Latest ArticlesThe chiral phosphoric acid catalyzed asymmetric[3 + 2] annulation of substituted 2-vinylindoles with azlactones has been established. This reaction represented a practical approach for the synthesis of structurally diverse pyrrolo[1, 2-a]indoles with two vicinal stereocenters including one tetrasubstituted stereocenter in good yields and good stereoselectivities under mild conditions.
The series of salen-bridged bis-pillar[1]arenes were conveniently prepared by condensation reaction of 5, 5'-methylenebis(2-hydroxybenzaldehyde) or 5, 5'-(propane-2, 2-diyl)bis(2-hydroxybenzaldehyde) with mono-amido-functionalized pillar[5]arenes containing different terminal aminoalkyl groups in refluxing ethanol. The 1H NMR and 2D-NOESY spectra indicated that the salen-bridged bis-pillar[5]arenes with longer alkylene linker (n=3, 4, 6) formed the fascinating bis-[1]rotaxanes, while the salenbridged bis-pillar[5]arenes with short hydrazine and ethylenediamino linker (n=0, 2) predominately existed in free form. The single crystal structure of the bis-pillar[5]arene ambiguously indicated that two propylenediamino linker inserted in to two cavities of pillar[5]arene to form a novel bis-[1]rotaxanes.
A versatile and efficient telescoped reaction sequence for the synthesis of tetrahydroisoquinolines (THIQs) is reported that uses TiCl4 to promote cyclization of a benzylaminoacetal derivative and Et3SiH for reduction of the intermediate 4-hydroxy-THIQ. This method is complimentary to the classical Pomeranz-Fritsch and related reactions since it tolerates electron-withdrawing substituents and allows access to 8-substituted THIQs.
A ferrocene-initiated radical reaction of benzoquinone with amines has been successfully developed for the direct access to diaminobenzoquinone imines in high yields, in which the commercially available and cheap ferrocene was employed as a radical initiator and TBHP was used as an oxidant. Moreover, this reaction could be achieved with low loading of ferrocene (0.5 mol%). This protocol is highly efficient with good substrate tolerance and provides a new approach for the construction of benzoquinone imines with potential pharmaceutical interest.
Herein, the origin of the diastereoselectivity of N-heterocyclic carbene (NHC)-catalyzed cross-benzoin reactions between an α-amino aldehyde and furfural was studied by density functional theory. The computational results showed that the reaction proceeded through four steps:nucleophilic addition of NHC onto furfural, formation of a Breslow intermediate, cross-coupling reaction between Breslow intermediate and α-amino aldehyde, and dissociation of the catalyst. The cross-coupling was identified as the diastereoselectivity-determining step, with the R-configured product generated preferentially. Noncovalent interaction (NCI) analysis showed that the C-H ··· O and C-H ··· F interactions were responsible for determining the diastereoselectivity.
A series of novel phenylpyrazole carboxylic acid derivatives containing fluorine moiety, i.e., diamides 11, simple aryl-bearing amides 12 and acylthioureas 14 were successfully synthesized based on the key fluoro-containing phenylpyrazole acid intermediate. The new compounds were identified and confirmed by melting point, 1H NMR, 13C NMR and elemental analysis or HRMS. The bioassay results indicated that some of the compounds possessed excellent insecticidal activities towards oriental armyworm, diamondback moth and corn borer at low concentrations. For examples, compounds 11a, 11e-g and 14b exhibited remarkable larvicidal activities with LC50 values of 0.13-0.39 mg/L and 0.0002-0.0014 mg/L against oriental armyworm and diamondback moth, respectively, were comparable with those of the control chlorantraniliprole. Particularly, 11e were found superior to chlorantraniliprole in oriental armyworm tests (LC50:0.23 mg/L vs. 0.26 mg/L); 11a, 11e, 11f and 14c in diamondback moth tests with LC50 values of 0.0002 mg/L, 0.0002 mg/L, 0.0008 mg/L and 0.0005 mg/L, respectively, were more effective than that of chlorantraniliprole. In addition, 12a also showed a promising insecticidal potential and development/optimization advantage. Compounds 11a, 11e-g, 12a, 14b and 14c could be considered as possible new leading structures for further study. The SAR investigation indicated that the compounds with fluorine motif (e.g., -F, -CF2H, -CF3) held apparently favorable insecticidal potentials, which provided useful guidance for further design/development of new phenylpyrazole-containing agrochemicals.
