Highly visible-light luminescence properties of the carboxyl-functionalized short and ultrashort MWNTs

Luminescence of the short multiwalled carbon nanotubes (MWNTs) conjugated with carboxylic acid groups has been studied. The results show that the carboxyl-functionalized short MWNTs could emit luminescence and the emission peak appears at 500 nm with a corresponding optimal excitation wavelength centering at 310 nm. When the short MWNTs are filtered through 0.15 μm polytetrafluoroethylene (PTFE) membrane, the ultrashort MWNTs are obtained from the filtrate. An interesting feature for the ultrashort MWNTs is that the emission intensity is strengthened and the peak is slightly blue shifted to 460 nm. This result indicates that the luminescence properties of MWNTs are strongly affected by the tube length. After chemical oxidization cutting, defects and carboxylic acid groups at the tube end and/or sidewall can be produced; the more shorten of MWNTs, the better dispersion and carboxylic passivation of the nanotubes, and the more intense luminescence emissions. The broad emissions are logically attributed to the trapping of excitation energy by defect sites in the carboxyl-functionalized nanotube structure.     

Structural mining: self-consistent design on flexible protein-peptide docking and transferable binding affinity potential

A flexible protein-peptide docking method has been designed to consider not only ligand flexibility but also the flexibility of the protein. The method is based on a Monte Carlo annealing process. Simulations with a distance root-mean-square (dRMS) virtual energy function revealed that the flexibility of protein side chains was as important as ligand flexibility for successful protein-peptide docking. On the basis of mean field theory, a transferable potential was designed to evaluate distance-dependent protein-ligand interactions and atomic solvation energies. The potential parameters were developed using a self-consistent process based on only 10 known complex structures. The effectiveness of each intermediate potential was judged on the basis of a Z score, approximating the gap between the energy of the native complex and the average energy of a decoy set. The Z score was determined using experimentally determined native structures and decoys generated by docking with the intermediate potentials. Using 6600 generated decoys and the Z score optimization criterion proposed in this work, the developed potential yielded an acceptable correlation of R(2) = 0.77, with binding free energies determined for known MHC I complexes (Class I Major Histocompatibility protein HLA-A(*)0201) which were not present in the training set. Test docking on 25 complexes further revealed a significant correlation between energy and dRMS, important for identifying native-like conformations. The near-native structures always belonged to one of the conformational classes with lower predicted binding energy. The lowest energy docked conformations are generally associated with near-native conformations, less than 3.0 Angstrom dRMS (and in many cases less than 1.0 Angstrom) from the experimentally determined structures.     

Study on flame-retardant mechanism of polycarbonate containing sulfonate-silsesquioxane-fluoro retardants by TGA and FTIR

The flame retardancy of bisphenol A polycarbonate (PC) containing potassium diphenylsulfone sulfonate (KSS), poly(aminopropyl/phenylsilsesquioxane) (PAPSQ) and poly(vinylidenefluoride) (PVDF) was measured by limited oxygen index (LOI) and examined according to UL94. A high LOI and UL94 V-0 rating for 1.6 mm thickness samples were obtained by a combined use of equivalent KSS, PAPSQ and PVDF at 0.1-0.3 wt% loading, respectively. The improvement in flame retardancy of PC compositions arose from the synergistic interaction of three additives. Thermogravimetric analysis (TGA) indicated that the combination decreased the activation energy (E) of PC degradation and elevated the thermal degradation rate of PC to ensure the formation of an insulating carbon layer. FTIR analysis showed that the LOI char of PC containing the three additives took on a highly cross-linking aromatic ester and ether structure.     

Catalytic asymmetric synthesis of 3,2′-pyrrolinyl spirooxindoles via conjugate addition/Schmidt-type rearrangement of vinyl azides and (E)-alkenyloxindoles

A catalytic asymmetric conjugate addition/Schmidt-type rearrangement of vinyl azides and (E)-alkenyloxindoles was realized. It afforded a variety of optically active 3,2′-pyrrolinyl spirooxindoles with high yields (up to 98%), and excellent diastereo- and enantioselectivities (up to 98% ee, >19 : 1 dr), even at the gram-scale in the presence of a chiral N,N′-dioxide–nickel(ii) complex. In addition, a possible catalytic cycle and transition state model were proposed to rationalize the stereoselectivity.

Lewis acid catalyzed asymmetric synthesis of 3,2′-pyrrolinyl spirooxindole skeletons via conjugate addition/Schmidt-type rearrangement of vinyl azides and (E)-alkenyloxindoles.     

