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21.
Maria Pizzoli Giovanni Pezzin Giuseppina Ceccorulli 《Journal of Macromolecular Science: Physics》2013,52(2):241-250
Samples of poly(vinyl chloride) plasticized with variable amounts of either dibutyl phthalate (DPB) or dicyclohexyl phthalate (DCHP) were investigated by dynamic-mechanical measurements in the β relaxation temperature range. In this range of temperature, a superposition of the relaxation due to the cyclohexyl group with the PVC β peak was found for the samples plasticized with DCHP. By studying the dependence of the activation energy and of the peak broadness on the DCHP concentration it was possible to show that the PVC β relaxation is reduced to zero at the critical plasticizer weight fraction W1 = 0.2. For the PVC-DBP series the β peak disappears at the same plasticizer content. These results strengthen the hypothesis that the β peak of PVC is due to a kind of cooperative motion since 1 mole of plasticizer for every 20 repeating units of the polymer is sufficient to suppress the PVC β relaxation. 相似文献
22.
Dr. Laura Ielo Prof. Dr. Vittorio Pace Prof. Dr. Wolfgang Holzer Md. Mahbubur Rahman Dr. Guangrong Meng Dr. Roman Szostak Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16246-16250
The structure and properties of amides are of tremendous interest in organic synthesis and biochemistry. Traditional amides are planar and the carbonyl group non-electrophilic due to nN→π*C=O conjugation. In this study, we report electrophilicity scale by exploiting 17O NMR and 15N NMR chemical shifts of acyclic twisted and destabilized acyclic amides that have recently received major attention as precursors in N-C(O) cross-coupling by selective oxidative addition as well as precursors in electrophilic activation of N-C(O) bonds. Most crucially, we demonstrate that acyclic twisted amides feature electrophilicity of the carbonyl group that ranges between that of acid anhydrides and acid chlorides. Furthermore, a wide range of electrophilic amides is possible with gradually varying carbonyl electrophilicity by steric and electronic tuning of amide bond properties. Overall, the study quantifies for the first time that steric and electronic destabilization of the amide bond in common acyclic amides renders the amide bond as electrophilic as acid anhydrides and chlorides. These findings should have major implications on the fundamental properties of amide bonds. 相似文献
23.
In Korchmáros et al. (2018)one-factorizations of the complete graph are constructed for with any odd prime power such that either or . The arithmetic restriction is due to the fact that the vertices of in the construction are the points of a conic in the finite plane of order . Here we work on the Euclidean plane and describe an analogous construction where the role of is taken by a regular -gon. This allows us to remove the above constraints and construct one-factorizations of for every even . 相似文献
24.
Mariangela Potenza Giuseppina Sabatino Francesca Giambi Luca Rosi Anna Maria Papini Luigi Dei 《Analytical and bioanalytical chemistry》2013,405(2-3):691-701
The chemical analysis of egg-based wall paintings—the mezzo fresco technique—is an interesting topic in the characterisation of organic binders. A revised procedure for a dot-enzyme-linked immunosorbent assay (dot-ELISA) able to detect protein components of egg-based wall paintings is reported. In the new dot-ELISA procedure we succeeded in maximizing the staining colour by adjusting the temperature during the staining reaction. Quantification of the colour intensity by visible reflectance spectroscopy resulted in a straight line plot of protein concentration against reflectance in the wavelength range 380–780 nm. The modified dot-ELISA procedure is proposed as a semi-quantitative analytical method for characterisation of protein binders in egg-based paintings. To evaluate its performance, the method was first applied to standard samples (ovalbumin, whole egg, egg white), then to model specimens, and finally to real samples (Giotto’s wall paintings). Moreover, amino acid analysis performed by innovative ultra-performance liquid chromatography was applied both to standards and to model samples and the results were compared with those from the dot-ELISA tests. In particular, after protein hydrolysis (24 h, 114 °C, 6 mol L?1 HCl) of the samples, amino acid derivatization by use of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate enabled reproducible analysis of amino acids. This UPLC amino acid analysis was rapid and reproducible and was applied for the first time to egg-based paintings. Because the painting technique involved the use of egg-based tempera on fresh lime-based mortar, the study enabled investigation of the effect of the alkaline environment on egg-protein detection by both methods. Figure
Model wall paintings specimens and typical dot-ELISA stains for egg proteins. 相似文献
25.
Crystal L. Pace Kenneth P. Garrard David C. Muddiman 《Journal of mass spectrometry : JMS》2022,57(7):e4872
Untargeted analyses in mass spectrometry imaging produce hundreds of ion images representing spatial distributions of biomolecules in biological tissues. Due to the large diversity of ions detected in untargeted analyses, normalization standards are often difficult to implement to account for pixel-to-pixel variability in imaging studies. Many normalization strategies exist to account for this variability, but they largely do not improve image quality. In this study, we present a new approach for improving image quality and visualization of tissue features by application of sequential paired covariance (SPC). This approach was demonstrated using previously published tissue datasets such as rat brain and human prostate with different biomolecules like metabolites and N-linked glycans. Data transformation by SPC improved ion images resulting in increased smoothing of biological features compared with commonly used normalization approaches. 相似文献
26.
