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We present two novel porphyrin (Porp)-based conjugated microporous polymers (CMPs; Porp-TPE-CMP and Porp-Py-CMP), formed via an FeCl3-catalyzed cross-coupling reaction between pyrrole and aromatic aldehyde. The resultant CMPs exhibited high CO2 selectivity compared with N2 and CH4, and good capacity for organic vapors.

A rational synthetic strategy to construct two supramolecular isomers based on polyoxovanadate organic polyhedra with tetrahedral symmetries is presented. VMOP-α, a low-temperature product, has an extremely large cell volume (470 842 A3 ), which is one of the top three for well-defined MOPs. The corner-to-corner packing of tetrahedra leads to a quite low density of 0.174 g cm-3 with 1D channels (ca. 5.4 nm). The effective pore volume is up to 93.6 % of cell volume, nearly the largest found in MOPs. For the high-temperature outcome, VMOP-β, the cell volume is only 15 513 A3 . The packing mode of tetrahedra is corner-to-face, giving rise to a high-density architecture (1.324 g cm-3 ; channel 0.8 nm). Supramolecular structural transformation between VMOP-α and VMOP-β can be reversibly achieved by temperature-induced solvent-mediated transformation. These findings give a good opportunity for understanding 3D supramolecular aggregation and crystal growth based on large molecular tectonics.

As the main component of syngas, reducing CO2 to CO with high selectivity through photocatalysis could provide a sustainable way to alleviate energy shortage issues. Developing a photocatalytic system with low cost and high performance that is environmentally friendly is the ultimate goal towards CO2 photoreduction. Herein, an efficient and economic three-component heterojunction photocatalyst is designed and fabricated for converting CO2 to CO in the absence of organic sacrificial agents. The heterojunction is made of Cu2-x S nanotubes coated with a carbon layer (C-Cu2-x S) and g-C3 N4 . By using the classical MOF material HKUST-1 as a precursor, hollow tubular-like metal sulfides (C-Cu2-x S) with carbon coating were synthesized and further loaded on g-C3 N4 , forming a three-component heterojunction C-Cu2-x S@g-C3 N4 . The carbon coat in C-Cu2-x S@g-C3 N4 acts as an electron reservoir, which facilitates electron-hole pair separation. The optimized C-Cu2-x S@g-C3 N4 acted as a photocatalyst in CO2 reduction with a high reactivity of 1062.6 μmol g-1 and selectivity of 97 %. Compared with bare g-C3 N4 (158.4 μmol g-1 ) and C-Cu2-x S, the reactivity is nearly 7 and 23-fold enhanced and this CO generation rate is higher than most of the reported Cu2 S or g-C3 N4 composites under similar conditions. The prominent activity may result from enhanced light adsorption and effective charge separation. This work might open up an alternative method for the design and fabrication of high-performance and low-cost photocatalysts for efficiently and durably converting CO2 to CO with high selectivity.

Nanoscale regular polyhedra with icosahedral symmetry exist naturally as exemplified by virus capsids and fullerenes. Nevertheless, their generation by supramolecular chemistry through the linking of 5-fold symmetry vertices remains unmet because of the absence of 5-fold symmetry building blocks with the requisite geometric features. This situation contrasts with that of tetrahedral and octahedral symmetry metal–organic polyhedra (MOPs), for which appropriate triangular and square molecular building blocks (MBBs) that can serve as vertices or faces are readily available. Herein, we report isolation of a pentagonal [WV5O11(SO4)6]8– cluster and reveal its utility to afford the first four examples of nanoscale Goldberg MOPs, based upon 5-fold MBBs. Two 32-faced Gv(1,1) MOPs and two 42-faced Gv(2,0) MOPs were formed using linear or triangular organic ligands, respectively. The largest Goldberg MOP-4, exhibits a diameter of 4.3 nm, can trap fullerene C60 molecules in its interstitial cavities.

