Tuning the solution structure of electrolyte for optimal solid-electrolyte-interphase formation in high-voltage lithium metal batteries

The continuous reduction of electrolytes by Li metal leads to a poor lifespan of lithium metal batteries(LMBs). Low Coulombic efficiency(CE) and safety concern due to dendrite growth are the challenging issues for LMB electrolyte design. Novel electrolytes such as highly concentrated electrolytes(HCEs) have been proposed for improving interphase stability. However, this strategy is currently limited for high cost due to the use of a large amount of lithium salts as well as their high viscosity, reduced ion mobility, and poor wettability. In this work, we propose a new type of electrolyte having a moderate concentration. The electrolyte has the advantage of HCEs as the anion is preferentially reduced to form inorganic solidelectrolyte-interphase(SEI). Such optimization has been confirmed through combined spectroscopic and electrochemical characterizations and supported with the first-principle molecular dynamics simulation. We have shown the intrinsic connections between solution structure and their electrochemical stability. The 2.0 M LiDFOB/PC electrolyte, as predicted by our characterizations and simulations, allows stable charge–discharge of LNMO|Li cells at 5C for more than 1500 cycles. The 2.0 M electrolyte generates a dense layer of SEI containing fluoro-oxoborates, Li_(3)BO_(3), LiF, Li_(2)CO_(3), and some organic species effectively passivating the lithium metal, as confirmed by electron microscopy, X-ray photoelectron spectroscopy,and solid-state nuclear magnetic resonance.

Realizing high-performance organic solar cells through precise control of HOMO driving force based on ternary alloy strategy

A good deal of studies have proven that effective exciton dissociation and fast hole transport can operate efficiently in non-fullerene organic photovoltaics(OPVs)despite nearly zero driving force.Even so,whether such a phenomenon is universal and how small the driving force can realize the best photovoltaic performance still require a thorough understanding.Herein,despite the zero driving force based on PM6:F8IC system,a maximum short-circuit current(J_(sc))of 23.0 mA/cm^(2) and high power conversion efficiency(PCE)of 12.2%can still be achieved.Due to the continuously adjustable energy levels can be realized in organic semiconducting alloys including F8IC:IT-4F and F8IC:Y6,the suitable third components can play the role of energy level regulator.Therefore,the HOMO energy level offset(DEHOMO(D A))from zero to 0.07 and 0.06 eV is accomplished in the optimized IT-4F and Y6 ternary devices.Consequently,both ternary devices achieved substantially increased PCE of 13.8%and Jsc of 24.4 and 25.2 mA/cm^(2),respectively.Besides,pseudo-planar heterojunction(PPHJ)devices based on alloyed acceptors through sequential spin-coating method further improve the photovoltaic performance.Our work puts forward the concept of energy level regulator and prove that the ternary alloy strategy has unique advantages and huge research potential in continuously adjusting the driving force.

Consideration of transmembrane water exchange in pharmacokinetic model significantly improves the accuracy of DCE-MRI in estimating cellular density:A pilot study in glioblastoma multiforme

Transmembrane water exchange(TWE)including transcytolemmal water exchange and transvascular water exchange is involved in many in vivo measurements and makes different contributions to the measuring results.In this study,we focus on the potential influence of TWE on the cell density parameter,intracellular water mole fraction pi,derived by dynamic contrast enhanced-magnetic resonance imaging(DCE-MRI)which has been reported as a technique to characterize perfusion and vascularization of tissues,but its accuracy in measuring cell density(or interstitial space)has been questioned.Sixteen patients with glioblastoma multiforme(GBM)were enrolled since GBM shows strong intratumor heterogeneity in both cell density and TWE.All the subjects were collected with DCE-MRI and apparent diffusion coefficient(ADC)map.The latter was considered as a valid surrogate of cell density.Extended Tofts(eTofts)model considering TWE as infinitely large variables and shutter-speed model(SSM)considering TWE as finite ones were used to fit DCE-MRI data.Monte Carlo(MC)and finite difference(FD)methods were used to simulate the influence of TWE on DCE-MRI-derived pi and ADC,respectively.The eTofts model shows a significant overestimation of pi in comparison with SSM in GBM(P<0.001),which is in accordance with MC simulations,and this overestimation shows dependence on the intra-to-extracellular water exchange rate constant(kio).Significant negative correlations between ADC and SSM-derived pi were found in both voxel-wise analyses(t-test P<0.001,average r=-0.74)and inter-subject comparisons(r=-0.63,P=0.009).But no consistent voxel-wise correlations(P>0.05)and a weaker inter-subject negative correlation(r=-0.56,P=0.02)were found between ADC and eTofts-derived pi.Further experimental and FD results revealed that kio made a limited contribution to ADC values in the physiological kio range in GBM,supporting ADC as a valid biomarker of cell density.These results suggest that the DCE-MRI pharmacokinetic shutter-speed model could significantly improve its accuracy in cell density estimation because of the considering transmembrane water exchange.

