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31.
Shefali Saxena Sanjana Panchagnula Dr. M. Eugenia Sanz Dr. Cristóbal Pérez Dr. Luca Evangelisti Prof. Brooks H. Pate 《Chemphyschem》2020,21(23):2579-2584
1,4-Naphthoquinone (1,4-NQ) is an important product of naphthalene oxidation, and it appears as a motif in many biologically active compounds. We have investigated the structure of 1,4-NQ using chirped-pulse Fourier transform microwave spectroscopy and quantum chemistry calculations. The rotational spectra of the parent species, and its 13C and 18O isotopologues were observed in natural abundance, and their spectroscopic parameters were obtained. This allowed the determination of the substitution rs, mass-weighted rm and semi-experimental reSE structures of 1,4-NQ. The obtained structural parameters show that the quinone moiety mainly changes the structure of the benzene ring where it is inserted, modifying the C−C bonds to having predominantly single or double bond character. Furthermore, the molecular electrostatic surface potential reveals that the quinone ring becomes electron deficient while the benzene ring remains a nucleophile. The most electrophilic areas are the hydrogens attached to the double bond in the quinone ring. Knowledge of the nucleophilic and electrophilic areas in 1,4-NQ will help understanding its behaviour interacting with other molecules and guide modifications to tune its properties. 相似文献
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Total syntheses of nine novel phospholipids were accomplished to facilitate the identification and biological testing of compounds that are generated upon oxidative cleavage of arachidonate and linoleate esters of 2-lysophosphatidylcholine, the two most abundant polyunsaturated phospholipids in low-density lipoprotein. An efficient general synthesis exploiting 2-lithiofuran as a 4-oxo-2-butenoyl carbanion equivalent provided phospholipids containing gamma-keto-alpha,beta-unsaturated carbonyl functional arrays. By exploiting facile cis-trans isomerizations, two commercially available cis alkenes, (2Z)-2-butene-1,4-diol and 2,5-dihydrofuran, could be employed as starting materials for preparing the Horner-Wadsworth-Emmons reagent 4-(diethoxyphosphoryl)-2E-butenal, a valuable building block for the synthesis of 2,4-dienals. The reagent was exploited in a total synthesis of 13-oxotridec-9E,11E-dienoic acid, confirming the identity of this product that is generated upon autoxidation of linoleic acid and by decomposition of 13-hydroperoxy-9,11-octadecadienoate (13-HPODE), especially in the presence of redox active transition metal ions, cytochrome p-450, or hydroperoxide lyase. 相似文献
34.
In this letter quantum chemical calculations are performed on fullerene derivatives with varying reduction potentials, successfully used as electron acceptor in bulk heterojunction solar cells with the aim to investigate the energy levels of the frontier orbitals. We have successfully correlated the theoretical lowest unoccupied molecular orbital (LUMO) levels of different fullerenes with the open circuit voltage of the photovoltaic device based on the polymer–fullerene blend. We have also proposed a new fullerene silirane derivative with a raised LUMO level useful to increase the open circuit voltage of a polymer solar cell. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
35.
