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Aqueous zinc metal batteries (AZMBs) directly utilizing Zn metal anode have been regarded as a promising candidate for the next generation commercial batteries featuring high safety, high theoretical capacity, and appealing chemical stability. However, narrow electrochemical stability windows of aqueous electrolytes, uncontrolled dendrite and limited reversibility still plague its practical applications. Herein, we present a strategy via engineering dilute aqueous Zn(OTf)2 solutions electrolytes with a polyethylene glycol (PEG) network, which substantially decreases the activity of water molecules, and simultaneously enables smooth Zn deposition with a (002) textured and a favorable ZnF2-rich SEI. As a result, symmetric cells with PEG-H2O system show record high cyclic performance (9000 h and 8000 h at current densities of 1 and 2 mA cm−2, respectively), superior interfacial stability and dendrite-free morphology after repeated plating/stripping. Additionally, Zn||70%PEG||V2O5 full batteries also deliver a remarkable energy density of 324.3 W h Kg−1 at a power density of 466.9 W Kg−1 and maintain 84.3% of the capacity over 500 cycles at a high current density of 15 A g−1. All these comprehensive results demonstrate that this electrolyte structural engineering can provide a promising direction for designing high reversibility, long-cycling life aqueous Zn metal batteries.

The design and synthesis of single-molecule amphiphilic and multifunctional phototherapeutic agents are important to cancer diagnosis and therapy. In this work, we developed three amphiphilic diketopyrrolopyrrole derivatives (TPADPP, DTPADPP, and TPADDPP) with different donor–acceptor structures and poly(ethylene glycol) side chains. The corresponding nanoparticles (NPs) were obtained via a self-assembly from three amphiphilic DPP derivatives and used as smart phototherapeutic agents for tumor diagnosis and treatment. The three amphiphilic DPP NPs exhibited near-infrared (NIR) emissions and good biocompatibility. Thus, they could be used as fluorescence (FL) imaging agents for guided therapy. DTPADPP NPs and TPADDPP NPs also displayed excellent photothermal performance and high accumulation in the tumor. Owing to these beneficial features, the DTPADPP NPs and TPADDPP NPs synthesized herein are suitable for NIR FL imaging and effective photothermal therapy against the tumor in vivo.

Cement brick is an essential construction component, which uses cement as the primary binder. The cement industry was identified as the major contributor to carbon dioxide emission, which is a greenhouse gas. The application of agro-industrial waste as partial cement replacement can reduce the negative impacts on the environment. In this study, the palm oil wastes, namely Palm Oil Clinker Powder (POCP) and Palm Oil Boiler Ash (POBA), were used as partial cement replacement. A total of 60 specimens were prepared with 0%, 10%, 20%, and 30% cement replacement by POCP and POBA. The physical and mechanical properties of bricks, such as density, water absorption, voids, and compressive strength, were investigated. The results show that the brick with 20% CP and BA could be used as a severe weathering brick.

In this work, an iron self-boosting polymer nanoenzyme was prepared by using pyrrole-3-carboxylic acid as a monomer and iron as an oxidizing agent via a simple and one-step method [hereafter referred to as FePPy nanoparticles (NPs)]. In fact, researchers previously paid negligible attention on the iron element during the polymerization reaction of polypyrrole, thus the intrinsically catalytic functions and enzymatic activities of the high iron content (wt %: 21.11%) are ignored and not fully explored. As expected, results demonstrate that the as-synthesized FePPy NPs can decompose H2O2 to generate hydroxyl radicals (•OH) which exhibit enzyme characteristics, further inducing a nonapoptotic ferroptosis pathway. Moreover, the nanoenzyme shows impressive photothermal properties which can accelerate the Fenton reactions to enhance ferroptosis. The combined photothermal and ferroptosis therapy of FePPy NPs was found to have high efficacy. With the properties of easy synthesis, high efficacy, and good biocompatibility, the FePPy NPs are considered as potential agents for cancer treatments.

Extensive recent efforts have been put on the design of high-performance organic near-infrared (NIR) photothermal agents (PTAs), especially over NIR-II bio-window (1000-1350 nm). So far, the development is mainly limited by the rarity of molecules with good NIR-II response. Here, we report organic nanoparticles of intermolecular charge-transfer complexes (CTCs) with easily programmable optical absorption. By employing different common donor and acceptor molecules to form CTC nanoparticles (CT NPs), absorption peaks of CT NPs can be controllably tuned from the NIR-I to NIR-II region. Notably, CT NPs formed with perylene and TCNQ have a considerably red-shifted absorption peak at 1040 nm and achieves a good photothermal conversion efficiency of 42 % under 1064 nm excitation. These nanoparticles were used for antibacterial application with effective activity towards both Gram-negative and Gram-positive bacteria. This work opens a new avenue into the development of efficient PTAs.

Triplet harvesting of organic materials is of great significance in many applications, including organic optoelectronic devices, anti-counterfeiting, and biological and chemical sensors. Aryl carbonyl-based luminescent materials have been widely studied in the above-mentioned fields because they possess intrinsic n–π* transitions as a result of the lone electron pairs of the carbonyl oxygen. Consequently, efficient intersystem crossing and reverse intersystem crossing can be achieved and triplet energy can be utilized through the narrow singlet–triplet offsets arose from the orthogonal overlaps between n and π* orbitals. It has also been revealed that they exhibit versatility in molecular tailoring and supramolecular engineering for various functional materials. This review presents a systematic summary of the recent research on aryl carbonyl (including moieties derived from aryl carbonyl) derivatives, with particular focus on their applications as electron acceptors, discussing the various strategies for the construction of luminescent materials with thermally activated delayed fluorescence and room-temperature phosphorescence, respectively. Finally, the perspectives and challenges concerning aryl carbonyl for triplet harvesting luminescent applications are also discussed.

