Biobased and biodegradable films exhibiting circularly polarized room temperature phosphorescence.

There is interest in developing sustainable materials displaying circularly polarized room-temperature phosphorescence, which have been scarcely reported. Here, we introduce biobased thin films exhibiting circularly polarized luminescence with simultaneous room-temperature phosphorescence. For this purpose, phosphorescence-active lignosulfonate biomolecules are co-assembled with cellulose nanocrystals in a chiral construct. The lignosulfonate is shown to capture the chirality generated by cellulose nanocrystals within the films, emitting circularly polarized phosphorescence with a 0.21 dissymmetry factor and 103 ms phosphorescence lifetime. By contrast with most organic phosphorescence materials, this chiral-phosphorescent system possesses phosphorescence stability, with no significant recession under extreme chemical environments. Meanwhile, the luminescent films resist water and humid environments but are fully biodegradable (16 days) in soil conditions. The introduced bio-based, environmentally-friendly circularly polarized phosphorescence system is expected to open many opportunities, as demonstrated here for information processing and anti-counterfeiting.

Design, synthesis, and evaluation of pirfenidone-NSAIDs conjugates for the treatment of idiopathic pulmonary fibrosis.

Idiopathic pulmonary fibrosis (IPF) is a fatal, chronic and progressive lung disease that threaten public health like many cancers. In this study, targeting the significant driving factor, inflammatory response, of the IPF, several conjugates of pirfenidone (PFD) with non-steroidal anti-inflammatory drugs (NSAIDs), along with their derivatives, were designed and synthesized to enhance the anti-IPF potency of PFD. Among these compounds, the (S)-ibuprofen-PFD conjugate 5b exhibited the most potent anti-proliferation activity against NIH3T3 cells, demonstrating up to a 343-fold improvement compared to PFD (IC50 = 0.04 mM vs IC50 = 13.72 mM). Notably, 5b exhibited superior activity in inhibiting the migration of macrophages induced by TGF-ß compared to PFD. Additionally, 5b demonstrated significant suppression of TGF-ß-induced migration of NIH3T3 cells and induction of apoptosis in NIH3T3 cells. Mechanistic studies revealed that 5b reduced the expression of collagen I and α-SMA by inhibiting the TGF-ß/SMAD3 pathway. In a bleomycin-induced pulmonary fibrosis model, treatment with 5b (40 mg/kg/day, orally) exhibited a more pronounced effect on reducing the degree of histopathological changes in lung tissue and alleviating collagen deposition compared to PFD (100 mg/kg/day, orally). Moreover, 5b could block the expression of collagen I, α-SMA, fibronectin, and pro-inflammatory factors (IL-6, IFN-γ, and TNF-α) compared to PFD, while demonstrating low toxicity in vivo. These preliminary results indicated that the hybridization of PFD with NSAIDs represented an effective modification approach to improve the anti-IPF potency of PFD. Consequently, 5b emerged as a promising candidate for the further development of new anti-IPF agents.

Liquid Crystal Assembly for Ultra-dissymmetric Circularly Polarized Luminescence and Beyond.

Circularly polarized luminescence (CPL) is attracting much interest because it can carry extensive optical information. CPL shows left- or right-handedness and can be regarded as part of high-level visual perception to supply an extra dimension of information with regard to regular light. A key to meeting the needs for practical applications is to develop the emerging field of ultra-dissymmetric CPL. Chiral liquid crystal (LC) assemblies─otherwise referred to as cholesteric liquid crystals (CLCs)─are essentially organized helical superstructures with a highly ordered one-dimensional orientation, and distinctly superior to regular helical supramolecules. CLCs can achieve a perfect equilibrium of molecular short-range interaction and long-range orientational order, enabling molecule-scale chirality on a helical pitch and observable scale. LC assembly could be an ideal strategy for amplifying chirality, making it accessible to ultra-dissymmetric CPL. Herein, we focused on some basic but important issues regarding CPL: (i) How can CPL be created from chiral dyes? (ii) Is the chirality of luminescent dyes an essential factor for the generation of CPL? That is, can all chiral dyes emit CPL and vice versa? (iii) How can CPL be transferred within intermolecular systems, and what principles of CPL transmission should be followed? Given these queries and our work, in this Perspective we discuss the generation, transmission, and modulation of CPL with chiral LC assembly, aiming to design and build up novel chiroptical materials. Recent applications of CPL-active LC microstructures in three-dimensional displays, circularly polarized lasers, and asymmetric catalysis are also discussed.

Molecular Insights into the Improved Bioactivity of Interferon Conjugates Attached to a Helical Polyglutamate.

