RESUMEN
In this study, we explorethe synthesis of binaphthyl-based chiral macrocyclic hosts for the first time. They exhibited the selective recognition abilities of iodide anions which can be favored over those of other anions (AcO-, NO3-, ClO4-, HSO4-, Br-, PF6-, H2PO4-, BF4-, and CO3F3S-), as confirmed by UV-vis, HRMS, and 1H NMR spectroscopy experiments, as well as DFT calculations. Neutral aryl C-H···anion interactions play an important role in the formation complexes. The recognition process can be observed by the naked eye.
RESUMEN
A turn-on fluorescent probe, cage 1, was efficiently self-assembled by condensing 4,4'-(benzothiadiazole-4,7-diyl)dibenzaldehyde and TREN in chloroform. The formation of cage 1 was characterized and confirmed by NMR spectroscopy, mass spectrometry, and theoretical calculations. The yield of cage 1 could be controlled by tuning the reaction conditions, such as the precursor concentration. Interestingly, the addition of 10 equiv of Cd2+ relative to cage 1 could increase the fluorescence almost seven-fold. 1H NMR and fluorescence experiments indicating fluorescence enhancement may be caused by the decomposition of cage 1. Such a high selectivity toward Cd2+ implies that the cage could potentially be employed in cadmium detection.
Asunto(s)
Cadmio , Tiadiazoles , Cadmio/química , Microscopía Fluorescente/métodos , Cloroformo , Colorantes Fluorescentes/química , Espectrometría de Fluorescencia/métodosRESUMEN
BACKGROUND: In previous studies, scientists found that, when spirotetramat was introduced into plants or animals, it was mainly metabolised at positions C-4 and C-8. That is to say, these two functional positions potentially played an important role in spirotetramat's bioactivities. In order to develop novel insecticides or miticides, the present authors designed and synthesised 35 spirotetramat analogues based on metabolite structures. RESULTS: All of the analogues have been identified on the basis of (1)H NMR, ESI-MS and elemental analysis data. The activities of these analogues were evaluated against three organisms, and biological assays indicated that compounds 5f, 5h and 5u possessed better insecticidal activities against bean aphids (Aphis fabae) than the lead compound spirotetramat. The LC50 of 5f, 5h and 5u against bean aphids reached 0.42, 0.28 and 2.53 mg L(-1) respectively. Moreover, some compounds possessed comparable activities against carmine spider mite (Tetranychus cinnabarinus) and oriental armyworm (Mythimna sepatara) with spirotetramat. The structure-activity relationships (SARs) indicated that the flexible bridge at position C-4 of spirotetramat was important for its bioactivities, and the size of the group at position C-8 would have great influence on the activities. Furthermore, the log P values lower than 6.0 may be favourable for insecticidal activities. CONCLUSION: The present work demonstrates that some spirotetramat analogues can be used as potential lead compounds for developing novel insecticides, and preliminary SAR analysis would provide information for the utilisation of spirotetramat analogues as potential lipid biosynthesis inhibitors.
Asunto(s)
Compuestos Aza/química , Compuestos Aza/toxicidad , Insecticidas/química , Insecticidas/toxicidad , Lípidos/antagonistas & inhibidores , Compuestos de Espiro/química , Compuestos de Espiro/toxicidad , Animales , Áfidos/efectos de los fármacos , Áfidos/metabolismo , Bioensayo , Diseño de Fármacos , Lípidos/biosíntesis , Estructura Molecular , Mariposas Nocturnas/efectos de los fármacos , Mariposas Nocturnas/metabolismo , Relación Estructura-Actividad , Tetranychidae/efectos de los fármacos , Tetranychidae/metabolismoRESUMEN
BACKGROUND: The development of environmentally friendly and novel structural pesticides is now an area of intense research in the agriculture field. Spirocyclic tetronic acids such as spiromesifen are typical compounds of this kind. In order to discover novel compounds with improved and broader-spectrum insecticidal activities, a series of spiromesifen derivatives were synthesised and bioassayed. RESULTS: The derivatives were identified by (1) H NMR and MS. Preliminary bioassays demonstrated that some bioactivities of compounds 5a to 5u were better and had a broader spectrum than the lead compound spiromesifen. Moreover, these compounds showed better insecticidal activities against Mythimna sepatara and Aphis fabae than acaricidal activities against Tetranychus cinnabari. Furthermore, LC(50) of 5s against Aphis fabae reached 1.09 mg L(-1) . At the same time, compounds 5g, 5i, 5k and 5r also warrant further study because of their superior bioactivities to spiromesifen. What is more, suitable carbon chain length in the 4-position ester and the log P value of these spiromesifen derivatives dramatically influenced their insecticidal activities. Butyric or pentanoic ester and a log P value of 4.0-6.0 may be preferred. CONCLUSION: The present work demonstrates that some spiromesifen derivatives can be used as potential lead compounds for developing novel insecticides and acaricides.