High efficiency and stable blue phosphors have been a persistent pursuit in the field of organic light-emitting diodes (OLEDs). Bis-tridentate Ir(III) complexes are considered as promising alternatives because of their excellent emission efficiency and good photostability. However, the emission colors of photostable bis-tridentate Ir(III) emitters reported so far do not reach the deep blue region. Herein, fluorene is introduced in the design of blue bis-tridentate Ir(III) complexes. By modifying a fluorene-based dianionic chelate with tert-butyl, methoxy, pyrrolidinyl and triazolyl appendages, five blue emitting bis-tridentate Ir(III) phosphors were successfully designed and prepared. Emissions of the new phosphors exhibited a gradual blue shift from the sky blue to the deep blue region according to the electron donating abilities of the added substituents. A deep blue OLED was successfully fabricated based on Flu-4 and presented an excellent maximum external quantum efficiency of 22.3% with CIE coordinates of (0.17, 0.19), which are comparable to the state-of-the-art deep blue phosphors.

A novel electrochemical method for the synthesis of α,β-epoxy ketones is reported. With KI as the redox mediator, methyl ketones reacted with aldehydes under peroxide- and transition metal-free electrolytic conditions and afforded α,β-epoxy ketones in one pot (36 examples, 52-90% yield). This safe and environmental-friendly method has a broad substrate scope and can readily provide a variety of α,β-epoxy ketones in gram-scales for evaluation of their anti-cancer activities.

Developing highly efficient red thermally activated delayed fluorescence (TADF) emitters remains a formidable challenge due to strict molecular design principles. In this contribution, two red emitters PXZ-AQPy and PXZ-AQPhPy with high structural rigidity and linear configurations are designed and synthesized based on phenoxazine (PXZ) as a donor and acenaphtho[1,2-b]quinoxaline (AQ) as an acceptor. Both molecules with horizontal orientation are endowed with TADF and aggregation-induced emission (AIE) properties. By elongating the acceptor segment via phenyl decoration, PXZ-AQPhPy exhibits higher horizontal ratios of the emitting dipole orientation (Θ‖ = 85%), while the emission characteristics are almost unaltered. Consequently, the PXZ-AQPhPy based device achieves a high external quantum efficiency of 19.6% with an emission peak at 610 nm. This work provides a simple and effective design strategy to selectively promote the horizontal orientation of red TADF emitters.

Hypocrellin B (HB) derived from naturally produced hypocrellins has attracted considerable attention in photodynamic therapy (PDT) because of its excellent photosensitive properties. However, the weak absorption within a "phototherapy window" (600-900 nm) and poor water solubility of HB have limited its clinical application. In this study, two HB derivatives (i. e., HE and HF) were designed and synthesized for the first time by introducing two different substituent groups into the HB structure. The obtained derivatives showed a broad absorption band covering the near-infrared (NIR) region, NIR emission (peaked at 805 nm), and singlet oxygen quantum yields of 0.27/0.31. HE-PEG-NPs were also prepared using 2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethyleneglycol)-2000] (DSPE-mPEG2000) to achieve excellent dispersion in water and further explored their practical applications. HE-PEG-NPs not only retained their 1 O2 -generating ability, but also exhibited a photothermal conversion efficiency of 25.9%. In vitro and in vivo therapeutic results revealed that the synergetic effect of HE-PEG-NPs on PDT and photothermal therapy (PTT) could achieve a good performance. Therefore, HE-PEG-NPs could be regarded as a promising phototheranostic agent.

Pharmaceutical evaluations of nanomedicines are of great significance for their further launch into industry and clinic. Near-infrared (NIR) fluorescence imaging plays essential roles in preclinical drug development by providing important insights into the biodistributions of drugs in vivo with deep tissue penetration and high spatiotemporal resolution. However, NIR-II fluorescence imaging has rarely been exploited for in vivo real-time pharmaceutical evaluations of nanomedicine. Herein, we developed a highly emissive NIR-II luminophore to establish a versatile nanoplatform to noninvasively monitor the in vivo metabolism of nanomedicines bound various polyethylene glycol (PEG) ligands in a real-time manner. An alternative D-A-D conjugated oligomer (DTTB) was synthesized to achieve NIR-II emission peaked at ∼1050 nm with high fluorescence QYs of 13.4% and a large absorption coefficient. By anchoring with the DTTB molecule, intrinsically fluorescent micelles were fabricated and bound with PEG ligands at various chain lengths. In vivo NIR-II fluorescence and photoacoustic imaging results revealed that an appropriate PEG chain length could effectively contribute to the longer blood circulation and better tumor targeting. In vivo therapeutic experiments also confirmed the optimized nanomedicines have efficient photothermal elimination of tumors and good biosafety. This work offered an alternative highly fluorescent NIR-II material and demonstrated a promising approach for real-time pharmaceutical evaluation of nanomedicine in vivo.

Three donor–acceptor–donor molecular emitters have been designed by taking triphenylamine or N-phenylcarbazole as the donor and maleimide or phenyl maleimide as the acceptor, in which the highest o...

