Ru-catalyzed C-H activation/cyclization of oximes with sulfoxonium ylides to access isoquinolines.

An external oxidant free Ru(II)-catalyzed C-H activation followed by an intermolecular annulation between oximes and sulfoxonium ylides has been developed. This transformation proceeds smoothly with a broad range of substrates, affording a series of isoquinoline derivatives in moderate to good yields. This protocol was successfully applied to the synthesis of moxaverine.

Isoindolinone synthesis through Rh/Cu-catalyzed oxidative C-H/N-H annulation of N-methoxy benzamides with saturated ketones.

The synthesis of isoindolinones from N-methoxy benzamides and saturated ketones via a bimetallic tandem catalytic annulation has been accomplished. The reaction is catalyzed by a Rh/Cu-cocatalytic system and proceeds via the combination of Cu-catalyzed dehydrogenation of ketones and Rh-catalyzed direct C-H functionalization with the assistance of the N-methoxy amide group which also acts as an oxidant to regenerate the Rh catalyst. This method shows good compatibility with a wide range of substrates and functional groups, and provides an alternative strategy to obtain diverse isoindolinones.

The Role of Interface Ions in the Control of Water Transport through a Carbon Nanotube.

Controlling the water transport toward a given direction is still challenging, particularly due to thermal fluctuations of water motion at the nanoscale. While most of the previous works focus on the symmetric hydrophobic membrane systems, the role of the membrane in affecting the water transport remains largely unexplored. In this work, by using extensive molecular dynamics simulations, we find an interesting electropumping phenomenon, that is, the flowing counterions on an asymmetric hydrophobic-hydrophilic membrane can significantly drive the single-file water transport through a carbon nanotube, suggesting a nanometer water pump in a highly controllable fashion. The ion-water coupling motion in electric fields on the charged surface provides an indirect driving force for this pumping phenomenon. The water dynamics and thermal dynamics demonstrate a unique behavior with the change in electric fields, surface charge density, and even charge species. Particularly, due to the ion flux bifurcation for the positive and negative surfaces, the water dynamics such as the water flow, flux, and translocation time also exhibit similar asymmetry. Surprisingly, the positive surface charge induces an abnormal three-peak dipole distribution for the confined water and subsequent high flipping frequency. This can be attributed to the competition between the surface charge and interface water orientation on it. Our results indicate a new strategy to pump water through a nanochannel, making use of the counterion flowing on an asymmetric charged membrane, which are promising for future studies.

Moisture-Resistant Mn4+ -Doped Core-Shell-Structured Fluoride Red Phosphor Exhibiting High Luminous Efficacy for Warm White Light-Emitting Diodes.

K2 TiF6 :Mn4+ is a highly efficient narrow-band emission red phosphor with promising applications in white light-emitting diodes (LEDs) and wide-gamut displays. Nevertheless, the poor moisture-resistant properties of this material hinder commercialization. A convenient reverse cation-exchange strategy is introduced for constructing a core-shell-structured K2 TiF6 :Mn4+ @K2 TiF6 phosphor. The outer K2 TiF6 shell acts as a shield for preventing moisture in the air from hydrolyzing the internal MnF6 2- group, while effectively cutting off the path of energy migration to surface defects, thereby increasing the emission efficiency (especially for the phosphors doped with high concentrations of Mn4+ ). Employed as a red phosphor, the packaged white LED exhibits an extraordinarily high luminous efficacy of 162 lm W-1 , a correlated color temperature (CCT) of 3510 K, and a color rendering index of 93 (Ra ). Aging tests performed on this device at 85 °C and 85 % humidity for 480 h retain up to 89 % luminous efficacy. The findings could facilitate commercial application of K2 TiF6 :Mn4+ @K2 TiF6 phosphor.

Ultra-fast single-file transport of a simple liquid beyond the collective behavior zone.