Asunto(s)
Áfidos/efectos de los fármacos , Insecticidas/síntesis química , Insecticidas/toxicidad , Mariposas Nocturnas/efectos de los fármacos , Compuestos de Espiro/síntesis química , Compuestos de Espiro/toxicidad , Animales , Bioensayo , Insecticidas/química , Estructura Molecular , Compuestos de Espiro/químicaRESUMEN
The title tetronic acid derivative, C(20)H(23)ClO(4), which is a spiro-diclofen analogue, has two crystallographically independent mol-ecules in the asymmetric unit (Z' = 2). The cyclo-hexane rings in the respective mol-ecules A and B adopt chair conformations [four C atoms are planar with mean deviations of 0.013â (2) and 0.001â (2)â Å, and the flap positions deviate by 0.653â (4) and -0.663â (3)â Å (mol-ecule A) and 0.642â (4) and -0.643â (5)â Å (mol-ecule B) from the plane]. The furan ring makes dihedral angles of 86.9â (1) (mol-ecule A) and 85.4â (1)° (mol-ecule B) with the respective benzene rings.
RESUMEN
OBJECTIVE: To further explore the application, approach, indication and prognosis of neuroendoscope treatment for skull base chordoma. METHODS: A total of 101 patients of skull base chordoma were admitted at our hospital from May 2000 to April 2010. There were 59 males and 42 females. Their major clinical manifestations included headache, cranial nerve damage and dyspnea. They were classified according to the patterns of tumor growth: Type I (n = 13): tumor location at a single component of skull base, i. e. clivus or sphenoid sinus with intact cranial dura; Type II (n = 56): tumor involving more than two components of skull e. g clivus, sphenoid and nasal/oral cavity, etc. But there was no intracranial invasion; Type III (n = 32) : tumor extending widely and intradurally forming compression of brain stems and multiple cranial nerves. Based on the types of chordoma, different endoscopic approaches were employed, viz. transnasal, transoral, trans-subtemporal fossa and plus microsurgical craniotomy for staging in some complex cases. RESULTS: Among all patients, total resection was achieved (n = 19), subtotal (n = 58) and partial (n = 24). In partial resection cases, 16 cases were considered to be subtotal due to a second-stage operation. Most cases had conspicuous clinical improvements. Self-care recovery within one week post-operation accounted for 58.4%, two weeks 30.7%, one month 6.9% and more than one month 1.9%. Postoperative complications occurred in 13 cases (12.8%) and included CSF leakage (n = 4) cranial nerve palsy (n = 5), hemorrhagic nasal wounds (n = 3) and delayed intracranial hemorrhage (n = 1). All of these were cured or improved after an appropriate treatment. A follow-up of 6 - 60 months was conducted in 56 cases. CONCLUSION: Early detection and early treatment are crucial for achieving a better outcome in chordoma. Neuroendoscopic treatment plays an important role in managing those complicated cases. Precise endoscopic techniques plus different surgical approaches and staging procedures are required to improve the post-operative quality of life for patients.
Asunto(s)
Cordoma/cirugía , Neuroendoscopía , Neoplasias de la Base del Cráneo/cirugía , Adolescente , Adulto , Anciano , Niño , Femenino , Humanos , Masculino , Persona de Mediana Edad , Adulto JovenRESUMEN
In the title compound, C(24)H(24)O(4), a derivative of the potent insecticide and miticide spiro-mesifen, one cyclo-pentane C atom is disordered over two positions with occupancies of 0.574â (12) and 0.426â (12), resulting in respective envelope and twisted conformations for the cyclo-pentane ring. The atom at the flap position is 0.620â (5)â Å out of the mean plane formed by the other four atoms of the envelope form. The furan ring makes dihedral angles of 68.26â (3) and 69.38â (2)°, respectively, with the 2,4,6-trimethyl-phenyl and benzene rings. The dihedral angle between the two benzene rings is 62.27â (3)°.
RESUMEN
IN THE TITLE TRICHODERMIN COMPOUND (SYSTEMATIC NAME: 12,13-ep-oxy-trichothec-9-en-4ß-yl 4-fluoro-benzoate), C(22)H(25)FO(4), the five-membered ring displays an envelope conformation, whereas the two six-membered rings show the different conformations, viz. chair and half-chair. As for the seven-membered ring, the dihedral angle between the mean planes formed by the four C atoms of the envelope unit and the three C and one O atoms of the six-membered chair is 68.67â (2)°; these two mean planes are nearly perpendicular to the ep-oxy ring with angles of 87.97â (2)and 88.14â (2)°, respectively.