Effective multimodality phototheranostics under deep-penetration laser excitation is highly desired for tumor medicine, which is still at a deadlock due to lack of versatile photosensitizers with absorption located in the long-wavelength region. Herein, we demonstrate a stable organic photosensitizer nanoparticle based on molecular engineering of benzo[c]thiophene (BT)-based photoactivated molecules with strong wavelength-tunable absorption in the near-infrared region. Via molecular design, the absorption and singlet oxygen generation of BT molecules would be reliably tuned. Importantly, the nanoparticles with a red-shifted absorption peak of 843 nm not only show over 10-fold reactive oxygen species yield compared with indocyanine green but also demonstrate a notable photothermal effect and photoacoustic signal upon 808 nm excitation. The in vitro and in vivo experiments substantiate good multimodal anticancer efficacy and imaging performance of BT theranostics. This work provides an organic photosensitizer nanoparticle with long-wavelength excitation and high photoenergy conversion efficiency for multimodality phototherapy.

Cancer is the second leading cause of death globally, responsible for an estimated 9.6 million deaths in 2018, and this burden continues to increase. Therefore, there is a clear and urgent need for novel drugs with increased efficacy for the treatment of different cancers. Previous research has demonstrated that brevilin A (BA) exerts anticancer activity in various cancers, including human multiple myeloma, breast cancer, lung cancer, and colon carcinoma, suggesting the anticancer potential present in the chemical scaffold of BA. Here, we designed and synthesized a small library of 12 novel BA derivatives and evaluated the biological anticancer effects of the compounds in various cancer cell lines. The results of this structure–activity relationship study demonstrated that BA derivatives BA-9 and BA-10 possessed significantly improved anticancer activity toward lung, colon, and breast cancer cell lines. BA-9 and BA-10 could more effectively reduce cancer cell viability and induce DNA damage, cell-cycle arrest, and apoptosis when compared with BA. Our findings represent a significant step forward in the development of novel anticancer entities.

Maintaining the stability of tin halide perovskites is a major challenge in developing lead-free perovskite solar cells (PSCs). Adding extra SnX2 (X = F, Cl, or Br) in the precursor solution to inh...

Porous boron nitride (BN) materials have been considered as a promising material for CO₂ capture and storage. It was found that the Cu²⁺ ion can modify the nucleation mechanism during the synthetic reaction between boric acid and melamine leading to the formation of Cu-loaded BN nanofibers with uniform and smaller diameter. Interestingly, the introduction of Cu was found to dramatically enhance the CO₂ adsorption capacity of the BN nanofibers from 1.34 to 2.77 mmol g–¹ (at 1 bar, 273 K). The Cu-loaded BN nanofiber not only shows a CO₂ adsorption capacity comparable to those of state-of-the-art BN-based CO₂ absorbents but also shows unprecedented high recyclability for repeated uses. The mechanisms of the copper-induced CO₂ adsorption capacity enhancement were investigated with density-functional theory calculations. It was found that the incorporation of Cu can change the electron transfer between porous BN and CO₂ to promote the affinity and adsorption capacity of CO₂.

A novel light-emitting material, 4-(4-diphenylaminophenyl)-benzo[d,e]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one (4-TPA-BBI) is synthesized and characterized. 4-TPA-BBI exhibits excellent polymorphis...

Traditional photosensitizers (PSs) show reduced singlet oxygen (1 O2 ) production and quenched fluorescence upon aggregation in aqueous media, which greatly affect their efficiency in photodynamic therapy (PDT). Meanwhile, non-targeting PSs generally yield low efficiency in antibacterial performance due to their short lifetimes and small effective working radii. Herein, a water-dispersible membrane anchor (TBD-anchor) PS with aggregation-induced emission is designed and synthesized to generate 1 O2 on the bacterial membrane. TBD-anchor showed efficient antibacterial performance towards both Gram-negative (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus). Over 99.8 % killing efficiency was obtained for methicillin-resistant S. aureus (MRSA) when they were exposed to 0.8 μm of TBD-anchor at a low white light dose (25 mW cm-2 ) for 10 minutes. TBD-anchor thus shows great promise as an effective antimicrobial agent to combat the menace of multidrug-resistant bacteria.

A method for synthesising cyclopenta[b]pyran-2-ones through direct (3 + 2) cycloaddition between 2-pyrones and vinyl cyclopropanes is described. In the presence of Pd2(dba)3/dppe in toluene, a series of 2-pyrones undergo chemoselective (3 + 2) cycloaddition with vinyl cyclopropanes and afford cyclopenta[b]pyran-2-ones in high yields (78–96%). The trans/cis ratio of the cycloadducts has been optimised up to 10 : 1. The proposed mechanism of this cycloaddition has been rationalised by computational studies.

N-Borylated emitters bearing both boron dimesityl acceptor (Mes)2B and phenoxazine or acridine donors are a class of efficient TADF emitters; however, switching to a carbazole donor nullifies the TADF characteristics. This work is targeted at improving the TADF characteristics of the carbazole based (Mes)2B emitters by introducing up to two methoxy substituents at the carbazoles. We hereby report the design and synthesis of three methoxy substituted carbazoles (Cz-1, Cz-2 and Cz-3) and the corresponding directly N-borylated emitters, CzBM-1, CzBM-2 and CzBM-3. Moreover, a p-phenylene spacer was also introduced between the (Mes)2B unit and carbazole, giving CzPBM-2 and CzPBM-3. As confirmed by the bi-exponential transient decay analyses, all title compounds exhibit prominent TADF character, while the parent molecules CzBM-0 and CzPBM-0 without methoxy groups show no TADF characteristics. The results manifest the importance of the donor strength of substituents and degrees of spatial orthogonality in harnessing the charge transfer properties, minimalizing the S1–T1 energy gap and facilitating the reverse intersystem crossing process. OLED devices with doped CzBM-2 and CzPBM-3 emitters exhibited a maximum external quantum efficiency of 12.5% and 13.3%, respectively, confirming the potential of methoxy substituents in improving their TADF characteristics.