Luana Malacaria Giuseppina Anna Corrente Amerigo Beneduci Emilia Furia Tiziana Marino Gloria Mazzone 《Molecules (Basel, Switzerland)》2021,26(9)
This review focuses on the ability of some natural antioxidant molecules (i.e., hydroxycinnamic acids, coumarin-3-carboxylic acid, quercetin, luteolin and curcumin) to form Al(III)- and Fe(III)-complexes with the aim of evaluating the coordination properties from a combined experimental and theoretical point of view. Despite the contributions of previous studies on the chemical properties and biological activity of these metal complexes involving such natural antioxidants, further detailed relationships between the structure and properties are still required. In this context, the investigation on the coordination properties of Al(III) and Fe(III) toward these natural antioxidant molecules might deserve high interest to design water soluble molecule-based metal carriers that can improve the metal’s intake and/or its removal in living organisms. 相似文献
27.
Giuseppina La Ganga Fausto Puntoriero Enza Fazio Mirco Natali Francesco Nastasi Antonio Santoro Maurilio Galletta Sebastiano Campagna 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):16904-16911
The luminophore Ru(bpy)2(dcbpy)2+ (bpy=2,2’-bipyridine; dcbpy=4,4’-dicarboxy-2,2’-bipyridine) is covalently linked to a chitosan polymer; crosslinking by tripolyphosphate produced Ru-decorated chitosan fibers (NS-RuCh), with a 20 : 1 ratio between chitosan repeating units and RuII chromophores. The properties of the RuII compound are unperturbed by the chitosan structure, with NS-RuCh exhibiting the typical metal-to-ligand charge-transfer (MLCT) absorption and emission bands of RuII complexes. When crosslinks are made in the presence of IrO2 nanoparticles, such species are encapsulated within the nanofibers, thus generating the IrO2⊂NS-RuCh system, in which both RuII photosensitizers and IrO2 water oxidation catalysts are within the nanofiber structures. NS-RuCh and IrO2⊂NS-RuCh have been characterized by dynamic light scattering, scanning electronic microscopy, and energy-dispersive X-ray analysis, which indicated a 2 : 1 ratio between RuII chromophores and IrO2 species. Photochemical water oxidation has been investigated by using IrO2⊂NS-RuCh as the chromophore/catalyst assembly and persulfate anions as the sacrificial species: photochemical water oxidation yields O2 with a quantum yield (Φ) of 0.21, definitely higher than the Φ obtained with a similar solution containing separated Ru(bpy)32+ and IrO2 nanoparticles (0.05) or with respect to that obtained when using NS-RuCh and “free” IrO2 nanoparticles (0.10). A fast hole-scavenging process (rate constant, 7×104 s−1) involving the oxidized photosensitizer and the IrO2 catalyst within the IrO2⊂NS-RuCh system is behind the improved photochemical quantum yield of IrO2⊂NS-RuCh. 相似文献
28.
Gram‐Scale Enantioselective Formal Synthesis of Morphine through an ortho–para Oxidative Phenolic Coupling Strategy
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Dr. Matthieu Tissot Dr. Robert J. Phipps Dr. Catherine Lucas Dr. Rafael M. Leon Dr. Robert D. M. Pace Dr. Tifelle Ngouansavanh Prof. Matthew J. Gaunt 《Angewandte Chemie (International ed. in English)》2014,53(49):13498-13501
A gram‐scale catalytic enantioselective formal synthesis of morphine is described. The key steps of the synthesis involve an ortho–para oxidative phenolic coupling and a highly diastereoselective “desymmetrization” of the resulting cyclohexadienone that generates three of the four morphinan ring junction stereocenters in one step. The stereochemistry is controlled from a single carbinol center installed through catalytic enantioselective hydrogenation. These transformations enabled the preparation of large quantities of key intermediates and could support a practical and scalable synthesis of morphine and related derivatives. 相似文献
29.
Vladislav V. Klepov Anna A. Berseneva Kristen A. Pace Vancho Kocevski Mengqi Sun Peng Qiu Hui Wang Fanglin Chen Theodore M. Besmann Hans‐Conrad zur Loye 《Angewandte Chemie (International ed. in English)》2020,59(27):10836-10841
Most ternary sulfides belonging to the MGaS2 structure‐type have been known for many years and are well‐characterized. Surprisingly, there have been no reports of the NaGaS2 composition, which contains Na, a monovalent cation slightly larger in size than Li, found in LiGaS2, a compound known for its non‐linear optical properties. Now it is demonstrated for the first time that the unique reversible water absorption in NaGaS2 has resulted in its absence from previous reports owing to difficulties encountered when characterizing this compound by SC XRD. The layered structure of this compound coupled with uniquely easy migration of water molecules between the layers allows for ion exchange with 3d and 5f metal cations. Some cations, for example, Ni2+, facilitate exfoliation of the layers, providing a facile synthetic route to a new class of 2D chalcogenide materials and furthermore demonstrating that NaGaS2 can readily uptake uranyl species from aqueous solutions. 相似文献
30.
Curulli Antonella Montesperelli Giampiero Ronca Sara Cavalagli Nicola Ubertini Filippo Padeletti Giuseppina Vecchio Ciprioti Stefano 《Journal of Thermal Analysis and Calorimetry》2020,142(5):1721-1737
Journal of Thermal Analysis and Calorimetry - In the frame of the HERACLES (HEritage Resilience Against CLimate Events on Site) project, a set of cultural heritage sites was studied to improve... 相似文献