Vortex-induced vibration of a circular cylinder with nonlinear stiffness: prediction using forced vibration data

Nonlinear Dynamics - Vortex-induced vibration (VIV) systems with stiffness nonlinearity have received increasing attention because the stiffness nonlinearity can broaden the effective flow velocity...     

Enantioselective Synthesis of Isoxazolines Enabled by Palladium-Catalyzed Carboetherification of Alkenyl Oximes

Reported here is a highly efficient Pd/Xiang-Phos catalyzed enantioselective carboetherification of alkenyl oximes with either aryl or alkenyl halides, delivering various chiral 3,5-disubstituted and 3,5,5-trisubstituted isoxazolines in good yields with up to 97 % ee. The sterically bulky and electron-rich (S,Rs)- NMe-X2 ligand is responsible for the excellent reactivities and enantioselectivities. The salient features of this transformation include mild reaction conditions, general substrate scope, good functional-group tolerance, good yields, high enantioselectivities, easy scale-up, and application in the late-stage modification of bioactive compounds. The obtained products can be readily transformed into useful chiral 1,3-aminoalcohols.     

Cobalt(II)-Catalyzed C(sp3)−C(sp3) Coupling for the Direct Stereoselective Synthesis of 2-Deoxy-C-Glycosides from Glycals

We report a ligand-controlled Co^II-catalyzed C(sp³)−C(sp³) coupling hydroalkylation for direct and β-selective synthesis of 2-deoxy-C-glycosides from glycals. This reaction proceeds by a radical pathway for alkyl halide activation and is β-selective through ligand control. This approach may inspire the development of further stereoselective coupling reactions with potential application in the field of carbohydrates.     

Dearomative Ring-Fused Azafulleroids and Carbazole-Derived Metallofullerenes: Reactivity Dictated by Encapsulation in a Fullerene Cage

Herein, we report divergent additions of 2,2′-diazidobiphenyls to C₆₀ and Sc₃N@I_h-C₈₀. In stark contrast to that of the previously reported bis-azide additions, the unexpected cascade reaction leads to the dearomative formation of azafulleroids 2 fused with a 7-6-5-membered ring system in the case of C₆₀. In contrast, the corresponding reaction with Sc₃N@I_h-C₈₀ switches to the C−H insertion pathway, thereby resulting in multiple isomers, including a carbazole-derived [6,6]-azametallofulleroid 3 and a [5,6]-azametallofulleroid 4 and an unusual 1,2,3,6-tetrahydropyrrolo[3,2-c]carbazole-derived metallofullerene 5 , whose molecular structures have been unambiguously determined by single-crystal X-ray diffraction analyses. Among them, the addition type of 5 is observed for the first time in all reported additions of azides to fullerenes. Furthermore, unexpected isomerizations from 3 to 5 and from 4 to 5 have been discovered, providing the first examples of the isomerization of an azafulleroid to a carbazole-derived fullerene rather than an aziridinofullerene. In particular, the isomerism of the [5,6]-isomer 4 to the [5,6]-isomer 5 is unprecedented in fullerene chemistry, contradicting the present understanding that isomerization generally occurs between [5,6]- and [6,6]-isomers. Control experiments have been carried out to rationalize the reaction mechanism. Furthermore, representative azafulleroids have been applied in organic solar cells, thereby resulting in improved power conversion efficiencies.     

Comparative Analysis of Chemical Constituents in Different Parts of Lotus by UPLC and QToF-MS

Six parts of lotus (seeds, leaves, plumule, stamens, receptacles and rhizome nodes) are herbal medicines that are listed in the Chinese Pharmacopoeia. Their indications and functions have been confirmed by a long history of clinical practice. To fully understand the material basis of clinical applications, UPLC-QToF-MS combined with the UNIFI platform and multivariate statistical analysis was used in this study. As a result, a total of 171 compounds were detected and characterized from the six parts, and 23 robust biomarkers were discovered. The method can be used as a standard protocol for the direct identification and prediction of the six parts of lotus. Meanwhile, these discoveries are valuable for improving the quality control method of herbal medicines. Most importantly, this was the first time that alkaloids were detected in the stamen, and terpenoids were detected in the cored seed. The stamen is a noteworthy part because it contains the greatest diversity of flavonoids and terpenoids, but research on the stamen is rather limited.     

Integrating Time-Resolved Imaging Information by Single-Luminophore Dual Thermally Activated Delayed Fluorescence

The fact that the lifetime of photoluminescence is often difficult to access because of the weakness of the emission signals, seriously limits the possibility to gain local bioimaging information in time-resolved luminescence probing. We aim to provide a solution to this problem by creating a general photophysical strategy based on the use of molecular probes designed for single-luminophore dual thermally activated delayed fluorescence (TADF). The structural and conformational design makes the dual TADF strong in both diluted solution and in an aggregated state, thereby reducing sensitivity to oxygen quenching and enabling a unique dual-channel time-resolved imaging capability. As the two TADF signals show mutual complementarity during probing, a dual-channel means that lifetime mapping is established to reduce the time-resolved imaging distortion by 30–40 %. Consequently, the leading intracellular local imaging information is serialized and integrated, which allows comparison to any single time-resolved signal, and leads to a significant improvement of the probing capacity.     

