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41.
Interaction between a monodispersed poly(acrylic acid) (PAA) (M(W) = 5670 g/mol, M(w)/M(n) = 1.02) with sodium dodecyl sulfate (SDS) was investigated using isothermal titration calorimetry (ITC), ion-selective electrode (ISE), and dynamic light scattering measurements. Contrary to previous studies, we report for the first time evidence of interaction between SDS and PAA when the degree of neutralization (alpha) of PAA is lower than 0.2. Hydrocarbon chains of SDS cooperatively bind to apolar segments of PAA driven by hydrophobic interaction. The interaction is both enthalpy and entropy favored (deltaH is negative but deltaS is positive). In 0.05 wt % PAA solution, the SDS concentration corresponding to the onset of binding (i.e., CAC) is approximately 2.4 mM and the saturation concentration (i.e., C(S)) is approximately 13.3 mM when alpha = 0. When PAA was neutralized and ionized, the binding was hindered by the enhanced electrostatic repulsion between negatively charged SDS and PAA chains and improved solubility of the polymer. With increasing alpha to 0.2, CAC increases to approximately 6.2 mM, C(S) drops to 8.6 mM, and the interaction is significantly weakened where the amount of bound SDS on PAA is reduced considerably. The values of CAC and C(S) derived from different techniques are in good agreement. The binding results in the formation of mixed micelles on apolar PAA coils, which then expands and dissociates into single PAA chains. The majority of unneutralized PAA molecules exist as single polymer chains stabilized by bound SDS micelles in solution after the saturation concentration. 相似文献
42.
Laser-induced fluorescence spectrum of NiI in the near infrared region of 714-770 nm has been recorded. Seven bands belonging to three electronic transition systems were observed and analyzed: the (0,0), (1,0), and (2,0) bands of [13.3] (2)Sigma(+)-A (2)Pi(3/2) system; the (1,1) and (0,1) bands of [13.9] (2)Pi(3/2)-X (2)Delta(5/2) system; and the (0,0) and (1,0) bands of [13.9] (2)Pi(3/2)-A (2)Pi(3/2) system. Spectra of isotopic molecules confirmed the vibrational quantum number assignment of the observed bands. Least-squares fit of rotationally resolved transition lines yielded accurate molecular constants for the v=0-2 levels of the [13.3] (2)Sigma(+) state, the v=0 level of the A (2)Pi(3/2), and the v=1 level of the X (2)Delta(5/2) state. The vibrational separation, DeltaG(1/2), of the ground state was measured to be 276.674 cm(-1). With the observation of the [13.9] (2)Pi(3/2)-A (2)Pi(3/2) and [13.9] (2)Pi(3/2)-X (2)Delta(5/2) transitions, we accurately determined the energy separation between the A (2)Pi(3/2) and the X (2)Delta(5/2) to be 163.847 cm(-1). This confirms that the order of the A (2)Pi(3/2) and X (2)Delta(5/2) states in NiI is reversed when compared with other nickel monohalides. 相似文献
43.
Justin Z. Tam Talulla Palumbo Julie M. Miwa Brian Y. Chen 《Molecules (Basel, Switzerland)》2022,27(19)
Protein-protein interactions often involve a complex system of intermolecular interactions between residues and atoms at the binding site. A comprehensive exploration of these interactions can help reveal key residues involved in protein-protein recognition that are not obvious using other protein analysis techniques. This paper presents and extends DiffBond, a novel method for identifying and classifying intermolecular bonds while applying standard definitions of bonds in chemical literature to explain protein interactions. DiffBond predicted intermolecular bonds from four protein complexes: Barnase-Barstar, Rap1a-raf, SMAD2-SMAD4, and a subset of complexes formed from three-finger toxins and nAChRs. Based on validation through manual literature search and through comparison of two protein complexes from the SKEMPI dataset, DiffBond was able to identify intermolecular ionic bonds and hydrogen bonds with high precision and recall, and identify salt bridges with high precision. DiffBond predictions on bond existence were also strongly correlated with observations of Gibbs free energy change and electrostatic complementarity in mutational experiments. DiffBond can be a powerful tool for predicting and characterizing influential residues in protein-protein interactions, and its predictions can support research in mutational experiments and drug design. 相似文献
44.
