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131.
132.
Understanding solvation in hydrofluoroalkane (HFA) propellants is of great importance for the development of novel pressurized metered-dose inhaler (pMDI) formulations. HFA-based pMDIs are not only the most widely used inhalation therapy devices for delivering small drug molecules to the respiratory tract, but they also hold promise as vehicles for the delivery of therapeutic biomolecules to and through the lungs. In this work we use binding energy calculations to determine the degree of interaction between HFA propellants and candidate HFA-philes, including a methyl-based tail (isohexane, ISO), and fragments of poly(ethylene oxide) (EO), poly(propylene oxide) (PO), and poly(lactide) (LA). The distinct nature of solvation forces of the two HFA propellants approved by the FDA for use in pMDIs, 1,1,1,2-tetrafluoroethane (HFA134a) and 1,1,1,2,3,3,3-heptafluoropropane (HFA227), is also studied. Binding energy (Ebst) calculations demonstrated that an increase in tail polarity through the addition of oxygen atoms in the fragment backbone provides for sites capable of interacting with the HFA propellant molecules, thus enhancing the stabilization energy of the complexes. The interaction energy between HFA227 and LA (EbHFA227-LA = -24.7 kJ.mol(-1)) is significantly more favorable than that between HFA227 and its hydrocarbon analog (EbHFA227-ISO = -10.0 kJ.mol(-1)). However, it was shown that not only the fragment polarity is of relevance in stabilizing the complexes. The accessibility of the oxygen atoms in the fragments of interest is also relevant. Cluster studies indicate that although both oxygen atoms in the LA fragment are available to form H-bonds with the propellant molecules, the ether oxygen in PO is accessible to only one propellant molecule, thus decreasing significantly the stabilization energy of the cluster. The results shown here serve as a guide for the design of novel HFA-philes for HFA-based pMDIs. 相似文献
133.
Antônio Gomes dos Santos Neto Franciele de Matos Morawski Ana Caroline Ferreira Santos Cláudia Quintino da Rocha Roberto Batista de Lima Marília Oliveira Fonseca Goulart Clenilton Costa dos Santos Flávio Colmati Antônio Euzébio Goulart Santana Marco Aurélio Suller Garcia Auro Atsushi Tanaka 《Electroanalysis》2023,35(5):e202200390
Here, we report multiwalled carbon nanotubes (MWCNTs) functionalized with γ-cyclodextrins (γCD) as a novel electrochemical strategy for Rutin determination, showing superior performance than β-cyclodextrins (βCD) modified MWCNTs, suggesting an adequate environment for host-guest interactions. Under optimized conditions, the sensor showed a linear range of 39–975 nmol L−1 and a limit of detection of 7 nmol L−1. When tested with quercetin, catechin, and caffeine, the platform presented high selectivity with an interference response <10 %. The method was employed to quantify Rutin in spiked pharmaceutical and herbal extracts, providing recovery of 93–98.4 %. Also, HPLC-PDA confirmed the method‘s accuracy. 相似文献
134.
Nikolaos S. Papageorgiou Eugénio M. Rocha Vasile Staicu 《Calculus of Variations and Partial Differential Equations》2008,33(2):199-230
In this paper we study second order elliptic equations driven by the Laplacian and p-Laplacian differential operators and
a nonlinearity which is (p-)superlinear (it satisfies the Ambrosetti–Rabinowitz condition). For the p-Laplacian equations
we prove the existence of five nontrivial smooth solutions, namely two positive, two negative and a nodal solution. Finally
we indicate how in the semilinear case, Morse theory can be used to produce six nontrivial solutions.
This paper was completed while the first author was visiting the University of Aveiro as an Invited Scientist. The hospitality
and financial support of the host institution are gratefully acknowledged. The second and third authors acknowledge the partial
financial support of the Portuguese Foundation for Science and Technology (FCT) under the research project POCI/MAT/55524/2004. 相似文献
135.