Photoluminescence quantum yield (PLQY) and the reverse intersystem crossing (RISC) process are critical for next-generation highly efficient organic light-emitting diodes (OLEDs). However, it is not easy to simultaneously obtain high PLQY and fast RISC, especially in TADF emitters with twisted donor–acceptor structures due to their conflicting requirements for wave function overlapping. Herein, based on a rigid planar dibenzo[a,c]phenazine (DPPZ) unit as an acceptor, four emitters (isomers of DMAC-11-DPPZ and DMAC-10-DPPZ, and isomers of PXZ-11-DPPZ and PXZ-10-DPPZ) with 9,9-dimethylacridine (DMAC) and 10H-phenoxazine (PXZ) as donors substituted via 11- and 10-positions were designed and synthesized to balance the wave function overlapping and explore the relationship between their structures and luminescence properties. Photophysical characterization and theoretical calculations suggest small energy gaps (ΔEST) featuring fast RISC rates in all these compounds. Meanwhile, DMAC-11-DPPZ and PXZ-11-DPPZ achieve higher PLQYs due to the largely suppressed non-radiative transition as revealed by the decreased Huang–Rhys factors. As a result, high external quantum efficiencies (EQEmax) of 23.8% for DMAC-11-DPPZ and 13.7% for PXZ-11-DPPZ are obtained. This work provides a promising strategy to improve the PLQY of TADF materials by adjusting the substituted site, and also shows the potential of phenazine derivatives for OLED applications.

(4 + 3) cycloadditions between allenyl ethers and furans are described. The reaction features an in situ formation of oxygen-stabilized oxyallyls via epoxidations of allenyl ethers in the presence of H2PO4−. The multiple interactions between the oxygen-stabilized oxyallyl species and H2PO4− were studied using DFT calculations for rationalization of the regio- and diastereoselectivity of this cycloaddition. The utilities of this cycloaddition have been demonstrated by converting the (4 + 3) cycloadduct into the cyclohepta[b]benzofuran skeleton of frondosin B in two steps.

Rational manipulation of energy utilization from excited-state radiation of theranostic agents with a donor–acceptor structure is relatively unexplored. Herein, we present an effective strategy to tune the exciton dynamics of radiative excited state decay for augmenting two-photon nanotheranostics. As a proof of concept, two thermally activated delayed fluorescence (TADF) molecules with different electron-donating segments are engineered, which possess donor–acceptor structures and strong emissions in the deep-red region with aggregation-induced emission characteristics. Molecular simulations demonstrate that change of the electron-donating sections could effectively regulate the singlet–triplet energy gap and oscillator strength, which promises efficient energy flow. A two-photon laser with great permeability is used to excite TADF NPs to perform as theranostic agents with singlet oxygen generation and fluorescence imaging. These unique performances enable the proposed TADF emitters to exhibit tailored balances between two-photon singlet oxygen generation and fluorescence emission. This result demonstrates that TADF emitters can be rationally designed as superior candidates for nanotheranostic agents by the custom controlling exciton dynamics., Exciton dynamics can be manipulated rationally in the design of TADF materials for nanotheranostics. Regulating the ΔEST and f promises efficient energy flow for tailoring balances between singlet oxygen generation and fluorescence emission.

A concise synthesis of the tetracyclic skeleton of palhinine alkaloids is described. The approach features a bifunctional Lewis acid promoted Diels–Alder/carbocyclization cascade for the rapid construction of the isotwistane (tricyclo[4.3.1.03,7]decane) core. This key reaction is highly diastereoselective and could be carried out on gram scale. The cyclization product already possesses the completed ring system of palhinine alkaloids and could potentially be further functionalized to palhinine A.

Novel charge transport properties distinguished from their parental materials are intriguing features of charge transfer complexes (CTCs). In this work, co-evaporated molybdenum(VI)oxide and sexithiophene (MoO3 : 6T) CTC thin film is prepared and its electron and hole transport properties are studied. While the MoO3 : 6T CTC material shows both electron and hole transport, detailed changes in molecular orbital hybridization are further studied under an external stimulus. Using a simple rubbing process, the intermolecular interaction of the CTC material can be tuned such that changes in optical properties, vibrational modes, chemical states and electronic structures are observed. These changes in properties and charge transport behaviors enable us to understand the influences of CTC frontier molecular orbitals (FMOs) and their degree of coupling on the charge transport properties. This work provides insight into the understanding of the intermolecular interactions and their influence on the charge transport properties of thin film CTCs.

Although piperine-an extract from pepper-has a mild chemotherapeutic effect, its poor water solubility has limited its applications for cancer therapy. With self-assembling of piperine into nanoparticles along with PEG (Pip NPs), both the water dispersibility and the chemotherapeutic efficacy can be substantially enhanced. It is further shown that the NPs can generate reactive oxygen species (ROS) with or without additional white light irradiation. Interestingly, the Pip NP induced cell death can be suppressed by ferroptosis inhibitors such as liproxstatin-1 and deferoxamine. Lipid ROS production is also observed in Pip NP treated cells. In addition to their cancer cell killing ability, the Pip NPs also show strong green fluorescence. These multiple functions make the Pip NPs a promising and low-cost nanotheranostic agent with herbal origin.

Synthesis of the multidentate coordinated chelate N3C–H2, composed of a linked functional pyridyl pyrazole fragment plus a peripheral phenyl and pyridyl unit, was obtained using a multistep protoco...