We use molecular dynamics simulations to analyze the single-file transport behavior of a simple liquid through a narrow membrane channel. With the decrease of the liquid-channel interaction, the liquid flow exhibits a remarkable maximum behavior owing to the competition of liquid-liquid and liquid-channel interactions. Surprisingly, this maximum flow is coupled to a sudden reduce of the liquid occupancy, where the liquid particle is moving through the channel alone at nearly constant velocity, rather than in a collective motion mode. Further investigation on the encountered energy barrier suggests that this maximum flow should be induced by particles having large instant velocities (or thermal fluctuation) that overcome the liquid-liquid and liquid-channel interaction barriers. Further decreasing the liquid-channel interaction leads to the decrease and ultimate stabilization of the liquid flow, since the energy barrier will increase and becomes steady. These results suggest that the breakdown of collective behavior can be a new rule for achieving fast single-file transportation, especially for simple or nonpolar liquids with relatively weak liquid-liquid interactions, and is thus helpful for the design of high flux nanofluidic devices.

A highly sensitive and selective fluorescent sensor for detection of Al(3+) using a europium(III) quinolinecarboxylate.

Eu2PQC6 has been developed to detect Al(3+) by monitoring the quenching of the europium-based emission, with the lowest detection limit of ∼32 pM and the quantitative detection range to 150 µM. Eu2PQC6 is the first ever example that the europium(III) complex serves as an Al(3+) fluorescent sensor based on "competition-displacement" mode.

Near-Infrared Nanophosphors Based on CuInSe2 Quantum Dots with Near-Unity Photoluminescence Quantum Yield for Micro-LEDs Applications.

Highly efficient near-infrared (NIR) luminescent nanomaterials are urgently required for portable mini or micro phosphors-converted light-emitting diodes (pc-LEDs). However, most existing NIR-emitting phosphors are generally restricted by their low photoluminescence (PL) quantum yield (QY) or large particle size. Herein, a kind of highly efficient NIR nanophosphors is developed based on copper indium selenide quantum dots (CISe QDs). The PL peak of these QDs can be exquisitely manipulated from 750 to 1150 nm by altering the stoichiometry of Cu/In and doping with Zn2+ . Their absolute PLQY can be significantly improved from 28.6% to 92.8% via coating a ZnSe shell. By combining the phosphors with a commercial blue chip, an NIR pc-LED is fabricated with remarkable photostability and a record-high radiant flux of 88.7 mW@350 mA among the Pb/Cd-free QDs-based NIR pc-LEDs. Particularly, such QDs-based nanophosphors acted as excellent luminescence converter for NIR micro-LEDs with microarray diameters below 5 µm, which significantly exceeds the resolutions of current commercial inkjet display pixels. The findings may open new avenues for the exploration of highly efficient NIR micro-LEDs in a variety of applications.

Spin Brazil-nut effect and its reverse in a rotating double-walled drum.

The segregation of binary mixtures in a filled rotating double-walled drum is explored by simulations. Based on the characteristics of self-gravity and the centrifugal force, we argue that both percolation and buoyancy effects dominate the segregation process. The simulational results show that up to long enough times the segregation state is controlled by the rotational speed, the particle radius and density. At low rotational speeds, the smaller and heavier particles tend to accumulate towards the inner drum wall and the bigger and lighter ones towards the outer drum wall, while the segregation pattern reverses completely at higher rotational speeds. Two typical phase diagrams in the space of the density and radius ratio of bigger particles to smaller particles further confirm the predictions.

Characteristics of the colony structure of A2O processes under different ultraviolet conditions in plateau areas.

In this text, a laboratory-scale A2O was performed in Linzhi City at a 3000-m altitude. During the test operation, the UV irradiation was carried out in oxic tank for 0, 5, 10, 30, and 180 min. The 16SrRNA gene sequencing was performed on the activated sludge in anaerobic, anoxic, and oxic tanks, and the colony structure characteristics of phyla, genera, and species classification levels in the sludge were analyzed. There were significant differences in the numbers of genera and species (p ≤ 0.05). The community richness, uniformity, diversity, and other indicators differed to some degree compared with those of other regions. The analysis of composition of bacterial colonies revealed different levels. The significance test of the difference between the groups, the significance of the dominant species, and the mechanism of UV was analyzed. A CCA diagram was used to verify that UV is an important factor in the colony structure composition, and the correlation heatmap diagram was used to analyze the microorganisms that are significantly related to UV. A sample hierarchical cluster analysis showed that the time of UV exposure can be divided into two categories, and the effects of UV exposure increase sequentially as the time of exposure increases. A comprehensive analysis found that the enhancing and inhibitory effects of UV affect the composition of the colony structure in the sample, and the time of irradiation will affect the enhancing or inhibitory effect, that is, the colony structure from the samples that were irradiated for different amounts of time differs greatly.