Photocatalytic carbon dioxide reduction (CO

The solid-solid conversion of Li

Mechanochromic luminescent (MCL) materials are promising in pressure sensors, security papers, photoelectric devices and optical data recording. Although some kinds of MCL-active iridium(III) complexes with various soft substituent functional ligands (e.g., dendritic carbazole, flexible chains, and Schiff base ligands) were reported, the MCL mechanism is still not clear and mainly ascribes to the physical phase transformations from crystalline state to amorphous state in response to force stimulus at present stage, and deserves further study in order to obtain more intelligent MCL materials. Herein, two new iridium(III) complex isomers are tactfully constructed and show distinctly opposite MCL properties in spite of the same physical phase transformations happening on them. The absolutely out of the ordinary MCL mechanism has been presented on account of molecular level for the first time via the comparative study of photophysical properties based on isomers

In the present work, T-Si, a silicon-based counterpart of T-carbon, has been designed with the aid of density functional theory (DFT) calculations. Its stability has been fully confirmed from energetic, mechanical, lattice dynamic, and thermodynamic aspects. Due to the space extrusion, the delocalized electrons on the ${\mathrm{Si}}_{4}$ tetrahedrons are squeezed onto the inter-tetrahedron $\mathrm{Si}\ensuremath{-}\mathrm{Si}$ bonds, which therefore leads T-Si to be metallic. Furthermore, the electronic conductivity of this new material has also been predicted and discussed in this work. This new silicon allotrope with a low density of $0.869\mathrm{g}/{\mathrm{cm}}^{3}$ can even floats on water. This designed ultralight form of Si paves the way for the applications in the fields of spacecraft and automobiles in the future.

Quantum mechanical and molecular dynamics simulations have been carried out on a series of anthracene-o-carborane derivatives (ANT-H, ANT-Ph, ANT-Me and ANT-TMS) with rare red-light emission in the solid state. The simulation of the heating process of the crystals and further comparison of the molecular structures and excited-state properties before and after heating help us to disclose the thermochromic behavior, that is, the red-shift emission is caused by elongation of the C1-C2 bond in the carborane moiety after heating. Thus, we believe that the molecular structure in the crystal is severely affected by heating. Transformation of the molecular conformation appears in the ANT-H crystal with increasing temperature. More specifically, the anthracene moiety moves from nearly parallel to the C1-C2 bond to nearly perpendicular, causing the short-wavelength emission to disappear after heating. As for the aggregation-induced emission phenomenon, the structures and photophysical properties were investigated comparatively in both the isolated and crystal states; the results suggested that the energy dissipation in crystal surroundings was greatly reduced through hindering structure relaxation from the excited to the ground state. We expect that discussion of the thermochromic behavior will provide a new analysis perspective for the molecular design of o-carborane derivatives.

Near-infrared (NIR) emitters are important probes for biomedical applications. Nanoparticles (NPs) incorporating mono- and tetranuclear iridium(III) complexes attached to a porphyrin core have been synthesized. They possess deep-red absorbance, long-wavelength excitation (635 nm) and NIR emission (720 nm). TD-DFT calculations demonstrate that the iridium–porphyrin conjugates herein combine the respective advantages of small organic molecules and transition metal complexes as photosensitizers (PSs): (i) the conjugates retain the long-wavelength excitation and NIR emission of porphyrin itself; (ii) the conjugates possess highly effective intersystem crossing (ISC) to obtain a considerably more long-lived triplet photoexcited state. These photoexcited states do not have the usual radiative behavior of phosphorescent Ir(III) complexes, and they play a very important role in promoting the singlet oxygen (1O2) and heat generation required for photodynamic therapy (PDT) and photothermal therapy (PTT). The tetranuclear 4-Ir NPs exhibit high 1O2 generation ability, outstanding photothermal conversion efficiency (49.5%), good biocompatibility, low half-maximal inhibitory concentration (IC50) (0.057 μM), excellent photothermal imaging and synergistic PDT and PTT under 635 nm laser irradiation. To our knowledge this is the first example of iridium–porphyrin conjugates as PSs for photothermal imaging-guided synergistic PDT and PTT treatment in vivo.