In this work, we report a series of bis-tridentate Ir(III) metal complexes, comprising a dianionic pyrazole-pyridine-phenyl tridentate chelate and a monoanionic chelate bearing a peripheral carbene and carboline coordination fragment that is linked to the central phenyl group. All these Ir(III) complexes were synthesized with an efficient one-pot and two-step method, and their emission hue was fine-tuned by variation of the substituent at the central coordination entity (i.e., pyridinyl and phenyl group) of each of the tridentate chelates. Their photophysical and electrochemical properties, thermal stabilities and electroluminescence performances are examined and discussed comprehensively. The doped devices based on [Ir(cbF)(phyz1)] (Cb1) and [Ir(cbB)(phyz1)] (Cb4) give a maximum external quantum efficiency (current efficiency) of 16.6% (55.2 cd/A) and 13.9% (43.8 cd/A), respectively. The relatively high electroluminescence efficiencies indicate that bis-tridentate Ir(III) complexes are promising candidates for OLED applications.

Upon fusing the pyrazinyl pyrazole entity in giving pyrazolo[3,4- f ]quinoxaline chelate, the corresponding Os(II) based NIR emitter exhibited "invisible" and efficient electroluminescence with peak max. at 811 nm and a maximum external quantum efficiency of 0.97% and suppressed efficiency roll-off till a current density of 300 mA cm -2 .

Single atom catalysts have received widespread attention for their fascinating performance in terms of metal atom efficiency as well as their unique catalysis mechanisms comparing to conventional catalysts. Here, we prepared a high-performance catalyst of single-Cu-atom-decorated boron nitride nanofibers (BNNF-Cu) via a facile calcination method for the first time. The as-prepared catalyst shows excellent catalytic activity and good stability for converting different nitro compounds into their corresponding amines both with and without photoexcitation. By combined studies using synchrotron radiation analysis, high-resolution high-angle annular dark-field transmission electron microscopy studies and DFT calculation, dispersion and coordination of Cu atoms as well as their catalytic mechanisms are explored. The BNNF-Cu catalyst is found to have a record high turn-over frequency comparing to previously reported nonprecious-metal-based catalysts. While the performance of the BNNF-Cu catalyst is only of the middle range level among the state-of-the-art precious-metal-based catalysts, due to the much lower cost of the BNNF-Cu catalyst, its cost-efficiency is the highest among these catalysts. This work provides a new choice of support material which can promote the development of single atoms catalysts.

We developed a biodegradable photothermal therapeutic (PTT) agent, π-conjugated oligomer nanoparticles (F8-PEG NPs), for highly efficient cancer theranostics. By exploiting an oligomer with excellent near-infrared (NIR) absorption, the nanoparticles show a high photothermal conversion efficiency (PCE) up to 82%, surpassing those of reported inorganic and organic PTT agents. In addition, the oligomer nanoparticles show excellent photostability and good biodegradability. The F8-PEG NPs are also demonstrated to have excellent biosafety and PTT efficacy both in vitro and in vivo. This contribution not only proposes a promising oligomer-based PTT agent but also provides insight into developing highly efficient nanomaterials for cancer theranostics.

Bis-tridentate Ir(III) metal complexes bring forth interesting photophysical properties, among which the orthogonal arranged, planar tridentate chelates could increase the emission efficiency due to the greater rigidity and, in the meantime, allow strong interligand stacking that could deteriorate the emission efficiency. We bypassed this hurdle by design of five bis-tridentate Ir(III) complexes (-), to which both of their monoanionic ancillary and dianionic chromophoric chelate were functionalized derivative of 2-pyrazolyl-6-phenylpyridine, i.e. pzpyphH parent chelate. Hence, addition of phenyl substituent to the pyrazolyl fragment of pzpyphH gave rise to the precursors of monoanionic chelate (A1H-A3H), on which the additional -butyl and/or methoxy groups were introduced at the selected positions for tuning their steric and electronic properties, while precursors of dianionic chelates was judiciously prepared with an isoquniolinyl central unit on pziqphH in giving the red-shifted emission (cf. L1H and L2H). Factors affected their photophysical properties were discussed by theoretical methods based on DFT and TD-DFT calculation, confirming that the T excited state of all investigated Ir(III) complexes shows a mixed metal-to-ligand charge transfer (MLCT), intraligand charge transfer (ILCT), ligand-to-ligand charge transfer (LLCT), and ligand-centered (LC) transition character. In contrast, the poor quantum yield of is due to the facilitation of the nonradiative decay in comparison to the radiative process. As for potential OLED applications, Ir(III) complex gives superior performance with max. efficiencies of 28.17%, 41.25 cd·A and 37.03 lm·W, CIE = 0.63, 0.37 at 50 mA cm, and small efficiency roll-off.

The performance of wide-band gap perovskite solar cells has a profound impact on the multijunction tandem device efficiency. However, once bromide (Br–) has been adopted to substitute the iodide (I...

Neolaxiflorin L (NL) is a low-abundant Isodon 7,20-epoxy- ent-kuarenoid and was found to be a promising anticancer drug candidate in our previous study. In order to study its structure-activity relationship (SAR), a diversity-oriented synthetic route toward two libraries of (±)-NL analogs, including analogs containing different functionalities in the same 7,20-epoxy- ent-kuarene skeleton and analogs with skeletal changes, has been developed. The results of this total synthesis-enabled SAR successfully led to a bioactive alkyne-tagged NL derivative, which could be a useful probe for proteomics studies.

