art. As a result, a comprehensive survey of the alloy composition of the sculptures
of many prominent European artists of the early twentieth century is presented here for the first time. The sculptures in
this study consist of predominantly copper with two main alloying elements (zinc and tin). By plotting the concentrations
of these two elements (zinc and tin) against each other for all the sculptures studied, three clusters of data become apparent:
(A) high-zinc brass; (B) low-zinc brass; (C) tin bronze. These clusters correlate to specific foundries, which used specific
casting methods (sand or lost wax) that were influenced by individual preferences and technical skills of the foundry masters.
For instance, the high-zinc brass alloys (with the highest levels of tin and zinc and the lowest melting temperature) correspond
to most of the Picasso sculptures, correlate with the Valsuani foundry, and are associated with the most recent sculptures
(post-WWII) and with the lost-wax casting method. By expanding the ICP-OES database of objects studied, these material correlations
may become useful for identifying, dating, or possibly even authenticating other bronzes that do not bear foundry marks.
Figure
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
相似文献
Francesca CasadioEmail: |
143.
Sørensen LK 《Rapid communications in mass spectrometry : RCM》2006,20(7):1135-1143
A liquid chromatographic/tandem mass spectrometric method using pneumatically assisted electrospray ionisation (LC/ESI-MS/MS) was developed for determination of dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP), di-'isononyl' phthalate (DINP) and di-'isodecyl' phthalate (DIDP) in milk and milk products including infant formulas. The phthalates were extracted by a mixture of tert-butyl methyl ether and hexane from liquid samples. DBP, BBP and DEHP were removed from fats by liquid/liquid extraction into acetonitrile while DINP and DIDP were cleaned up on deactivated silica. The phthalates were detected in positive ion mode after separation on a reversed-phase C5 analytical column. Two transition products were monitored for each compound. The detection limits related to the transition products of lowest abundance were in the range 5-9 microg/kg. 相似文献
144.
Investigation of all O-methyl ethers of 1,2,3-benzenetriol and 4-methyl-1,2,3-benzenetriol (3-16) by 1H NMR spectroscopy and density-functional calculations disclosed practically useful conformational effects on 1H NMR chemical shifts in the aromatic ring. While the conversion of phenol (2) to anisole (1) causes only small positive changes of 1H NMR chemical shifts (Delta delta < 0.08 ppm) that decrease in the order Hortho > Hmeta > Hpara, the experimental O-methylation induced shifts in ortho-disubstituted phenols are largest for Hpara, Delta delta equals; 0.19 +/- 0.02 ppm (n = 11). The differences are due to different conformational behavior of the OH and OCH3 groups; while the ortho-disubstituted OH group remains planar in polyphenols due to hydrogen bonding and conjugative stabilization, the steric congestion in ortho-disubstituted anisoles outweighs the conjugative effects and forces the Ar-OCH3 torsion out of the ring plane, resulting in large stereoelectronic effects on the chemical shift of Hpara. Conformational searches and geometry optimizations for 3-16 at the B3LYP/6-31G** level, followed by B3LYP/6-311++G(2d,2p) calculations for all low-energy conformers, gave excellent correlation between computed and observed 1H NMR chemical shifts, including agreement between computed and observed chemical shift changes caused by O-methylation. The observed regularities can aid structure elucidation of partly O-methylated polyphenols, including many natural products and drugs, and are useful in connection with chemical shift predictions by desktop computer programs. 相似文献
145.
Lambert C. M. Ngoka Michael L. Gross 《Journal of the American Society for Mass Spectrometry》1999,10(8):732-746
Collisionally activated decomposition (CAD) of a protonated cyclic peptide produces a superposition spectrum consisting of fragments produced following random ring opening of the cyclic peptide to give a set of acylium ions (or isomeric equivalents) of the same m/z. Assignment of the correct sequence is often difficult owing to lack of selectivity in the ring opening. A method is presented that utilizes multiple stages of CAD experiments in an electrospray ion-trap mass spectrometer to sequence cyclic peptides. A primary acylium ion is selected from the primary product-ion spectrum and subjected to several stages of CAD. Amino-acid residues are sequentially removed, one at each stage of the CAD, from the C-terminus, until a b2 ion is reached. Results are presented for seven cyclic peptides, ranging in sizes from four to eight amino-acid residues. This method of sequencing cyclic peptides eliminates ambiguities encountered with other MS/MS approaches. The power of the strategy lies in the capability to execute several stages of CAD upon a precursor ion and its decomposition products, allowing the cyclic peptide to be sequenced in an unambiguous, stepwise manner. 相似文献
146.
147.
Clède S Lambert F Sandt C Gueroui Z Réfrégiers M Plamont MA Dumas P Vessières A Policar C 《Chemical communications (Cambridge, England)》2012,48(62):7729-7731
A rhenium tris-carbonyl derivative has been designed to couple infrared and luminescent detection in cells. Both spectroscopies are consistent with one another; they point out the reliability of the present SCoMPI (for Single Core Multimodal Probe for Imaging) for bimodal imaging and unambiguously indicate a localization at the Golgi apparatus in MDA-MB-231 breast cancer cells. 相似文献
148.
Papageorgiou AC Alavi A Lambert RM 《Chemical communications (Cambridge, England)》2012,48(28):3394-3396
Thermally stable nanoarchitectures are realized on the Ag(100) surface by self-assembly of asymmetrically substituted arenes. The process is instigated by adsorption-induced molecule → surface charge transfer that gives rise to in-plane dipole moments. Observation and calculation indicate that cooperative interactions further enhance the stability of these polarizable systems. 相似文献
149.
Sandra Hildebrandt Andreas Eva Philipp Komissinskiy Claudia Fasel Ingo Fritsch Lambert Alff 《Journal of Sol-Gel Science and Technology》2012,63(3):307-314
Sodium and lithium cobaltates are important materials for thermoelectric and battery applications due to their large thermoelectric power and ability to (de-) intercalate the alkali metal. For these applications, phase pure materials with controlled microstructure are required. We report on the sol?Cgel synthesis of sodium- and lithium-based materials by using acetate precursors. The produced Na2/3CoO2, Li(Ni1/3Mn1/3Co1/3)O2, and Li(Ni1/2Co1/2)O2 powders are phase pure with grain sizes below 1???m. X-ray diffraction and energy-dispersive spectral analyses show that the cation stoichiometry is preserved in the lithium-based compounds. Despite the low temperatures, the sodium content is reduced by 1/3 as compared to the initial value. Chemical phases of the investigated powders are formed in the sol?Cgel route at temperatures typically 100?C200?K lower than those used in the conventional solid-state synthesis of these materials. The suggested sol?Cgel synthesis is a low temperature process suited for production of phase pure and homogeneous materials with volatile cations. 相似文献
150.
Stanton MM Ducker RE MacDonald JC Lambert CR McGimpsey WG 《Journal of colloid and interface science》2012,367(1):502-508
Super-hydrophobic surfaces have been fabricated by casting polydimethylsiloxane (PDMS) on a textured substrate of known surface topography, and were characterized using contact angle, atomic force microscopy, surface free energy calculations, and adhesion measurements. The resulting PDMS has a micro-textured surface with a static contact angle of 153.5° and a hysteresis of 27° when using de-ionized water. Unlike many super-hydrophobic materials, the textured PDMS is highly adhesive, allowing water drops as large as 25.0 μL to be inverted. This high adhesion, super-hydrophobic behavior is an illustration of the "petal effect". This rapid, reproducible technique has promising applications in transport and analysis of microvolume samples. 相似文献