The rational design and construction of multifunctional electrocatalysts with high activity, low cost, and outstanding stability are highly desirable for the development of renewable energy but are still a big challenge. Bimetallic catalysts are a kind of promising candidates, like the hybrids of Co and VN nanoparticles (Co/VN). However, the inevitable aggregation during the preparation and electrochemical process lowers their reactivity and durability. Herein, small Co/VN nanoparticles (4-8 nm) embedded in porous graphitic carbon layers (Co/VN NPs@C) were obtained through the pyrolysis of metal-organic frameworks (MOFs). The synergistic effect of in situ generated Co and VN NPs together with fast electron transfer from graphitic carbon layers renders this catalyst to possess excellent trifunctional performance. More attractively, Co/VN NPs@C as both the anode and the cathode shows a low voltage of 1.58 V when the current density is up to 10 mA cm-2, exceeding most electrocatalysts based on non-noble metals. The rechargeable Zn-air batteries constructed by Co/VN NPs@C deliver high round-trip efficiency together with a peak power density of 130 mW cm-2, a specific capacity of 757 mAh g-1, and desirable stability, outperforming the traditional Zn-air batteries based on the Pt/C and RuO2 pair. This work opens a promising avenue toward constructing highly effective multifunctional electrocatalysts by designing small-sized nanoparticles with various active sites derived from MOFs.

Noncovalent interactions (NCIs) play crucial roles in supramolecular chemistries; however, they are difficult to measure and compute. Currently, reliable computational methods are being pursued to meet this challenge, but the accuracy of calculations based on low levels of theory is not satisfactory and calculations based on high levels of theory are often too costly. Accordingly, to reduce the cost and increase the accuracy of low-level theoretical calculations to describe NCIs, an efficient approach is proposed to correct NCI calculations based on the benchmark databases S22, S66, and X40. In this approach, machine learning methods, general regression neural network (GRNN), and support vector machine (SVM) are used to perform the correction for DFT methods on the basis of DFT calculations. Various DFT methods, including M06-2X, B3LYP, B3LYP-D3, PBE, PBE-D3, and ωB97XD, with two small basis sets (i.e., 6-31G* and 6-31+G*) were investigated. Moreover, the conductor-like polarizable continuum model (C-PCM) with two types of solvents (water and pentylamine) was considered in some DFT calculations. With the correction, the root mean square errors (RMSEs) of all DFT calculations were improved by at least 70%. Relative to CCSD(T)/CBS benchmark values (used as experimental NCI values because of its high accuracy), the mean absolute error (MAE) of the best GRNN result was 0.33 kcal/mol, which is comparable to high-level ab initio methods or DFT methods with fairly large basis sets. Notably, this level of accuracy is achieved within a fraction of the time required by other methods. Additionally, SVM is applied on datasets in the gas phase, which gave similar correction accuracy as GRNN. For all of the correction models based on various DFT approaches, the validation parameters according to OECD principles (i.e., the correlation coefficient R, the predictive squared correlation coefficient q2 and q cv 2 from cross-validation) were greater than 0.92, which suggests that the correction model has good stability, robustness, and predictive power. The correction can be added following DFT calculations. With the obtained molecular descriptors, the NCIs produced by DFT methods can be improved to achieve high-level accuracy. Moreover, only one parameter is introduced into the GRNN correction model, which makes it easily applicable. Overall, this work demonstrates that the machine learning correction model may be an alternative to the traditional means of correcting for NCIs.

Recent experimental work reported that visible-light photoredox catalysis coupled with primary sulfonamides and electron-deficient alkenes could efficiently construct C-C bonds at the α-position of primary amine derivatives under mild conditions. Here, a systematic study was conducted to explore the non-negligible excited-state single-electron-transfer (SET) processes and the catalytic cycle. Hydrogen atom transfer (HAT) catalysis containing different site-selective functionalization, involved as a critical process during the reaction, was computationally characterized. The superiorities of iridium-based photoredox catalysts in terms of photoabsorption properties, phosphorescence rates, and electron-transfer rates for SET processes were focused on. In addition, the function of quinuclidine in the entire photocatalytic reaction was also probed. These intrinsic properties and detailed insights into the mechanism are supposed to be helpful to the understanding of the C-C bond functionalization reaction and the future application of the iridium-based photoredox catalyst.