Driscoll JA Allard MM Wu L Heeg MJ da Rocha SR Verani CN 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(31):9665-9674
Herein, we describe the synthesis and characterization of a novel series of single-tail amphiphiles LPyCn (Py=pyridine, Cn=C18, C16, C14, C10) and their copper(II)-containing complexes, which are of relevance for patterned films. The N-(pyridine-2-ylmethyl)alkyl-1-amine ligands and their complexes [CuIICl2(LPyC18)] (1), [CuIICl2(LPyC16)] (2), [CuIICl2(LPyC14)] (3), [CuIIBr2(LPyC18)] (4), [CuIIBr2(LPyC16)] (5), and [CuIIBr2(LPyC10)] (6) were synthesized, isolated, and characterized by means of mass spectrometry, IR and NMR spectroscopies, and elemental analysis. Complexes 1, 2, 3, and 6 had their molecular structure solved by X-ray diffraction methods, which showed that the local geometry around the metal center is distorted square planar. With the aim of using these species as precursors for redox-responsive films, an assessment of their electrochemical properties involved cyclic voltammetry in different solvents, with different supporting electrolytes and scan rates. Density functional theory calculations of relevant species in bulk and at interfaces were used to evaluate their electronic structure and dipole moments. The morphology and order of the resulting films at the air/water interface were studied by isothermal compression and Brewster angle microscopy. Biphasic patterned Langmuir films were observed for all complexes except 3 and 6, and dependence on the chain length and the nature of the halogen coligand determine the characteristics of the isotherms and their intricate topology. Complexes 3 and 6, which have shorter chain lengths, failed to exhibit organization. These results exemplify the first comprehensive study of the behavior of single-tail metallosurfactants, which are likely to lead to high-end technological applications based on their patterned films. 相似文献
136.
Doyle CD Rocha JD Weisman RB Tour JM 《Journal of the American Chemical Society》2008,130(21):6795-6800
The addition of diazonium salts to single-walled carbon nanotubes (SWCNTs) in aqueous surfactant suspensions quenches the intrinsic near-infrared fluorescence of semiconducting SWCNTs through sidewall chemical reactions. Spectrally resolved fluorescence spectroscopy of mixed SWCNT samples has been used to measure structure-dependent relative reactivities in the initial stages of these reactions. For several 4-substituted benzenediazonium salts, Ar-R (Ar = N 2 (+)-C 6H 4 and R = Cl, NO 2, OMe), reactivities at pH 10 were found to be greatest for SWCNTs having the largest band gaps. The magnitude of this band gap dependence varies according to the R-group of the salt, with R = OMe showing the strongest variation. For R = OH, acidification of the sample to pH 5.5 results in reversal of the structural trend, as smaller band gap SWCNTs show slightly greater reactivities. The derivatization reactions observed here proceed concurrently, although at different rates, for semiconducting and metallic SWCNT species. These results therefore provide insight into the difficulties of separating metallic and semiconducting SWCNTs through selective reaction schemes and underscore the need for fluorescence spectroscopy to be used in assessing semiconducting SWCNT reactions. 相似文献
137.
Shi FN Cunha-Silva L Ferreira RA Mafra L Trindade T Carlos LD Paz FA Rocha J 《Journal of the American Chemical Society》2008,130(1):150-167
Isostructural modular microporous Na2[Y(hedp)(H2O)0.67] and Na4[Ln2(hedp)2(H2O)2].nH2O (Ln = La, Ce, Nd, Eu, Gd, Tb, Er) framework-type, and layered orthorhombic [Eu(H2hedp)(H2O)2].H2O and Na0.9[Nd0.9Ge0.10(Hhedp)(H2O)2], monoclinic [Ln(H2hedp)(H2O)].3H2O (Ln = Y, Tb), and triclinic [Yb(H2hedp)].H2O coordination polymers based on etidronic acid (H5hedp) have been prepared by hydrothermal synthesis and characterized structurally by (among others) single-crystal and powder X-ray diffraction and solid-state NMR. The structure of the framework materials comprises eight-membered ring channels filled with Na+ and both free and lanthanide-coordinated water molecules, which are removed reversibly by calcination at 300 degrees C (structural integrity is preserved up to ca. 475 degrees C), denoting a clear zeolite-type behavior. Interesting photoluminescence properties, sensitive to the hydration degree, are reported for Na4[Eu2(hedp)2(H2O)2].H2O and its fully dehydrated form. The 3D framework and layered materials are, to a certain extent, interconvertable during the hydrothermal synthesis stage via the addition of HCl or NaCl: of the 3D framework Na4[Tb2(hedp)2(H2O)2].nH2O, affords layered [Tb(H2hedp) (H2O)].3H2O, whereas layered [Tb(H2hedp)(H2O)2].H2O reacts with sodium chloride yielding a material similar to Na4[Tb2(hedp)2(H2O)2].nH2O. In layered [Y(H2hedp)(H2O)].3H2O, noncoordinated water molecules are engaged in cooperative water-to-water hydrogen-bonding interactions, leading to the formation of a (H2O)13 cluster, which is the basis of an unprecedented two-dimensional water network present in the interlayer space. 相似文献
138.