Attaching polymers, especially polyethylene glycol (PEG), to protein drugs has emerged as a successful strategy to prolong circulation time in the bloodstream. The hypothesis is that the flexible chain wobbles on the protein's surface, thus resisting potential nonspecific adsorption. Such a theoretical framework may be challenged when a helical polyglutamate is used to conjugate with target proteins. In this study, we investigated the structure-activity relationships of polyglutamate-interferon conjugates P(EG3Glu)-IFN using molecular simulations. Our results show that the local crowding effect induced by oligoethylene glycols (i.e., EG3) is the primary driving force for helix formation in P(EG3Glu), and its helicity can be effectively increased by reducing the free volume of the two termini. Furthermore, it was found that the steric hindrance induced by IFN is not conductive to the helicity of P(EG3Glu) but contributes to its dominant orientation relative to interferon. The orientation of IFN relative to the helical P(EG3Glu) can help to protect the protein drug from neutralizing antibodies while maintaining its bioactivity. These findings suggest that the helical structure and its orientation are critical factors to consider when updating the theoretical framework for protein-polymer conjugates.

A Double Atomic-Tuned RuBi SAA/Bi@OG Nanostructure with Optimum Charge Redistribution for Efficient Hydrogen Evolution.

Charge redistribution on surface of Ru nanoparticle can significantly affect electrocatalytic HER activity. Herein, a double atomic-tuned RuBi SAA/Bi@OG nanostructure that features RuBi single-atom alloy nanoparticle supported by Bi-O single-site-doped graphene was successfully developed by one-step pyrolysis method. The alloyed Bi single atom and adjacent Bi-O single site in RuBi SAA/Bi@OG can synergistically manipulate electron transfer on Ru surface leading to optimum charge redistribution. Thus, the resulting RuBi SAA/Bi@OG exhibits superior alkaline HER activity. Its mass activity is up to 65000 mA mg-1 at an overpotential of 150 mV, which is 72.2 times as much as that of commercial Pt/C. DFT calculations reveal that the RuBi SAA/Bi@OG possesses the optimum charge redistribution, which is most beneficial to strengthen adsorption of water and weaken hydrogen-adsorption free energy in HER process. This double atomic-tuned strategy on surface charge redistribution of Ru nanoparticle opens a new way to develop highly efficient electrocatalysts.

Modulating the Site Density of Mo Single Atoms to Catch Adventitious O Atoms for Efficient H2 O2 Oxidation with Light.

Coordination environment and site density have great impacts on the catalytic performance for single atoms (SAs). Herein, the site density of Mo-SAs on red polymeric carbon nitrides (RPCN) is modulated via a local carbonization strategy to controllably catch adventitious O atoms from open environment. The addition of melamine derivants with hydrocarbyl chains induces local carbonization during RPCN pyrolysis. These local carbonization regions bring abundant graphitic N3C to anchor Mo-SAs, and most of Mo-SAs catch the O atoms in air, forming the O2 -covered Mo-N3 coordination. The dopants of carbon source with different structures and amounts can modulate the site density of Mo-SAs, therefore controlling the amounts of coordinated O atoms. Furthermore, coordinated O atoms around Mo-SAs construct the catalytic environment with Lewis base and gather photo-generated electrons under light. Such O-covered Mo-SAs endow RPCN materials (Mo-RPCN) with a strong ability for hydrogen abstraction, leading to the 99.51% ratio (28.8 mmol min-1  g-1 ) rate for thioanisole conversion with H2 O2 assisted advance oxidation technology. This work brings a new sight on the coordinated atoms dominant oxidation process.

Design, synthesis and biological evaluation of 3-aryl-7-hydroxy scopoletin derivatives as autophagy activators against tumorigenesis.

A natural product scopoletin, which also contains an ortho-substituted phenolic structure in its skeleton, was found in some medicinal plants. In this study, to develop scopoletin-based autophagy activators, various aryl substitutes were introduced at the 3-positon or 4-position of scopoletin skeleton with the ortho-substituted phenolic structure retained. A total of twenty-three derivatives were synthesized, evaluated for their antiproliferation activity against four cancer cells (MCF-7, HeLa, PC3, and MGC803), and discussed for their structure-activity relationships (SARs). Among these derivatives, 5c was the most potent compound with an excellent improvement of antiproliferation activity against PC3 and MGC803 cells compared to the parental scopoletin. 5c displayed up to 17.9- and 5.7-fold improvement of antiproliferation activities against PC3 and MGC803 cells compared to 5-FU (IC50 = 0.14 µM vs IC50 = 2.50 µM, IC50 = 1.02 µM vs IC50 = 5.81 µM), respectively. Moreover, 5c showed excellent selectivity between cancer cells and one normal cell (GES-1). Further mechanism investigations confirmed that 5c inhibited PC3 and MGC803 cell proliferation via inducing autophagy. Interestingly, 5c also induced mitochondria-mediated apoptosis in PC3 cells but not in MGC803 cells. Moreover, 5c possessed the ability to suppress colony formation and migration of PC3 and MGC803 cells. In addition, 5c arrested the cell cycle at the G2/M phase of PC3 cells.