A novel molecule 3-(4-diphenylaminophenyl)-benzo[d,e]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one (3-TPA-BBI) is synthesized and found to exhibit mechanochromic luminescence properties. Its photoluminescence can be reversibly switched between orange and yellow upon external stimuli. More interestingly, a non-doped device utilizing 3-TPA-BBI as the emitter exhibits unprecedented color-tunable electroluminescence upon heat treatment.

Energy differences (ΔESTs) between the lowest singlet and triplet excited states as well as the oscillator strengths (fs) are two contradictory factors controlling performance of thermally activated delayed fluorescence (TADF) emitters. To figure out their optimum balance, we developed two orange–red isomeric TADF emitters 12-(13,13-dimethyl-5-phenyl-5,13-dihydro-11H-indolo[2,3-b]acridin-11-yl)dibenzo[a,c]dipyrido[3,2-h:2′,3′-j]phenazine (IDAC–BPPZ) and 12-(13,13-dimethyl-11-phenyl-11,13-dihydro-5H-indolo[2,3-b]acridin-5-yl)dibenzo[a,c]dipyrido[3,2-h:2′,3′-j]phenazine (ACID–BPPZ), which are constructed with the same electron-donor (D) and the same electron-acceptor (A) cores via different connecting sites. ACID–BPPZ has a weaker D–A conjugation and realizes an extremely small ΔEST of 0.02 eV, but its f is also very small (0.001). These factors are better compromised in IDAC–BPPZ which has a more conjugated D–A connections. This successfully realizes a much higher f of 0.068 and a reasonably small ΔEST of 0.07 eV. As a result, the orange–red OLEDs using IDAC–BPPZ as emitter achieve a maximum external quantum efficiency 18.3% comparing to that of 14.7% in the ACID–BPPZ-based device. The results suggest that a balance between ΔEST and f is important for developing high performance TADF emitters.

Nanomaterial-mediated phototherapy, including photodynamic therapy (PDT) and photothermal therapy (PTT), is an effective anticancer intervention that relies on light activation of photoactive nanomaterials localized in tumors. Recently, combinational PDT/PTT offered a practical pathway to relieve resistance of monotherapy, surmount undesirable side effects and provide a synergistic effect to enhance phototherapeutic efficiency. Herein, we report a facile strategy to integrate protoporphyrin IX (PpIX) into nanoscale metal-organic frameworks (NMOFs) and control their photoactive properties for combinational cancer PDT and PTT. With optimized PpIX conjugation, the as-fabricated nanoparticles (nPCU NPs) exhibit (1) improved dispersibility and particle stability, (2) simultaneous generation of reactive oxygen species and heat effectively through activation by a single-wavelength laser of 635 nm, and (3) maintenance of porosity for further application as drug delivery vehicles. Moreover, in vitro investigation of nPCU NPs demonstrates effective cellular uptake, successful endosomal escape and enhanced phototherapeutic efficacy under both normoxic and hypoxic conditions. Therefore, this study developed a novel type of phototherapeutic nanoplatform with optimal properties for applicable cancer phototherapy.

Two microporous anionic indium-based metal–organic frameworks, namely [Me2NH2][In(abtc)]·solvents (1) and [Me2NH2][In(bptc)]·solvents (2) (H4abtc = 3,3′,5,5′-azobenzenetetracarboxylic acid; H4bptc = biphenyl-3,3′,5,5′-tetracarboxylic acid), have been synthesized and characterized. Single-crystal X-ray analyses show that compounds 1 and 2 display isostructural three-dimensional anionic frameworks with PtS topology. With these structural features, both compound 1 and compound 2 can selectively separate cationic organic dyes with suitable size. White-light emission can be obtained by loading compound 2 with safranin O. In addition, compound 1 dispersed in dimethyl formamide not only retains the emission of the abtc4− ligand at about 402 nm, but also gives new emission centered at 623 nm. Based on these emissions, compound 1 was developed as an efficient dual-emitting sensor for probing Fe3+ ions.

A bench-stable combination of NaBH4-acetylacetone was developed for the efficient chemoselective reduction of aldehydes in the presence of ketones. This method offers a useful synthetic protocol for distinguishing carbonyl reaction sites, and its synthetic utility is reflected by its moisture tolerance and high efficiency in a variety of complex settings.

Three dihydrochalcone-derived polyphenols, huperolides A-C (1-3), along with thirteen known compounds (4-16) were isolated from the leaves of Malus hupehensis, the well-known tea crab apple in China. Their chemical structures were elucidated by extensive spectroscopic analysis including NMR (HSQC, HMBC, 1H-1H COSY and ROESY), HRMS and CD spectra. Huperolide A is a polyphenol with a new type of carbon skeleton, while huperolides B and C are a couple of atropisomers, which were isolated from natural sources for the first time. The antihyperglycemic effects of the isolated compounds were evaluated based on assaying their inhibitory activities against α-glucosidase. As a result, phlorizin (4), 3-hydroxyphloridzin (5), 3-O-coumaroylquinic acid (12) and β-hydroxypropiovanillone (15) showed significant concentration-dependent inhibitory effects on α-glucosidase. Therefore, those compounds might be responsible for the antihyperglycemic effect of this herb, and are the most promising compounds to lead discovery of drugs against diabetes.

Tin-based perovskites with excellent optoelectronic properties and suitable band gaps are promising candidates for the preparation of efficient lead-free perovskite solar cells (PSCs). However, it is challenging to prepare highly stable and efficient tin-based PSCs because Sn2+ in perovskites can be easily oxidized to Sn4+ upon air exposure. Here we report the fabrication of air-stable FASnI3 solar cells by introducing hydroxybenzene sulfonic acid or its salt as an antioxidant additive into the perovskite precursor solution along with excess SnCl2 . The interaction between the sulfonate group and the Sn2+ ion enables the in situ encapsulation of the perovskite grains with a SnCl2 -additive complex layer, which results in greatly enhanced oxidation stability of the perovskite film. The corresponding PSCs are able to maintain 80 % of the efficiency over 500 h upon air exposure without encapsulation, which is over ten times longer than the best result reported previously. Our results suggest a possible strategy for the future design of efficient and stable tin-based PSCs.