The heterobridged dinuclear complex cis,cis-[(bpy) 2Ru(mu-OCH 3)(mu-pyz)Ru(bpy) 2] (2+) ( 1; bpy = 2,2'-bipyridine; pyz = pyrazolate) was synthesized and isolated as a hexafluorophosphate salt. Its molecular structure was fully characterized by X-ray crystallography, (1)H NMR spectroscopy, and ESI mass spectrometry. The compound 1.(PF 6) 2 (C 44H 38F 12N 10OP 2Ru 2) crystallizes in the monoclinic space group P2 1/ c with a = 13.3312(4) A, b = 22.5379(6) A, c = 17.2818(4) A, beta = 99.497(2) degrees , V = 5121.3(2) A (3), and Z = 4. The meso diastereoisomeric form was exclusively found in the crystal structure, although the NMR spectra clearly demonstrated the presence of two stereoisomers in solution (rac and meso forms at approximately 1:1 ratio). The electronic properties of the complex in acetonitrile were investigated by cyclic voltammetry and UV-vis and NIR-IR spectroelectrochemistries. The stepwise oxidation of the Ru (II)-Ru (II) complex into the mixed-valent Ru (II)-Ru (III) and fully oxidized Ru (III)-Ru (III) states is fully reversible on the time scale of the in situ (spectro)electrochemical measurements. The mixed-valent species displays strong electronic coupling, as evidenced by the large splitting between the redox potentials for the Ru(III)/Ru(II) couples (Delta E 1/2 = 0.62 V; K c = 3 x 10 (10)) and the appearance of an intervalence transfer (IT) band at 1490 nm that is intense, narrow, and independent of solvent. Whereas this salient band in the NIR region originates primarily from highest-energy of the three IT transitions predicted for Ru(II)-Ru(III) systems, a weaker absorption band corresponding to the lowest-energy IT transition was clearly evidenced in the IR region ( approximately 3200 cm (-1)). The observation of totally coalesced vibrational peaks in the 1400-1650 cm (-1) range for a set of five bpy spectator vibrations in Ru (II)-Ru (III) relative to Ru (II)-Ru (II) and Ru (III)-Ru (III) provided evidence for rapid electron transfer and valence averaging on the picosecond time scale. Other than a relatively short Ru...Ru distance (3.72 A for the crystalline Ru (II)-Ru (II) complex), the extensive communication between metal centers is attributed mostly to the pi-donor ability of the bridging ligands (pyz, OMe) combined with the pi-acceptor ability of the peripheral (bpy) ligands. 相似文献
139.
Josiney A. Souza Carlos J. Braga Barros Victor H. L. Rocha 《Mathematische Nachrichten》2016,289(10):1272-1287
The present paper is dedicated to the study of various aspects of attraction and stability for semigroup actions on topological spaces. The main purpose is to present the connections among the distinct notions of attractors and stable sets. The concept of Conley attractor is also investigated and related to the other notions of attractors. All the results are applied to the theory of control systems. 相似文献
140.
Teixeira RR Barbosa LC Maltha CR Rocha ME Bezerra DP Costa-Lotuf LV Pessoa C Moraes MO 《Molecules (Basel, Switzerland)》2007,12(5):1101-1116
3-Benzyl-furan-2(5H)-one (2a) and 3-(4-bromobenzyl)-furan-2(5H)-one (2b) were treated with TBDMSOTf and converted into the corresponding tert-butyldimethyl-silylfuran ethers. These furans were further condensed with several aromatic aldehydes affording compounds 5-14 with general 3-benzyl-5-arylidene-furan-2(5H)-one structures in 31% to 98% yields. Such compounds are analogues of the naturally occurring nostoclide lactones, reported to present moderate cytotoxic activity. Compounds 5-14 were submitted to an in vitro bioassay against the HL-60, HCT-8, SF295 and MDA-MB-435 cancer cell lines using the MTT cytotoxicity assay. 相似文献