The mercury ions in waste water have threatened public health and environmental protection. In this sense, novel materials with outstanding performances for removal of Hg

Stimuli-responsive supramolecular gels (SRSGs) are an important class of smart materials. It is of practical importance to develop an SRSG which can both detect and remove toxic metal ions. We have designed and synthesized an aggregation induced emission (AIE)-active oligourethane (OU) gelator which self-assembles into a supramolecular gel (OUG), through hydrogen-bonding, π–π stacking and van der Waals interactions. By taking advantage of the weak and dynamic nature of these non-covalent bonds, OUG shows stimuli-response to multiple factors. Importantly, OUG has the capacity for real-time detection and high selectivity for Fe3+, HSO4− and F−. The lowest detection limits are in the range of 5.89 × 10−9 to 8.17 × 10−8 M, indicating high sensitivity. More importantly, OUG is shown to adsorb and separate Fe3+ from aqueous solution, with an absorbing rate of up 97.5%. A simple writing board was fabricated, which could be written repeatedly and reused. OUG acts as a reversible and recyclable “on–off–on” fluorescence sensor via competitive cation–π and cation–anion interactions. OUG has great potential as an environmentally sustainable probe for ions.

Charge dissociation in the active layer is one of the key factors for the power conversion efficiency of bulk heterojunction organic solar cells (OSCs). Numerous charge-transfer mechanisms have been proposed based on one of few microscopic models. Here, we would explore possible charge-transfer mechanisms for 155 models of donor/acceptor (D/A) interfaces, built via materials DCV-1 and C60 as the donor and acceptor, respectively. After the calculations of the key parameters related to the charge dissociation and a statistical analysis for the correlation between these parameters were carried out, we can obtain a more robust description of the charge dissociation in practical OSCs. The complicated relationship among the key parameters not only illustrates the important correlation between the D/A stacking pattern and charge-transfer mechanism but also suggests that different charge-transfer mechanisms take place more likely depending on the specific arrangements of the donor and acceptor.

Inspired by the structures of virus capsids, chemists have long pursued the synthesis of their artificial molecular counterparts through self–assembly. Building nanoscale hierarchical structures to simulate double-shell virus capsids is believed to be a daunting challenge in supramolecular chemistry. Here, we report a double-shell cage wherein two independent metal–organic polyhedra featuring Platonic and Archimedean solids are nested together. The inner (3.2 nm) and outer (3.3 nm) shells do not follow the traditional “small vs. large” pattern, but are basically of the same size. Furthermore, the assembly of the inner and outer shells is based on supramolecular recognition, a behavior analogous to the assembly principle found in double-shell viruses. These two unique nested characteristics provide a new model for Matryoshka–type assemblies. The inner cage can be isolated individually and proves to be a potential molecular receptor to selectively trap guest molecules., Supramolecular constructs that mimic complex biological assemblies are synthetically challenging. Here, the authors present a double-shell cage wherein two independent metal-organic polyhedra are nested together in a manner analogous to that found in double-shell virus capsids.

We present a theoretical design of the singlet-fission (SF) interconversion between two hydrogen tautomers to attract attention to electronic devices such as switches in the SF field. We develop a tuned π-electron conjugation strategy based on single-hydrogen migration to introduce diradical character and yield low-lying

We prepare a novel COF for CO2 photoreduction with 99.9% CO selectivity in aqueous solution without a cocatalyst. DFT shows that the preferential adsorption of H+ on the COF results in increased CO2 adsorption energy providing an anchoring site of CO2, and with the cooperation of an ethylene group, CO2 reduction is triggered.