In this paper, norbornene imidazolium hexafluorophosphate (NM-MIm-PF6) was modified on the surface of aminopropyl silica by ring-opening metathesis polymerization (ROMP), and then oligo(ethylene glycol) methacrylate (OEGMA) were grafted on the surface by atom transfer radical polymerization (ATRP). Some characterizations in this article confirmed that the synthesis of P(NM-MIm-PF6)-SiPOEGMA (P1-Si-P2) is successful. The P1-Si-P2 can separate sugars, amino acids, sulfonamides in a hydrophilic interaction mode and alkyl benzene, polycyclic aromatic hydrocarbon in a reverse phase mode. The experiment also found that the column has typical characteristics of hydrophobic/hydrophilic separation mechanism. Compared to single hydrophobic C18 column and single hydrophilic Si-NH2 column, this P1-Si-P2 shows certain advantages.
It is of a great challenge to develop semiconductor photocatalysts with potential possibilities to simultaneously enhance photocatalytic efficiency and inhibit generation of toxic intermediates. In this study, we developed a facile method to induce the La doping and cationic vacancie (VZn) on ZnO for the highly efficient complete NO oxidation. The photocatalytic NO removal efficiency increases from 36.2% to 53.6%. Most importantly, a significant suppressed NO2 production also has been realized. According to the DFTcalculations, ESR spectra and in situ FTIR spectra, the introduction of La3+ induce the redistribution of charge carriers in La-ZnO, which promote the production of·O2- and lead to the formation of VZn for the formation of·OH, contributing to the complete oxidation of NO to nitrate. Besides, the conversion pathway of photocatalytic NO oxidation has been elaborated. This work paves a new way to simultaneously realize the photocatalytic pollutants removal and the inhibition of toxic intermediates generation for efficient and safe air purification.
Fluorescence switch plays a vital role in bioelectronics and bioimaging. Herein, we presented a new kind of facile electrostatic complex nanoparticles (ECNs) for fluorescence switching in cells and marking of individual cell. The ECNs were prepared by mixing positively charged poly(6-(2-(thiophen-3-yl)ethoxy) hexyl trimethylammonium bromide) (PT) and negatively charged diarylethene sodium salt (DAECOONa). DAE-COONa is a photoswitchable molecule which can be transformed between the ring-closed form and ring-open form under the irradiation of UV or visible light. The closed-form of DAE-COONa can efficiently quench the fluorescence of PT through intermolecular energy transfer, while the open form of DAE-COONa does not influence the emission of PT. Thus, the fluorescence of ECNs can be modulated by light irradiation, and the ECNs with good fluorescence switching performance have been employed for fluorescence imaging and individual cell lighting up process successfully. We demonstrate that the electrostatic complex strategy provides a facile method to construct fluorescence switch for selective cell marking and imaging applications.
Direct, in situ selective detection of intracellular formaldehyde (FA) is of great significance for understanding its function in FA-related diseases. Herein, red carbon dots (RCD) are reported as label-free two-photon fluorescent nanoprobes for detecting and imaging of FA. Upon addition of FA, the -NH2 groups of RCD could quickly and specially react with aldehydes to form Schiff base and then the strong fluorescence of RCD with blue-shift emission is recovery due to the destruction of the hydrogen bond interaction between RCD and water. In addition, the nanoprobes exhibit outstanding photostability, rapid response (< 1 min), high sensitivity (~9.9 μmol/L) and excellent selectivity toward FA over other aldehyde group compounds. Notably, owing to the good cell-membrane permeability and biocompatibility, as well as the large two-photon absorption cross-section, the as-prepared RCD can be used as label-free nanoprobes for selectively detecting and imaging FA in living cells and zebrafishes through one-photon and two-photon excitation. Moreover, RCD could stain the tissue of zebrafishes at depths interval of up to 240 mm under two-photon excitation. This research implied that RCD are promising tools for directly and in situ imaging FA in vivo, thus providing critical insights into FA-related pathophysiological processes.
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