Mechanochemistry of an Interlocked Poly[2]catenane:From Single Molecule to Bulk Gel

Mechanically interlocked molecules(MIMs)are prototypical molecular machines with parts that enable controlled,large-amplitude movement with one component positioned relative to another.Incorporating MIMs into polymeric matrices is promising for the designing of functional materials with unprecedented properties.However,the central issue is the challenges involved with establishing the mechanistic linkage between the single-molecule and the bulk material.Herein,we explore the mechanochemical properties and energetic details of a linear poly[2]catenane with strong intercomponent hydrogen bonding(IHB)revealed by single-molecule force spectroscopy.Our results showed that the individual linear poly[2]catenane chain exhibited typical sawtooth pattern,corresponding to the reversible unlocking and relocking transitions under external force or upon stimulations to dissociate or re-form the strong IHB.Furthermore,when a poly[2]catenane-based polymer gel was prepared using a thiol-ene click reaction between thiol-ended poly[2]catenane and a low-molecule-weight cross-linker,the resultant gel showed excellent mechanical adaptability and dynamic properties,which correlated well with the molecular-level observations.The unique poly[2]catenane structure also contributed to the gel formation with an extraordinary IHB-mediated swelling behavior and shape memory property.Thus our present results demonstrate the functioning of bulk material in a linear tandem manner from the behavior of a single molecule,a finding which should be applicable to other systems with versatile properties and promising applications.

Low-dose real-time X-ray imaging with nontoxic double perovskite scintillators

X-rays are widely used in probing inside information nondestructively,enabling broad applications in the medical radiography and electronic industries.X-ray imaging based on emerging lead halide perovskite scintillators has received extensive attention recently.However,the strong self-absorption,relatively low light yield and lead toxicity of these perovskites restrict their practical applications.Here,we report a series of nontoxic double-perovskite scintillators of Cs_(2)Ag_(0.6)Na_(0.4)In_(1-y)Bi_(y)Cl_(6).By controlling the content of the heavy atom Bi^(3+),the X-ray absorption coefficient,radiative emission efficiency,light yield and light decay were manipulated to maximise the scintillator performance.A light yield of up to 39,000±7000 photons/MeV for Cs_(2)Ag_(0.6)Na_(0.4)In_(0.85)Bi_(0.15)Cl_(6) was obtained,which is much higher than that for the previously reported lead halide perovskite colloidal CsPbBr_(3)(21,000 photons/MeV).The large Stokes shift between the radioluminescence(RL)and absorption spectra benefiting from self-trapped excitons(STEs)led to a negligible selfabsorption effect.Given the high light output and fast light decay of this scintillator,static X-ray imaging was attained under an extremely low dose of ∼1μGy_(air),and dynamic X-ray imaging of finger bending without a ghosting effect was demonstrated under a low-dose rate of 47.2μGy_(air) s^(−1).After thermal treatment at 85℃ for 50 h followed by X-ray irradiation for 50 h in ambient air,the scintillator performance in terms of the RL intensity and X-ray image quality remained almost unchanged.Our results shed light on exploring highly competitive scintillators beyond the scope of lead halide perovskites,not only for avoiding toxicity but also for better performance.

Fluorescent Supramolecular Polymersomes Based on Pillararene/Paraquat Molecular Recognition for pH-controlled Drug Release

Researchers have put significant efforts on developing versatile fluorescent polymeric systems due to their promising biological/biomedical labelling, tracking, monitoring, imaging, and diagnostic applications. However, complicated organic/polymeric synthesis or post-modification of these functionalized platforms is still a big obstacle for their further application and thereby provides clear motivation for exploring alternative strategies for the design and fabrication of easily available fluorescent systems. The marriage of supramolecular polymers and fluorescent imaging can provide a facile and dynamic manner instead of tedious and time-consuming synthesis due to the dynamic and reversible nature of noncovalent interactions. Herein, based on water-soluble pillararene/paraquat molecular recognition, we successfully prepare two amphiphilic polypseudorotaxanes which can self-assemble into supramolecular polymersomes in water. These polymersomes can be reversibly destroyed and reformed by tuning the solution p H. Attributed to the aggregation-induced emission of tetraphenylethylene groups,intense fluorescence can be introduced into the obtained supramolecular polymersomes. Furthermore, p H-triggered release of an encapsulated water-insoluble drug(doxorubicin) from the self-assembled fluorescent supramolecular polymersomes is also investigated.