Retrieving Spectra of Pure Components from the DOSY-NMR Experiment via a Comprehensive Approach Involving the 2D Asynchronous Spectrum, 2D Quotient Spectrum, and Genetic Algorithm Refinement.

When diffusion coefficients of different components in a mixture are similar, NMR spectra of pure individual components are difficult to be obtained via a diffusion-ordered spectroscopy (DOSY) experiment. Two-dimensional correlation spectroscopy (2D-COS) is used to analyze the data from the DOSY experiment. Through the properties of the systematic absence of cross-peak (SACP) in the 2D asynchronous spectra, spectra of pure components can be obtained even if their diffusion coefficients are similar. However, fluctuations in peak-position and peak-width are often unavoidable in NMR spectra, which makes SACPs unrecognizable. To address the problem, a 2D quotient spectrum is used to identify the masked SACPs. However, undesirable interference peaks due to the fluctuations in peak-position and peak-width are still present when we extract a spectrum of a component by slicing the 2D asynchronous spectrum across the SACP. A genetic algorithm (GA) is used to select a suitable subset of spectra where the diversities of peak-position and peak-width are significantly reduced. Then, we used the selected spectra to construct a refined 2D asynchronous spectrum so that the spectra of pure components with significant attenuated interference can be obtained. The above approach has been proven to be effective on a model system and a real-world example, demonstrating that 2D-COS possesses a bright perspective in the analysis of the bilinear data from DOSY experiments.

Photo-thermo-induced room-temperature phosphorescence through solid-state molecular motion.

The development of smart-responsive materials, in particular those with non-invasive, rapid responsive phosphorescence, is highly desirable but has rarely been described. Herein, we designed and prepared a series of molecular rotors containing a triazine core and three bromobiphenyl units: o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ. The bromine and triazine moieties serve as room temperature phosphorescence-active units, and the bromobiphenyl units serve as rotors to drive intramolecular rotation. When irradiated with strong ultraviolet photoirradiation, intramolecular rotations of o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ increase, successively resulting in a photothermal effect via molecular motions. Impressively, the photothermal temperature attained by p-Br-TRZ is as high as 102 °C, and synchronously triggers its phosphorescence due to the ordered molecular arrangement after molecular motion. The thermal effect is expected to be important for triggering efficient phosphorescence, and the photon input for providing a precise and non-invasive stimulus. Such sequential photo-thermo-phosphorescence conversion is anticipated to unlock a new stimulus-responsive phosphorescence material without chemicals invasion.

Synthesis and structure-activity relationships of pirfenidone derivatives as anti-fibrosis agents in vitro.

Pirfenidone (PFD) was the first approved drug by FDA for the treatment of idiopathic pulmonary fibrosis (IPF). However, the rapid metabolism of 5-methyl of PFD increases the risk of side effects in clinics. Thus, in this paper, a common practice that a stable amide bond linking various groups used to replace 5-methyl of PFD in medicinal chemistry was applied, and total 18 PFD derivatives were synthesized. All compounds were investigated for their antiproliferation activities against NIH3T3 cells and the structure-activity relationships of the target compounds were also discussed. Among them, YZQ17 possessed potent antiproliferation activity compared to PFD and better potency in inhibiting TGF-ß-induced migration of NIH3T3 cells at a much lower concentration than that of PFD. In addition, YZQ17 dramatically inhibited the expression levels of fibrotic markers α-SMA, collagen I, and fibronectin. Moreover, further mechanistic studies confirmed that YZQ17 exhibited this considerable anti-fibrosis activity via the TGF-ß/Smad2/3 dependent pathway. Finally, the results of human and rat liver microsomes assay in vitro and pharmacokinetic assay in rats confirmed that YZQ17 showed better pharmacokinetics than that of PFD. Collectively, the preliminary study of PFD derivatives modified by the amide group indicated that YZQ17 could be regarded as a lead compound for further investigation and optimization.

Novel Method for Extracting the Spectrum of a Supramolecular Complex via a Comprehensive Approach Involving Two-Dimensional Correlation Spectroscopy, Genetic Algorithm, and Grid Searching.

