Mononuclear and Dinuclear Copper Complexes of Tridentate Redox-active Ligands with Tunable H-bonding Donors: Structure,Spectroscopy and H+/e− Reactivity

In this research article, we describe the synthesis and characterization of mononuclear and dinuclear Cu complexes bound by a family of tridentate redox-active ligands with tunable H-bonding donors. The mononuclear Cu-anion complexes were oxidized to the corresponding “high-valent” intermediates by oxidation of the redox-active ligand. These species were capable of oxidizing phenols with weak O−H bonds via H-atom abstraction. Thermodynamic analysis of the H-atom abstractions, which included reduction potential measurements, pK_a determination and kinetic studies, revealed that modification of the anion coordinated to the Cu and changes in the H-bonding donor did not lead to major differences in the reactivity of the “high-valent” CuY complexes (Y: hydroxide, phenolate and acetate), which indicated that the tridentate ligand scaffold acts as the H⁺ and e⁻ acceptor.     

Atomic-scale simulations for lithium dendrite growth driven by strain gradient

Dendrite formation is a major obstacle, e.g., capacity loss and short circuit, to the next-generation high-energy-density lithium (Li)-metal batteries. The development of successful Li dendrite mitigation strategies is impeded by an insufficient understanding in Li dendrite growth mechanisms. The Li-plating-induced internal stress in Li-metal and its effects on dendrite growth have been widely studied, but the underlying microcosmic mechanism is elusive. In the present study, the role of the plating-induced stress in dendrite formation is analyzed through first-principles calculations and ab initio molecular dynamic (AIMD) simulations. It is shown that the deposited Li forms a stable atomic nanofilm structure on the copper (Cu) substrate, and the adsorption energy of Li atoms increases from the Li-Cu interface to the deposited Li surface, leading to more aggregated Li atoms at the interface. Compared with the pristine Li-metal, the deposited Li in the early stage becomes compacted and suffers the in-plane compressive stress. Interestingly, there is a giant strain gradient distribution from the Li-Cu interface to the deposited Li surface, making the deposited atoms adjacent to the Cu surface tend to press upwards with perturbation and causing the dendrite growth. This provides an insight into the atomicscale origin of Li dendrite growth, and may be useful for suppressing the Li dendrite in Li-metal-based rechargeable batteries.     

The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes

By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A₂L₃ complexes (A represents anion, here orthophosphate PO₄^3?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes.     

The High Energy X-ray telescope (HE) onboard the Insight-HXMT astronomy satellite

The Insight-Hard X-ray Modulation Telescope(Insight-HXMT) is a broadband X-ray and γ-ray(1-3000 ke V) astronomy satellite. One of its three main telescopes is the High Energy X-ray telescope(HE). The main detector plane of HE comprises 18 Na I(Tl)/Cs I(Na) phoswich detectors, where Na I(Tl) is used as the primary detector to measure ~ 20-250 ke V photons incident from the field of view(FOV) defined by collimators, and Cs I(Na) is used as the active shielding detector to Na I(Tl) by pulse shape discrimination. Additionally, Cs I(Na) is used as an omnidirectional γ-ray monitor. The HE collimators have a diverse FOV,i.e. 1.1°×5.7°(15 units), 5.7°×5.7°(2 units), and blocked(1 unit). Therefore, the combined FOV of HE is approximately5.7°×5.7°. Each HE detector has a diameter of 190 mm resulting in a total geometrical area of approximately 5100 cm2, and the energy resolution is ~15% at 60 ke V. For each recorded X-ray event by HE, the timing accuracy is less than 10 μs and the deadtime is less than 10 μs. HE is used for observing spectra and temporal variability of X-ray sources in the 20-250 ke V band either by pointing observations for known sources or scanning observations to unveil new sources. Additionally, HE is used for monitoring the γ-ray burst in 0.2-3 Me V band. This paper not only presents the design and performance of HE instruments but also reports results of the on-ground calibration experiments.     

Direct Transformation of Arenols Based on C—O Activation

In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation.     

Polypyrrole Shell@3D‐Ni Metal Core Structured Electrodes for High‐Performance Supercapacitors

Three‐dimensional (3D) nanometal films serving as current collectors have attracted much interest recently owing to their promising application in high‐performance supercapacitors. In the process of the electrochemical reaction, the 3D structure can provide a short diffusion path for fast ion transport, and the highly conductive nanometal may serve as a backbone for facile electron transfer. In this work, a novel polypyrrole (PPy) shell@3D‐Ni‐core composite is developed to enhance the electrochemical performance of conventional PPy. With the introduction of a Ni metal core, the as‐prepared material exhibits a high specific capacitance (726 F g^?1 at a charge/discharge rate of 1 A g^?1), good rate capability (a decay of 33 % in C_sp with charge/discharge rates increasing from 1 to 20 A g^?1), and high cycle stability (only a small decrease of 4.2 % in C_sp after 1000 cycles at a scan rate of 100 mV s^?1). Furthermore, an aqueous symmetric supercapacitor device is fabricated by using the as‐prepared composite as electrodes; the device demonstrates a high energy density (≈21.2 Wh kg^?1) and superior long‐term cycle ability (only 4.4 % and 18.6 % loss in C_sp after 2000 and 5000 cycles, respectively).     

Photons can hide where they have been

Recently,the nested Mach–Zehnder interferometer[Phys.Rev.Lett.111,240402(2013)]was modified by adding Dove prisms in a paper[Quantum Stud.:Math.Found.2,255(2015)],and an interesting result is that,after the Dove prisms were inserted,a signal at the first mirror of the nested interferometer was obtained.But,according to the former original paper,the photons have never been present near that mirror.In this work,we interpret this result naturally by resorting to the three-path interference method.Moreover,we find that even though the photons have been somewhere,they can hide the trace of being there.     

A Ru(II)-Based Nanoassembly Exhibiting Theranostic PACT Activity in NIR Region

Photoactivated chemotherapy (PACT) has appealing merits over traditional chemotherapy as well as photodynamic therapy (PDT) by virtue of its spatial and temporal control on drug activity and oxygen-independent mechanisms of action. However, the short photoactivation wavelengths, e.g., visible light–activated Ru(II)-based PACT agents, limit the clinical application severely. In this work, a facile construction of supramolecular nanoparticles from a poly(ethylene glycol) (PEG)-modified [Ru(dip)₂(py-SO₃)]⁺ (abbreviated as Ru-PEG, dip = 4,7-diphenyl-1,10-phenanthroline, py-SO₃ = pyridine-2-sulfonate) and 1,3-phenylenebis(pyren-1-ylmethanone) (BP) is shown. While Ru-PEG may undergo photoinduced ligand dissociation and release anticancer species of [Ru(dip)₂(H₂O)₂]²⁺, BP has extremely large two-photon absorption cross sections (δ₂) in the NIR region and intense fluorescence over the wavelengths where Ru-PEG has strong absorption. Thus, two-photon excitation of BP followed by an efficient Förster resonance energy transfer (FRET) from BP to Ru-PEG may lead to a potent inactivation against cisplatin-resistant cancer cells and 3D multicellular tumor spheroids (MCTSs). The residue fluorescence of BP also allows the cellular uptake of the particles to be visualized. This work provides a universal and convenient strategy to realize theranostic PACT in the ideal phototherapeutic window of 650–900 nm.     

Dynamic analysis of the double crank mechanism with a 3D translational clearance joint employing a variable stiffness contact force model

Nonlinear Dynamics - Oblique collisions are more likely to happen in the realistic translational joint with clearance, compared to the full front impacts. It can be a quite demanding task to...