Monge ME Bulone D Giacomazza D Negri M Bernik DL 《Combinatorial chemistry & high throughput screening》2004,7(4):337-344
Multicomponent essential oils Tagetes Minuta and Poleo as well as pure limonene were encapsulated in Tween doped-high methoxylated pectin gels. Optical microscopy reveals that the obtained gels containing limonene consisted in a highly heterogeneous oil-in-water emulsion stabilised by the gelled medium. The influence of limonene encapsulation in pectin gelation kinetics and the gel structural properties were followed by dynamic rheological measurements. An electronic nose device developed in our laboratory was used to follow the flavour release of the three systems in order to discriminate the samples according to the main components released to the headspace. PCA and Neural Network Analysis allowed us to discriminate Tagetes Minuta from Poleo due to the difference in their limonene content. It is remarkable that the fingerprints of encapsulated complex mixtures differ from those obtained for the non-encapsulated oils, showing a preferential release of some components. In the case of limonene, the effect of the encapsulated concentration on the detected odour was also studied. 相似文献
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Effectiveness of Photodynamic Therapy in Elimination of HPV‐16 and HPV‐18 Associated with CIN I in Mexican Women 下载免费PDF全文
Elizabeth Maldonado Alvarado Martha Olivia Osorio Peralta Alejandra Moreno Vázquez Lydia Alejandra Martínez Guzmán Maria Eugenia Melo Petrone Zulma Iveth Enriquez Mar Dora Estela Jovel Galdamez Bárbara Carrión Solana Guadalupe Balderas Martínez Eduarda Parra Rossana Inés Castellanos Oliveros Rosa Linda Bello Leiva Araceli Espinosa Montesinos Citlalli Barrera Mendoza Selma Eugenia Medina García Eva Ramón Gallegos 《Photochemistry and photobiology》2017,93(5):1269-1275
This study aimed to determine the effectiveness of photodynamic therapy (PDT), using δ‐aminolevulinic acid (5‐ALA), in the elimination of premalignant cervical lesions in Mexican patients with human papillomavirus (HPV) infection and/or cervical intraepithelial neoplasia (CIN). Thirty women diagnosed with CIN I and/or positive for HPV participated in the study. Topical 6% 5‐ALA in gel form was applied to the uterine cervix; after 4 h, the lesion area was irradiated with a light dose of 200 J cm?2 at 635 nm. This procedure was performed three times at 48‐h intervals. Clinical follow‐up was performed at 3, 6, and 12 months after the initial PDT administration, by colposcopy, cervical cytology, histopathological analysis, polymerase chain reaction, and hybrid capture. Of HPV‐infected patients without evidence of CIN I, 80% cleared the infection, while HPV associated with CIN I was eliminated in 83% of patients (P < 0.05). At 12 months, CIN I had regressed in 57% of patients, although this response was not statistically significant. PDT using 6% 5‐ALA is concluded to be effective in eliminating HPV infection associated or not with CIN I. 相似文献
38.
Mata S Cortijo V Caminati W Alonso JL Sanz ME López JC Blanco S 《The journal of physical chemistry. A》2010,114(43):11393-11398
The Fourier transform microwave spectra of the hydrated forms of the tautomeric pair 2-pyridinone/2-hydroxypyridine (2PO/2HP) have been investigated in a supersonic expansion. Three hydrated species, 2PO-H?O, 2HP-H?O, and 2PO-(H?O)?, have been observed in the rotational spectrum. Each molecular complex was confidently identified by the features of the 1?N quadrupole hyperfine structure of the rotational transitions. The presence of water affects the tautomeric equilibrium -N═C(OH)- ? -NH-C(═O)-, which is shifted to the enol form for the bare molecules 2PO/2HP but to the keto tautomer for the hydrated forms. 相似文献
39.
This paper addresses two different but related questions regarding an unbounded symmetric tridiagonal operator: its self-adjointness and the approximation of its spectrum by the eigenvalues of its finite truncations. The sufficient conditions given in both cases improve and generalize previously known results. It turns out that, not only self-adjointness helps to study limit points of eigenvalues of truncated operators, but the analysis of such limit points is a key help to prove self-adjointness. Several examples show the advantages of these new results compared with previous ones. Besides, an application to the theory of continued fractions is pointed out. 相似文献
40.
Zygfryd Smiatacz Eugenia Paszkiewicz Iwona Chrzczanowicz 《Journal of carbohydrate chemistry》2013,32(3):315-327
ABSTRACT 3,6-Di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2-deoxy-2-hydroxyimino-α- and -β-D-arabino-hexopyranosides of N-benzyloxycarbonyl-L-serine methyl ester as well as of ethanol have been synthesised from D-lactal hexaacetate via nitrosyl chloride, followed by condensation with L-serine derivatives and ethanol, respectively. The compounds of L-serine thus obtained were modified at C-2 and C-3 to afford L-serine derivatives attached to disaccharides containing terminal α-D-gluco-, 2-acetamido-α-D-gluco-, β-D-manno, 2-acetamido-β-D-manno-pyranosyl, 3-azido-2-hydroxyimino-α-D-arabino-, and α-D-ribo-hexopyranosyl residues. 相似文献