19.34 cm2 large-area quaternary organic photovoltaic module with 12.36% certified efficiency

In this study, a quaternary blending strategy was applied in the fabrication of organic photovoltaic devices and large-area modules. As a result, the ultimate quaternary organic solar cells(OSCs) deliver 16.71% efficiency for small-area devices and 13.25% for large-area(19.34 cm2) modules(certified as 12.36%), which is one of the highest efficiencies for organic solar modules to date. Our results have proved the synergistic effects of multiple components in OSCs, providing an effective strategy for achieving high-performance organic photovoltaic devices and modules.

Cyclic Ether Contaminant Removal from Water Using Nonporous Adaptive Pillararene Crystals via Host-Guest Complexation at the Solid-Solution Interface

Te removal of soluble cyclic ether contaminants,such as dioxane and THF,produced in industrial chemical processes from water is of great importance for environmental protection and human health.Here we report that nonporous adaptive crystals of perethylated pillar[5]arene(EtP5)and pillar[6]arene(EtP6)work as adsorbents for cyclic ether contaminant removal via hostguest complexation at the solid-solution interface.Nonporous EtP6 crystals have the ability to adsorb dioxane from water with the formation of 1:2 host-guest complex crystals,while EtP5 crystals cannot.However,both guest-free EtP5 and EtP6 crystals remove THF from water with EtP5 having a better capacity.Tis is because EtP5 forms a 1:2 host-guest complex with THF via host-guest complexation at the solid-solution interface while EtP6 forms a 1:1 host-guest complex with THF.EtP6 also shows the ability to selectively remove dioxane from water even in the presence of THF.Moreover,the reversible transitions between nonporous guestfree EtP5 and EtP6 structures and guest-loaded structures make them highly recyclable.

Inhibition of furin by bone targeting superparamagnetic iron oxide nanoparticles alleviated breast cancer bone metastasis

Breast cancer bone metastasis poses significant challenge for therapeutic strategies.Inside the metastatic environment,osteoclasts and tumor cells interact synergistically to promote cancer progression.In this study,the proprotein convertase furin is targeted due to its critical roles in both tumor cell invasion and osteoclast function.Importantly,the furin inhibitor is specifically delivered by bone targeting superparamagnetic iron oxide(SPIO)nanoparticles.Our in vitro and in vivo data demonstrate that this system can effectively inhibit both osteoclastic bone resorption and breast cancer invastion,leading to alleviated osteolysis.Therefore,the bone targeting&furin inhibition nanoparticle system is a promising therapeutic and diagnostic strategy for breast cancer bone metastasis.

Reducing energy barriers of chemical reactions with a nanomicrocell catalyst consisting of integrated active sites in conductive matrices

Reducing energy barriers of chemical reactions is the never-ending endeavor of chemists.Inspired by the high reactivity of primary cells,we develop a nanosized fuel cell catalyst(denoted as nanomicrocell catalyst),consisting of integrated electrode pairs,conductive matrices and electrolytes,to improve the chemical reactivity.Specifically,the anodes are Pd species which is combining with the electron-rich N atoms in B-and-N co-doped carbon dots;the cathodes are electron-deficient B atoms;and the conductive matrices are B-and-N co-doped carbon dots which are connecting with the electrode pairs.Similar to the reactivity of primary cells,the catalytic properties of the nanomicrocell catalyst in hydrogenation of benzaldehyde are depending on the properties of electrode pairs,conductive matrices and electrolytes.The unique catalytic properties are attributed to the different substrate adsorption capability and catalytic properties of paired electrodes,and the easy migration of electrons and charge carriers,which could improve the synergetic effect between paired active sites.Therefore,this work may open up a new window for designed synthesis of advanced catalysts which could highly lower the energy barriers of chemical reactions.

Supramolecular control over thermo-responsive systems with lower critical solution temperature behavior

Lower critical solution temperature(LCST)is the critical temperature below which the solution is miscible for all compositions and above which the solution becomes a suspension.The study of LCST properties has become a central research topic due to its profound impact on the applications of stimuli-responsive materials.Inspired by the marriage between materials science and supramolecular chemistry,the introduction of supramolecular pairs and interactions into polymeric LCST systems is increasingly practiced.Especially,supramolecular interactions provide precise control over LCST behavior in both water and organic solvents.Furthermore,supramolecular interactions not only control or adjust LCST behavior(supramolecular interaction controlled LCST),but also induce LCST phase behavior in species lack of thermo-sensitive properties(supramolecular interaction induced LCST).In this review,we summarize the applications of supramolecular interactions in LCST systems.By examining the relationship between supramolecular interactions and LCST changes,we further discuss the differences between supramolecular interaction controlled LCST and supramolecular interaction induced LCST.We hope this review will give our readers a snapshot on how the supramolecular interactions influence the LCST behavior in various systems,and benefit them with different applications.