The development of inexpensive and efficient bifunctional electrocatalysts is significant for widespread practical applications of overall water splitting technology. Herein, a one-pot solvothermal method is used to prepare hollow porous MnFe

Multifunctional spherical aggregated gold nanoclusters encapsulated by polyacrylic acid/mesoporous silica shell nanoparticles (A-AuNC@PAA/mSiO2 NPs) with aggregation enhanced fluorescence (AEF) properties were fabricated by a facile and reproducible synthetic strategy. The as-prepared NPs were employed as novel theranostic agents for synergistic fluorescence/X-ray computed tomography imaging and chemo-therapy of liver cancer in vitro and in vivo.

In the present work, a new 3D metal-organic framework (MOF) has been synthesized and characterized. The MOF exhibits good chemical stability in aqueous solutions with the pH scale ranging from 3 to 11. Interestingly, the MOF shows high catalytic activities for the degradation of azo dyes (MO, CR and CBR) under visible light without H2O2. The Ea values of the MOF for MO, CR and CBR degradation are obtained to be 23.49, 52.68 and 15.19 kJ mol-1, respectively. In addition, the MOF can be reused in the catalytic process without the catalytic activity decreasing obviously.

A system containing polyoxometalate ([Co-POM]

We synthesized a novel MOF with an sqc1575 topology as an ideal host matrix that exhibits luminescence energy transfer with polycyclic aromatic hydrocarbons (PAHs). What's more, the PAHs@MOF composites display an interesting quenching behavior in the presence of the electron donor triethanolamine (TEOA). We report for the first time that the well-defined porosity of a luminescent MOF enables it to serve as a host matrix for encapsulating chromophoric PAH molecules to modulate luminescence properties, and further exploit its reductive quenching properties by using a photocatalytic sacrificial electron donor.

Halide perovskites have been employed as photocatalysts for CO

A nanosized Ta/W mixed addendum polyoxometalate (Cs12K3H7[MnTa18Si6W54O231]·61H2O) based on the unprecedented {MnTa18} cluster was fabricated successfully under hydrothermal conditions. An excellent electrochemical performance of this compound was found in lithium-ion batteries (LIBs) as an anode material. The discharge capacity was 829.9 mA h g-1 at a current density of 100 mA g-1 in the first cycle and stable at 428.4 mA h g-1 after 100 cycles, which suggests the potential application of this new compound in LIBs.

The carbon nanostructure with heteroatom doping having well-designed porosity and a large pore volume plays a vital role in high-performance supercapacitors. Herein, we synthesize hierarchical nitrogen and sulfur-codoped micromesoporous carbon nanospheres (N,S-HPCNSs) with an ultralarge pore volume of 3.684 cm

Two new cucurbit[6]uril (CB[6])-based metal-organic rotaxane networks (MORNs) were successfully obtained by tuning the coordination sphere of metal copper clusters. Compounds 1 and 2 exhibited relatively high proton conductivity at 85 °C and 97% relative humidity (RH), providing great promise for fuel cell electrolyte materials.

Porous covalent organic frameworks (COFs), as an emerging material, have the characteristics of high stability, large series of components, easy synthesis, modification, and adjustable amplitude. They have the potential to become good catalysts. Bromine, as a halogen, has attracted intensive interest for the modification of photocatalysts for photocatalytic reactions. It is feasible to enhance the activity and selectivity of the material by facile functionalization of the reticular parent structure's electron-withdrawing groups. In addition, the conjugation effect of bromine, further delocalizing the electrons of the COF, is beneficial to the progress of many photocatalytic reactions. Reports on the modification of COFs by bromine functional groups to improve the catalytic performance have not been found so far. Here, TAPP [5,10,15,20-tetrakis(4-aminophenyl)porphyrin] and 2,5-dibromo-1,4-benzenedialdehyde instead of terephthalaldehyde were chosen to synthesize a porphyrin-based COF (TAPBB-COF) by the solvothermal method. As expected, the valence band (VB) of TAPBB-COF is thus adjusted to a more suitable position. Additionally, the CO production when using TAPBB-COF under full-wavelength light for 12 h was 295.2 μmol g