A highly diastereoselective cascade cyclization reaction has been developed for establishing a series of oxatricyclic compounds using Chan’s diene and simple keto alkynal substrates with only 1 mol % of In(OTf)3 as the catalyst in 82–92% yields. The potential utility of this synthetic strategy has been demonstrated in model studies for the construction the core structures of 1α,8α:4α,5α-diepoxy-4,5-dihydroosmitopsin and cortistatin A.

A bromine-substituted thermally activated delayed fluorescent (TADF) molecule AQCzBr2 is designed with both small singlet-triplet splitting (ΔEST) and increased spin-orbit coupling (SOC) to boost intersystem crossing (ISC) for singlet oxygen generation. AQCzBr2 nanoparticles (NPs) demonstrate high productivity of singlet oxygen generation (ΦΔ = 0.91) which allows highly efficient photodynamic therapy toward cancer cells.

Hydrophobic photosensitizers greatly affect cell permeability and enrichment in tumors, but they cannot be used directly for clinical applications because they always aggregate in water, preventing their circulation in the blood and accumulation in tumor cells. As a result, amphiphilic photosensitizers are highly desirable. Although nanomaterial-based photosensitizers can solve water solubility, they have the disadvantages of complicated operation, poor reproducibility, low drug loading, and poor stability. In this work, an efficient synthesis strategy is proposed that converts small molecules into nanoparticles in 100 % aqueous solution by molecular assembly without the addition of any foreign species. Three photosensitizers with triphenylphosphine units and ethylene glycol chains of different lengths, TPP-PPh3 , TPP-PPh3 -2PEG and TPP-PPh3 -4PEG, were synthesized to improve amphiphilicity. Of the three photosensitizers, TPP-PPh3 -4PEG is the most efficient (singlet oxygen yield: 0.89) for tumor photodynamic therapy not only because of its definite constituent, but also because its amphiphilic structure allows it to self-assemble in water.

Thermally activated delayed fluorescence (TADF) has been considered an important development in organic light-emitting diodes (OLEDs) for significantly enhancing efficiency of pure organic emitters. However, TADF is often associated with boarder emission spectra not meeting the requirements of modern high-performance flat-panel displays. A recent breakthrough in TADF emitters is the development of multiple resonance (MR) emitters which have a narrow spectral band width, i.e., good colour purities. However, so far molecular design for MR emitters is still much restricted and their emission peaks are covering only in a very limited range between ~ 460 to 510 nm. Herein, by exploiting a new emitting mechanism of densely packed dimer enhanced MR TADF, we demonstrate for the first time of highly efficient electroluminescence covering the RGB full colour with narrow spectral widths using pure organic emitters. MR-structured compounds with symmetry-forbidden n-π* transition for fluorescence are employed. They form intimate molecular interaction in their dimer states, leading to substantial changes in the S1 electronic structure into π-π* transition and much smaller singlet-triplet energy offset, which can significantly enhance TADF characteristics. The fluorescence efficiency increases tremendously to approach unity upon dimer formation. More importantly, molecular relaxations are strongly restricted in the systems due to their robust MR typed monomer frameworks as well as their strong dimer interaction. By applying these MR dimers in OLEDs, highly efficient narrow emission spectra can be achieved with full-width at half maximum of 32, 44, and 64 nm for blue, green, and red, respectively. Particularly, the green OLED realizes a remarkable maximum external quantum efficiency of 31%. Our strategies not only provide a pathway for realizing narrow emission covering full RGB emission range via intermolecular emitting systems (dimers, excimers, exciplexes, etc.) for the first time, but also exploit a new emitting mechanism leading to state-of-the-art performance among all reported OLEDs.

Excess PbI2 management is critical to the performance and stability of perovskite solar cells (PSCs). However, typical post treatment method remains the nature of instability induced by the photolysis of PbI2. Herein, by forming robust self-assembled supramolecules ([BMIM]PbI2X5 and [BMIM]PbX3) with 1-butyl-3-methylimidazolium based ionic liquids ([BMIM]X), we report a novel “Ionic Liquid assisted Supramolecular Complex engineering” (ILaSC) approach to effectively modulate the unreacted PbI2. The formation process and mechanism of supramolecules are elucidated. With effective Pb interstitial defects passivation and tensile strain relaxation simultaneously, the ILaSC approach achieves significant enhancements in both PCE (from 21.9% to 23.5%) and device stability (retaining 95% of the initial PCE after 4080 h in ambient dry-air storage, and 80% after 1400 h continuous light illumination). The generality of the supramolecular complex engineering methodology in broader ionic salt systems is further demonstrated, representing a new direction towards highly stable and efficient PSCs.