Can (H2O) n (n = 1–2) as effective catalysts in the CH2OO + H2S reaction under tropospheric conditions?

The addition reaction of CH₂OO?+?H₂S → HSCH₂OOH without and with catalyst X (X?=?H₂O and (H₂O)₂) has been investigated by CCSD(T)-F12a/VTZ-F12//B3LYP/aug-cc-pVTZ method and canonical variational transition state theory with small curvature tunneling correction. When H₂O was introduced in the CH₂OO?+?H₂S reaction, it not only acts as a catalyst for producing HSCH₂OOH, but also plays as a reactant to forming HOCH₂OOH. The formation channel of HSCH₂OOH is more important than the formation channel of HOCH₂OOH with its calculated rate constant larger by 11.0–43.2 times within the temperature 280–320?K. Then, (H₂O)₂ catalysed CH₂OO?+?H₂S → HSCH₂OOH reaction has been taken into account with its rate lower 1.9–4.2 times than the reaction of CH₂OO?+?H₂S → HSCH₂OOH with water. Also, CH₂OO?+?H₂S with H₂O cannot compete with the CH₂OO?+?H₂S reaction without water. This is different from CH₂OO?+?(H₂O)₂ reaction, which is about 4 orders of magnitude larger than the rate constant for CH₂OO?+?H₂O reaction. Such discrepancy is possible because C(CH₂OO)···O(H₂O) interaction has been enhanced more obviously by H₂O as compared to that of C(CH₂OO)···O(H₂S) interaction.     

Effect of ammonia,ammonia-water,and sulfuric acid on the HO2 + HO2 → H2O2 + 3O2 reaction in troposphere: Competition between stepwise and one-step mechanisms

A detailed theoretical study on the reaction mechanisms for the formations of H₂O₂ + ³O₂ from the self-reaction of HO₂ radicals under the effect of NH₃, H₃N···H₂O, and H₂SO₄ catalysts was performed using the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ method. The rate constant was computed using canonical variational transition state theory (CVT) with small curvature tunneling (SCT). Our results indicate that NH₃-, H₃N···H₂O-, and H₂SO₄-catalyzed reactions could proceed through both one-step and stepwise routes. Calculated rate constants show that the catalyzed routes in the presence of the three catalysts all prefer stepwise pathways. Compared to the catalytic efficiency of H₂O, the efficiencies of NH₃, H₃N···H₂O, and H₂SO₄ are much lower due to their smaller relative concentrations. The present results have provided a definitive example of how basic and acidic catalysts influence the atmospheric reaction of HO₂ + HO₂ → H₂O₂ + ³O₂. These results further encourage one to consider the effects of basic and acidic catalysts on the related atmospheric reactions. Thus, the present investigation should have broad implications in the gas-phase reactions of the atmosphere.     

Silica nanoparticle supported molecularly imprinted polymer layers with varied degrees of crosslinking for lysozyme recognition

Surface imprinting over nanosized support materials is particularly suitable for protein templates, considering the problems with mass transfer limitation and low binding capacity. Previously we have demonstrated a strategy for surface protein imprinting over vinyl-modified silica nanopartiles with lysozyme as a model template by polymerization in high-dilution monomer solution to prevent macrogelation. Herein, the synthesis process was further studied toward enhancement of the imprinting performance by examining the effect of several synthesis conditions. Interestingly, the feed crosslinking degree was found to have a great impact on the thickness of the formed imprinting polymer layers and the recognition properties of the resulting imprinted materials. The imprinted particles with a crosslinking degree up to 50% showed the best imprinting effect. The imprinting factor achieved 2.89 and the specific binding reached 23.3 mg g⁻¹, which are greatly increased compared to those of the lowly crosslinked imprinted materials reported previously. Moreover, the relatively high crosslinking degree led to no significant retarding of the binding kinetics to the imprinted particles, and the saturated adsorption was reached within 10 min. Therefore, this may be a promising method for protein imprinting.     

3种香叶基取代黄烷酮的合成及抗肿瘤活性

3种香叶基黄烷酮是从毛泡桐(Paulownia tomentosa)水果中分离出的3种具有相似结构的黄酮类化合物。我们以廉价的2,4,6-三羟基苯乙酮,羟基苯甲醛为原料经过取代、氯甲基甲基醚保护、羟醛缩合、分子内的麦克加成反应以及脱甲基甲基醚合成了3个香叶基取代黄烷酮。其结构经过核磁共振氢谱及碳谱(1H NMR,13C NMR)和高分辨质谱(HRMS)等技术手段进行了表征,并采用四氮唑蓝(MTT)法测试了合成化合物对肺癌细胞A459的体外抗肿瘤活性。结果表明,所合成的化合物均具有一定的抗肺癌细胞活性,其中化合物2抗肺癌活性明显优于化合物1和3,其半数抑制浓度为25.6μmol/L,为临床疾病的治疗和药物的研发提供了参考。