Yaron Haviv Olga Georgiev Tal Gaver-Bracha Sharleen Hamad Alina Nemirovski Rivka Hadar Yair Sharav Doron J. Aframian Yariv Brotman Joseph Tam 《Molecules (Basel, Switzerland)》2022,27(14)
Background: the endocannabinoid system (ECS) participates in many physiological and pathological processes including pain generation, modulation, and sensation. Its involvement in chronic orofacial pain (OFP) in general, and the reflection of its involvement in OFP in salivary endocannabinoid (eCBs) levels in particular, has not been examined. Objectives: to evaluate the association between salivary (eCBs) levels and chronic OFP. Methods: salivary levels of 2 eCBs, anandamide (AEA), 2-arachidonoylglycerol (2-AG), 2 endocannabinoid-like compoundsN-palmitoylethanolamine (PEA), N-oleoylethanolamine (OEA), and their endogenous precursor and breakdown product, arachidonic acid (AA), were analyzed using liquid chromatography/tandem mass spectrometry in 83 chronic OFP patients and 43 pain-free controls. The chronic OFP patients were divided according to diagnosis into musculoskeletal, neurovascular/migraine, and neuropathic pain types. Results: chronic OFP patients had lower levels of OEA (p = 0.02) and 2-AG (p = 0.01). Analyzing specific pain types revealed lower levels of AEA and OEA in the neurovascular group (p = 0.04, 0.02, respectively), and 2-AG in the neuropathic group compared to controls (p = 0.05). No significant differences were found between the musculoskeletal pain group and controls. Higher pain intensity was accompanied by lower levels of AA (p = 0.028), in neuropathic group. Conclusions: lower levels of eCBs were found in the saliva of chronic OFP patients compared to controls, specifically those with neurovascular/migraine, and neuropathic pain. The detection of changes in salivary endocannabinoids levels related to OFP adds a new dimension to our understanding of OFP mechanisms, and may have diagnostic as well as therapeutic implications for pain. 相似文献
45.
The properties of iterative splitting with two bounded linear operators have been analyzed by Faragó et al. For more than two operators, iterative splitting can be defined in many different ways. A large class of the possible extensions to this case is presented in this paper and the order of accuracy of these methods are examined. A separate section is devoted to the discussion of two of these methods to illustrate how this class of possible methods can be classified with respect to the order of accuracy. 相似文献
46.
Expedient and Diastereodivergent Assembly of Terpenoid Decalin Subunits having Quaternary Stereocenters through Organocatalytic Robinson Annulation of Nazarov Reagent
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Barbara Berkes Kristóf Ozsváth Laura Molnár Tamás Gáti Tamás Holczbauer György Kardos Tibor Soós 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(50):18101-18106
We report an expedient approach to highly functionalized cis‐ and trans‐decalines that could function as key structural subunits toward the synthesis of various classes of terpenoids. Key to the strategy is an organocatalyzed Robinson annulation reaction of the Nazarov reagent that affords chiral enone building blocks with high enantioselectivities. The quaternary carbon stereogenic center can direct the subsequent reactions and allow the rapid and diastereoconvergent assembly of complex decalines with contiguous stereocenters. 相似文献
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Mihály V. Pilipecz Tamás R. Varga Péter Králl Zoltán Vincze Zoltán Mucsi Ruth Deme 《合成通讯》2020,50(11):1712-1723
AbstractThe novel push–pull alkene, the 2-(nitro-nitrosomethylene)-pyrrolidine with numerous aliphatic or aromatic amines as nucleophiles afforded amidoximes. Various substituted oxadiazaborole and oxadiazole derivatives were prepared starting from these amidoximes, widening the synthetic applicability of the push–pull alkenes. Acylation of the amidoximes was also examined. The mechanism of the amidoxime formation was investigated by computational methods. 相似文献