Passivating surface and bulk defects of perovskite films has been proven to be an effective way to minimize nonradiative recombination losses in perovskite solar cells (PVSCs). The lattice interference and perturbation of atomic periodicity at the perovskite surfaces often significantly affect the material properties and device efficiencies. By tailoring the terminal groups on the perovskite surface and modifying the surface chemical environment, the defects can be reduced to enhance the photovoltaic performance and stability of derived PVSCs. Here, we report a rationally designed bifunctional molecule, piperazinium iodide (PI), containing both R2NH and R2NH2+ groups on the same six-membered ring, behaving both as an electron donor and an electron acceptor to react with different surface-terminating ends on perovskite films. The resulting perovskite films after defect passivation show released surface residual stress, suppressed nonradiative recombination loss, and more n-type characteristics for sufficient energy transfer. Consequently, charge recombination is significantly suppressed to result in a high open-circuit voltage (VOC) of 1.17 V and a reduced VOC loss of 0.33 V. A very high power conversion efficiency (PCE) of 23.37% (with 22.75% certified) could be achieved, which is the highest value reported for inverted PVSCs. Our work reveals a very effective way of using rationally designed bifunctional molecules to simultaneously enhance the device performance and stability.

Contact lenses are widely used for visual corrections. However, while wearing contact lenses, eyes typically face discomforts (itching, irritation, burning, etc.) due to foreign object sensation, lack of oxygen permeability, and tear film disruption as opposed to a lack of wetting agents. Eyes are also prone to ocular infections such as bacterial keratitis (BK) and fungal keratitis (FK) and inflammatory events such as contact lens-related acute red eye (CLARE), contact lens peripheral ulcer (CLPU), and infiltrative keratitis (IK) caused by pathogenic bacterial and fungal strains that contaminate contact lenses. Therefore, a good design of contact lenses should adequately address the need for wetting, the supply of antioxidants, and antifouling and antimicrobial efficacy. Here, we developed multifunctional gallic acid (GA), phytomolecules-coated zinc oxide nanoparticles (ZN), and phytomolecules-coated zinc oxide nanoparticles + gallic acid + tobramycin (ZGT)-coated contact lenses using a sonochemical technique. The coated contact lenses exhibited significant antibacterial (>log10 5.60), antifungal, and antibiofilm performance against BK-causing multidrug resistant bacteria (Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia. coli) and FK-related pathogenic fungal strains (Candida albicans, Aspergillus fumigatus, and Fusarium solani). The gallic acid, tobramycin, and phytomolecules-coated zinc oxide nanoparticles have different functionalities (-OH, -NH2, -COOH, -COH, etc.) that enhanced wettability of the coated contact lenses as compared to that of uncoated ones and further enabled them to exhibit remarkable antifouling property by prohibiting adhesion of platelets and proteins. The coated contact lenses also showed significant antioxidant activity by scavenging DPPH and good cytocompatibility to human corneal epithelial cells and keratinocytes cell lines. Statement of significance • Multifunctional coated lenses were developed with an efficient sonochemical approach. • Lens surface was modified with nanocoatings of ZnO nanoparticles, gallic acid, and tobramycin. • This synergistic combination endowed the lenses with remarkable antimicrobial activity. • Coated lenses also showed noteworthy antifouling and biofilm inhibition activities. • Coated lenses showed good antioxidant, biocompatibility, and wettability characteristics.

Self-healing hydrogel systems usually suffer from poor mechanical performance stemmed from weaker and reversible non-covalent interactions or dynamic chemical bonds, which hamper their practical applications. This issue is addressed by adopting a double-crosslinking design involving both dynamic Schiff base bonds and non-dynamic photo-induced crosslinking. This leads to the formation of a special topological structure which simultaneously provide good self-healing capability and enhanced mechanical performance (elastic recovery and tensile modulus of 157.4 kPa, close to modulus of native skin). The quaternary ammonium and protonated amino groups can provide superior antibacterial capability; and Schiff base formation between residual aldehyde groups and amino groups on tissue surface contribute to hydrogel's adhesion to tissues (5.9 kPa). Furthermore, the multifunctional hydrogels with desirable mechanical performance, self-healing capability, superior antibacterial capability and tissue adhesion can significantly promote healing of infectious cutaneous wound, tissue remodeling and regeneration.

Due to their versatile applications, gold (Au) and silver (Ag) nanoparticles (NPs) have been synthesized by many approaches, including green processes using plant extracts for reducing metal ions. In this work, we propose to use plant extract with active biomedical components for NPs synthesis, aiming to obtain NPs inheriting the biomedical functions of the plants. By using leaves extract of Clerodendrum inerme (C. inerme) as both a reducing agent and a capping agent, we have synthesized gold (CI-Au) and silver (CI-Ag) NPs covered with biomedically active functional groups from C. inerme. The synthesized NPs were evaluated for different biological activities such as antibacterial and antimycotic against different pathogenic microbes (B. subtilis, S. aureus, Klebsiella, and E. coli) and (A. niger, T. harzianum, and A. flavus), respectively, using agar well diffusion assays. The antimicrobial propensity of NPs further assessed by reactive oxygen species (ROS) glutathione (GSH) and FTIR analysis. Biofilm inhibition activity was also carried out using colorimetric assays. The antioxidant and cytotoxic potential of CI-Au and CI-Ag NPs was determined using DPPH free radical scavenging and MTT assay, respectively. The CI-Au and CI-Ag NPs were demonstrated to have much better antioxidant in terms of %DPPH scavenging (75.85% ± 0.67% and 78.87% ± 0.19%), respectively. They exhibited excellent antibacterial, antimycotic, biofilm inhibition and cytotoxic performance against pathogenic microbes and MCF-7 cells compared to commercial Au and Ag NPs functionalized with dodecanethiol and PVP, respectively. The biocompatibility test further corroborated that CI-Ag and CI-Au NPs are more biocompatible at the concentration level of 1–50 µM. Hence, this work opens a new environmentally-friendly path for synthesizing nanomaterials inherited with enhanced and/or additional biomedical functionalities inherited from their herbal sources.