Suppression of Photoinduced Phase Segregation in Mixed-Halide Perovskite Nanocrystals for Stable Light-Emitting Diodes.

Halide segregation is a critical bottleneck that hampers the application of mixed-halide perovskite nanocrystals (NCs) in both electroluminescent and down-conversion red-light-emitting diodes. Herein, we report a strategy that combines precursor and surface engineering to obtain pure-red-emitting (peaked at 624 nm) NCs with a photoluminescence quantum yield of up to 92% and strongly suppresses the halide segregation of mixed-halide NCs under light irradiation. Red-light-emitting diodes (LED) using these mixed-halide NCs as phosphors exhibit color-stable emission with a negligible peak shift and spectral broadening during operation over 240 min. By contrast, a dramatic peak shift and spectral broadening were observed after 10 min of operation in LEDs based on mixed-halide NCs synthesized by a traditional method. Our strategy is critical to achieving photo- and band-gap-stable mixed-halide perovskite NCs for a variety of optoelectronic applications such as micro-LEDs.

Multiple emission bands NIR-persistent luminescence mSiO2@Zn0.6Ca0.4Ga2O4:Cr3+,Yb3+ nanoparticles for biological applications.

Persistent luminescence nanoparticles (PLNPs) emitting in the NIR window (700-1700 nm) have shown great promise in the field of fluorescence imaging due to their unique properties, including the absence of in situ excitation and low optical scattering in tissues. However, they are still facing some challenges, such as irregular shape, wide size distribution and poor persistent luminescence performance. Here, we report a facile mesoporous template method for synthesizing mSiO2@Zn0.6Ca0.4Ga2O4:Cr3+,Yb3+ (mSiO2@ZCGO) persistent luminescent nanoparticles, which show a regular morphology and a size of about 69 nm. In addition, these nanocrystals exhibit persistent luminescence in multi-NIR windows, the first infrared window (∼696 nm of Cr3+ emission) and second infrared window (∼1000 nm of Yb3+ emission). Under illumination of a 254 nm UV lamp for 10 min, the persistent time of Cr3+ ions and Yb3+ ions lasted more than 120 min and 10 min, respectively. In particular, the NIR persistent emission of mSiO2@ZCGO could be stimulated by soft X-ray, which is beneficial to long-term imaging in deep tissues. The optical penetration length of Yb3+ ions persistent luminescence was evaluated to be 2.8 mm. These results demonstrate the great promise of mSiO2@ZCGO for deep-tissue bio-imaging.

Osmotic Water Permeation through a Carbon Nanotube.

Osmosis are essential for not only the application of nanofluidic devices but also the understanding of working principles of biological transmembrane proteins. Despite considerable experimental interests, comprehensive simulation work is still lacking, possibly because of the periodic boundary condition that inevitably leads to the spontaneous exchange of two side reservoirs. To eliminate this disadvantage, herein we design a simple model system by introducing a dipalmitoylphosphatidylcholine bilayer into a common carbon-nanotube (CNT)-based setup, which allows long-time osmotic simulations. Interestingly, the osmotic water flux exhibits an excellent linear relation with the concentration gradient and an Arrhenius relation with the temperature, which highly coincides with recent experimental observations. Furthermore, the osmotic flux can be quantitatively comparable to not only the experimental CNTs and protein channels but also the theoretical estimation from the Hagen-Poiseuille equation. The designed simulation model could open a new window for future studies on osmosis.

Synthesis and optical properties of a Y3(Al/Ga)5O12:Ce3+,Cr3+,Nd3+ persistent luminescence nanophosphor: a promising near-infrared-II nanoprobe for biological applications.