Highly efficient light-emitting electrochemical cells (LECs) have attracted tremendous interest because of their simple structures and low-cost fabrication processing, showing great potential for full-color displays and solid-state lighting. In this work, we rationally designed and synthesized two red-emitting cationic Ir(III) complexes, [Ir(tBuPBI)

Two Ni/Co-substituted sandwich-type germanomolybdates, {[M

Covalent organic polymers (COPs) received much attention due to their application in diverse fields, especially in sensing. A highly efficient fluorescence sensor in selective detection of Fe3+ions is necessary to develop. In this work, we successfully synthesized a new covalent organic polymers named COP-TP, with the excellent performance in selective detection of Fe3+ions, the quenching mechanism mainly due to the energy transfer process. The above results show COP-TP has the possibility to be a new candidate in selective detection as Fe3+ions sensor.

Electrochemical reduction of CO2 (CO2RR) represents a fascinating route for converting atmospheric CO2 to valuable chemicals, and a variety of intermediates are involved in the different CO2RR pathways. However, it has been hampered by the lack of highly effective electrocatalysts so far. Here, the performance of single 3d non-precious transition metals supported on g-C(CN)3 monolayers [TM-C(CN)3, TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, respectively] as CO2RR electrocatalysts was systematically investigated by using density functional theory (DFT) calculations. The data indicate that all these TM atoms can strongly interact with the g-C(CN)3 substrate, and the TM active sites possess high CO2RR activity and specific selectivity through *OCHO intermediate. Particularly, Sc-, Co–, and Ni-C(CN)3 monolayers are identified as effective CO2RR electrocatalysts due to the low limiting potentials (- 0.28, − 0.42, and − 0.46 V, respectively), whose excellent performances are mainly attributed to the specific TMN3 active sites. Therefore, this work sheds light on g-C(CN)3 monolayer as an excellent supporting material , and will motivate more experimental and theoretical researches to further explore other potential two-dimensional porous carbon-based materials with specific TMN3 active sites for CO2RR.

In this work, three complexes C59Co, C59Rh and C59Ir are devised by the transition metals (Co, Rh and Ir) doped into fullerenes to study the structure–property relationships of the heterofullerenes...

The design and construction of metal–organic polyhedra has received much attention by chemists due to the intriguing diversity of architectures and topologies that can be achieved. There are several crucial factors which should be considered for the construction of metal–organic polyhedra, such as the starting materials, reaction time and temperature, solvent and suitable organic ligands. Recently, polyoxometalates (POMs), serving as secondary building units to construct POM-based metal–organic polyhedra, have been the subject of much interest. The title compound, dodecakis(dimethylammonium) octakis(μ-benzene-1,3,5-tricarboxylato)hexa-μ-chlorido-tetracosa-μ-oxido-triacontaoxidotriacontavanadium, (NH2Me2)12[(V5O9Cl)6(C9H3O6)8], was synthesized successfully by self-assembly of VOCl3 and benzene-1,3,5-tricarboxylic acid under solvothermal conditions. The title polyhedron has an rdo topology when the {V5O9Cl} building unit and the benzene-1,3,5-tricarboxylate (BTC3−) ligand were simplified into 4-connected and 3-connected vertices. Interestingly, when the {V5O9Cl} building unit and the BTC3− ligand are considered as quadrangular and triangular faces, the structure displays rhombicuboctahedral geometry with an outer diameter of 21.88 Å. The packing of the polyhedra produces a circular channel with a diameter of 8.2 Å. The title compound was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis and powder X-ray diffraction.

A novel porous coordination polymer compound [Cd0.5(tpy)]∙0.75H2O was prepared by hydrothermal synthesis, which exhibits excellent chemical stability under various organic solvents and aqueous solution with different pH values range from 3 to 13. Benefiting from guest water molecules existing in the crystal structure, this compound shows water-mediated proton (H+) ion-conducting with conductivity of 6.03 × 10−6 S·cm−1 under 97% relative humidity at 95 °C. The calculated thermal activation energy (1.09 eV) and strong dependency on the humidity indicates a vehicle mechanism in the proton conduction process.