Infrared-Visible Image Fusion Based on Semantic Guidance and Visual Perception

Infrared-visible fusion has great potential in night-vision enhancement for intelligent vehicles. The fusion performance depends on fusion rules that balance target saliency and visual perception. However, most existing methods do not have explicit and effective rules, which leads to the poor contrast and saliency of the target. In this paper, we propose the SGVPGAN, an adversarial framework for high-quality infrared-visible image fusion, which consists of an infrared-visible image fusion network based on Adversarial Semantic Guidance (ASG) and Adversarial Visual Perception (AVP) modules. Specifically, the ASG module transfers the semantics of the target and background to the fusion process for target highlighting. The AVP module analyzes the visual features from the global structure and local details of the visible and fusion images and then guides the fusion network to adaptively generate a weight map of signal completion so that the resulting fusion images possess a natural and visible appearance. We construct a joint distribution function between the fusion images and the corresponding semantics and use the discriminator to improve the fusion performance in terms of natural appearance and target saliency. Experimental results demonstrate that our proposed ASG and AVP modules can effectively guide the image-fusion process by selectively preserving the details in visible images and the salient information of targets in infrared images. The SGVPGAN exhibits significant improvements over other fusion methods.     

Pseudo-mono-axial ligand fields that support high energy barriers in triangular dodecahedral Dy(iii) single-ion magnets

The synthesis of air-stable, high-performance single-molecule magnets (SMMs) is of great significance for their practical applications. Indeed, Ln complexes with high coordination numbers are satisfactorily air stable. However, such geometries easily produce spherical ligand fields that minimize magnetic anisotropy. Herein, we report the preparation of three air-stable eight-coordinate mononuclear Dy(iii) complexes with triangular dodecahedral geometries, namely, [Dy(BPA-TPA)Cl](BPh₄)₂ (1) and [Dy(BPA-TPA)(X)](BPh₄)₂·nCH₂Cl₂ (X = CH₃O⁻ and n = 1 for 2; L = PhO⁻ and n = 2 for 3), using a novel design concept in which the bulky heptadentate [2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine (BPA-TPA) ligand enwraps the Dy(iii) ion through weak coordinate bonds leaving only a small vacancy for a negatively charged (Cl⁻), methoxy (CH₃O⁻) or phenoxy (PhO⁻) moiety to occupy. Magnetic measurements reveal that the single-molecule magnet (SMM) property of complex 1 is actually poor, as there is almost no energy barrier. However, complexes 2 and 3 exhibit fascinating SMM behavior with high energy barriers (U_eff = 686 K for 2; 469 K for 3) and magnetic hysteresis temperatures up to 8 K, which is attributed to the pseudolinear ligand field generated by one strong, highly electrostatic Dy–O bond. Ab initio calculations were used to show the apparent difference in the magnetic dynamics of the three complexes, confirming that the pseudo-mono-axial ligand field has an important effect on high-performance SMMs compared with the local symmetry. This study not only presents the highest energy barrier for a triangular dodecahedral SMM but also highlights the enormous potential of the pseudolinear Dy–L ligand field for constructing promising SMMs.

Air-stable triangular dodecahedral Dy(iii) single-ion magnets with pseudo-mono-axial linear ligand fields exhibit high energy barrier exceeding 600 K, which represent the highest energy barrier for mononuclear SMMs with triangular dodecahedron.     

Two-photon dual-channel fluorogenic probe for in situ imaging the mitochondrial H2S/viscosity in the brain of drosophila Parkinson’s disease model

H₂S is an essential gas signal molecule in cells, and viscosity is a key internal environmental parameter. Recent studies have shown that H₂S acts as a cytoarchitecture agent and gas transmitter in many tissues, e.g., as a regulator of neuroendocrine in the brain for mediating vascular tone in blood vessels. Mitochondrial viscosity is an important parameter for judging whether mitochondrial function is normal. It has been reported that oxidative stress and mitochondrial dysfunction are connected with Parkinson’s disease (PD), and the protective role of H₂S in PD models has been extensively demonstrated. Herein, Mito-HS, a new two-photon fluorescent probe was demonstrated to detect cross-talk between the two channels of mitochondrial viscosity and H₂S content. Moreover, this probe could detect the relative amount of and changes in mitochondrial H₂S in situ due to the reduced mitochondrial targeting ability after reaction with H₂S. The results show that H₂S in mitochondria is inversely related to viscosity. The PD model has a lower H₂S in mitochondria and a higher mitochondrial viscosity than did the normal. This result is important for our deep understanding of PD and its causes.     

CuFeS2 as an anode material with an enhanced electrochemical performance for lithium-ion batteries fabricated from natural ore chalcopyrite

Journal of Solid State Electrochemistry - Considering serious pollution from the traditional chemical synthesis process, the resource-rich, clean electrode materials are greatly desired....