Persistent luminescence nanophosphors (PLNPs) emitting in the second near-infrared window (1000-1700 nm, NIR-II) are emerging as one promising class of in vivo bio-imaging agents due to their unique advantages including non-autofluorescence and low optical scattering in tissues. Currently, it remains a great challenge to synthesize nanosized lanthanide-doped inorganic NIR-II phosphors with a good persistent luminescence performance. Herein, we present a salt microemulsion method for synthesizing Ce3+, Cr3+, Nd3+ codoped Y3(Al/Ga)5O12 nanocrystals, which generate multi-wavelength persistent luminescence in the visible (∼508 nm, 5d1→ 4f of Ce3+), the first near-infrared window (∼890 nm, 4F3/2→4I9/2 of Nd3+) and NIR-II (∼1063 nm, 4F3/2→4I11/2 of Nd3+) regions. Under illumination of a 410 nm diode (3 W) for 10 min, the observed duration time of NIR-II persistent luminescence is as long as 60 min at room temperature. Moreover, the persistent luminescence can be excited efficiently by multiple excitation sources including a blue diode, white LEDs and an X-ray generator, which is crucial for deep tissue imaging applications. By comparing the penetration depth between NIR-I and NIR-II persistent luminescence through chicken breast, we prove that NIR-II photons exhibit a deeper optical penetration length (3.9 mm) than that of the NIR-I ones (2.5 mm). In addition, the NIR signals can still be detected 3 min after ceasing the excitation source by a small animal imaging system (InGaAs detector) when the thickness of the covering chicken breast is 20 mm. These results show great promise for Y3(Al/Ga)5O12:Ce3+,Cr3+,Nd3+ nanocrystals as a PLNP for bio-imaging applications with deep penetration depth and a high signal-to-noise ratio.

Relationship between the flow rate and the packing fraction in the choke area of the two-dimensional granular flow.

Two-dimensional granular flow in a channel with small exit is studied by both experiments and simulations. We first observe the time variation of the transition from dilute flow state to dense flow state by both experiments and simulations. Then we obtain a relationship between the local flow rate and the local packing fraction in the choke area by use of molecular dynamics simulations. The relationship is a continuous function rather than a discontinuous one. The flow rate has a maximum at a moderate packing fraction and the packing fraction is terminated at high value with negative slope. According to the relationship, four flow states--i.e., stable dilute flow state, metastable dilute flow state, unstable dense flow state, and stable dense flow state--are defined for fixed inflow rate. The discontinuities and the complex time variation behavior occurring in the transition between dilute and dense flow states can be attributed to the abrupt variation through unstable flow state.

A novel method of artery stenosis diagnosis using transfer function and support vector machine based on transmission line model: A numerical simulation and validation study.

BACKGROUND AND OBJECTIVE: Transfer function (TF) is an important parameter for the analysis and understanding of hemodynamics when arterial stenosis exists in human arterial tree. Aimed to validate the feasibility of using TF to diagnose arterial stenosis, the forward problem and inverse problem were simulated and discussed. METHODS: A calculation method of TF between ascending aorta and any other artery was proposed based on a 55 segment transmission line model (TLM) of human artery tree. The effects of artery stenosis on TF were studied in two aspects: stenosis degree and position. The degree of arterial stenosis was specified to be 10-90% in three representative arteries: carotid, aorta and iliac artery, respectively. In order to validate the feasibility of diagnosis of artery stenosis using TF and support vector machine (SVM), a database of TF was established to simulate the real conditions of artery stenosis based on the TLM model. And a diagnosis model of artery stenosis was built by using SVM and the database. RESULTS: The simulating results showed the modulus and phase of TF were decreasing sharply from frequency 2 to 10Hz with the stenosis degree increasing and displayed their unique and nonlinear characteristics when frequency is higher than 10Hz. The diagnosis results showed the average accuracy was above 76% for the stenosis from 10% to 90% degree, and the diagnosis accuracies of moderate (50%) and serious (90%) stenosis were 87% and 99%, respectively. When the stenosis degree increased to 90%, the accuracy of stenosis localization reached up to 94% for most of arteries. CONCLUSIONS: The proposed method of combining TF and SVM is a theoretically feasible method for diagnosis of artery stenosis.

A theoretical study of the TiC5 cluster.

The geometric and electronic properties of the titanium carbide TiC(5) cluster in its neutral and anionic charge states have been investigated using density functional theory (DFT) at the B3LYP level. The nonplanar six-membered ring-type or "butterflylike" structures are found to be the equilibrium geometric structures of TiC(5) and TiC(5) (-). Time-dependent DFT is used in the calculation of the excited states. The theoretical assignment at the B3LYP level for the features in the photoelectron spectrum is given. All results obtained are in good agreement with the available experimental data.