Chlorination is often adopted in the synthesis of donor materials considering the obvious improvement on efficiency of organic photovoltaic (OPV) device. Thus the chlorination effect was firstly probed based on density functional theory (DFT) calculation, which shows that the chlorinated benzothiadiazole connected with two thiophene rings (BTClTT) fragment although has larger optical bandgap and relatively blue-shifted spectrum, its deeper frontier molecular orbital (FMO) energy level, larger charge transfer distance (DCT) and much more transferred charges (CT), obvious negative natural population analysis (NPA) charges, larger twisted dihedral angles and smaller value of BLA indicate its favorable properties for the application in OPVs. Then, we designed a series of donor materials 2–7 adopting two strategies based on the experimental polymer 1 which contains BTClTT fragment. The calculated physical parameters characterizing OPV performance such as open-circuit voltage (VOC) and absorption-properties manifest that the design through side chains modifications for 2–5 may have slight influence on their cell performance while the backbone replacements for 6 and 7 exhibit prominent enhancement whether on VOC and photon-absorption property or on the charge separation ability. Therefore, our calculations suggest feasible strategies of designing donor materials for the chlorinated BT-based donor materials in OPVs. We hope our work can provide some guidelines for the future study on chlorinated donor materials.

Co-delivery of two drugs with diverse physicochemical properties and specific administration order for cancer theranostics are vitally important for drug resistance conquering and side effects reducing. Consequently, we explored a unique amphiphilic PCL-AuNC/Fe(OH)3-PAA Janus nanoparticle (JNP) to simultaneously preserve the hydrophilic drug (doxorubicin) and hydrophobic drug (docetaxel) in their distinct domains. Owing to their extraordinary heterostructure and independent pH and NIR sensitive properties, the optional sequential drug release by a single inorganic JNP was realized for the first time, and the results presented the synchronous release of two drugs had 5% better therapeutic effect. In addition, the excellent computed X-ray tomography/magnetic resonance (CT/MR) imaging capabilities from AuNC and Fe(OH)3 suggested our JNPs could effectively guide the cancer therapy. Furthermore, the mice treated with dual drug loaded PCL-AuNC/Fe(OH)3-PAA JNPs under near infrared (NIR) laser irradiation showed better tumor inhibition than solo drug, cocktail and dual drug treated groups, indicating the effectivity and significance of combined cancer therapy.

Designing mixed metal oxides with uniform nanostructures as a significant electrode material in energy storage devices is a vital concern for the whole world. But achieving this goal is plagued by many problems such as tedious procedures, hard morphology control and poor conductivities. The NiCo2O4/NiFe2O4 hollow nanospheres (NSs) are prepared for the first time through a novel one-pot approach. The introduced NiFe2O4 has amazingly improved the electrochemical performance of NiCo2O4 hollow NSs in both Li-ion batteries (LIBs) and supercapacitors (SCs). And the ratio of Fe to Ni plays an important role for the improvement of electrochemical performance. The NiCo2O4/NiFe2O4 hollow NSs exhibit superior capacity/capacitance values (3795 F g−1 at a current density of 1 A g−1) and fine cycling performances (11.0% specific capacitance decay after 6000 cycles) which can be attributed to the larger specific surface area of hollow NSs and the synergistic effect of two components. This provides a feasible preview of their practical applications.

In contrast to the traditional view that the small organic molecules emit fluorescence, more and more experiments manifest their special luminescence types, such as the thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence. Why the similar organic molecules exhibit different luminescence types is focused on in this work on the basis of density functional theory/time-dependent density functional theory calculations on a series of small organic molecules with phenoxazine or carbazole as a donor and diphenyl-triazine as an acceptor. The deep analysis of the geometrical and electronic structures shows how the structure, especially for the donor–acceptor dihedral angle, determines the singlet–triplet energy gap and the property of excited states. The explorations on the electron–hole pairs of natural transition orbitals and the contribution of the key heteroatom (N) to different molecular orbitals reveal the distinct electron transition processes of excitation to singlet and trip...