A supramolecular complex may be formed by two solutes via a weak intermolecular interaction in a solution. The spectrum of the complex is often inundated by the spectra of the solutes that are not involved in the intermolecular interaction. Herein, a novel spectral analysis approach is proposed to retrieve the spectrum of the supramolecular complex. First, a two-dimensional (2D) asynchronous spectrum is constructed. Then, a genetic algorithm is used to obtain a heuristic spectrum of the supramolecular complex. The heuristic spectrum is a linear combination of the spectrum of the complex and the spectrum of a solute. The coefficients of the linear combination are then obtained, according to which the equilibrium constants are invariant among the sample solutions used to construct the 2D asynchronous spectrum. We have applied the approach to a supramolecular system formed by benzene and I2. In the analysis, several binding models are evaluated, and a benzene molecule interacting with two iodine molecules via halogen bonding turns out to be the only possible model. Hence, the characteristic band of the benzene/I2 supramolecular complex around 1819 cm-1 in the Fourier transform infrared (FTIR) spectrum and the corresponding equilibrium constant are obtained. The above results indicate that the novel approach provides a chance to get new insight into various intermolecular interactions studied by spectroscopy.

Circularly Polarized Fluorescence Resonance Energy Transfer (C-FRET) for Efficient Chirality Transmission within an Intermolecular System.

The occurrence and transmission of chirality is a fascinating characteristic of nature. However, the intermolecular transmission efficiency of circularly polarized luminescence (CPL) remains challenging due to poor through-space energy transfer. We report a unique CPL transmission from inducing the achiral acceptor to emit CPL within a specific liquid crystal (LC)-based intermolecular system through a circularly polarized fluorescence resonance energy transfer (C-FRET), wherein the luminescent cholesteric LC is employed as the chirality donor, and rationally designed achiral long-wavelength aggregation-induced emission (AIE) fluorophore acts as the well-assembled acceptor. In contrast to photon-release-and-absorption, the chirality transmission channel of C-FRET is highly dependent upon the energy resonance in the highly intrinsic chiral assembly of cholesteric LC, as verified by deliberately separating the achiral acceptor from the chiral donor to keep it far beyond the resonance distance. This C-FRET mode provides a de novo strategy concept for high-level information processing for applications such as high-density data storage, combinatorial logic calculation, and multilevel data encryption and decryption.

Peripherally Modified Tetraphenylethene: Emerging as a Room-Temperature Luminescent Disc-Like Nematic Liquid Crystal.

A blue-light-emitting liquid crystalline (LC) material was designed and prepared. By employing a twisted luminescent core (i.e., tetraphenylethene), four peripheral LC units with long alkyl chains and the small polar benzyl-ether-typed linking groups, the resulting material displayed a hexagonal columnar phase near room temperature and a disc-like nematic phase between 32 and 70 °C. The columnar LC showed a high quantum yield of 0.49 at 20 °C, and the efficient luminescence property was retained even in the isotropic phase at high temperature. Additionally, the fluidity of the nematic phase rendered the LC a non-volatile solvent, and the proper addition of a red dye led to the achievement of polarized white-light emission, which revealed a promising application prospect in LC display fabrication.

Quantitative Förster Resonance Energy Transfer: Efficient Light Harvesting for Sequential Photo-Thermo-Electric Conversion.

Light is essential to all life on the earth. Thus, highly efficient light-harvesting systems with the sequential energy transfer process are significant for using solar energy in photosynthesis. For developing an efficient light-harvesting system, a liquid aggregation-induced emission (AIE) dye TPE-EA is obtained, as a donor and solvent, which can light up the aggregation caused quenching (ACQ) Nile Red (NiR, acceptor) to construct a quantitative Förster resonance energy transfer (FRET) system in NiR⊂TPE-EA. Impressively, this FRET pair shows an impressive photothermal effect, producing a peak temperature of 119 °C while excited by UV light, with 37.8% of conversion efficiency. NiR⊂TPE-EA is quite different from most other photothermal materials, which require excitation with long wavelength light (>520 nm). Therefore, NiR⊂TPE-EA firstly converts the solar into thermal energy and then into electric energy to achieve sequential photo-thermo-electric conversion. Such sequential conversion, suitable for being excited by sunlight, is anticipated to unlock new and smart approaches for capturing solar energy.

Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer.

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal-optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system. Indeed, FRET exhibits strong S-curve dependence as temperature sweeps through the liquid crystal phase transformation. Such thermochromic materials, suitable for dynamic thermo-optical sensing and modulation, are anticipated to unlock new and smart approaches for controlling and directing light in stimuli-responsive devices.

Rapid Controllable Synthesis of Atomically Dispersed Co on Carbon under High Voltage within One Minute.

Developing a rapid and low cost approach to access atomically dispersed metal catalysts (ADMCs) supported by carbon is important but still challenging. Here, an electric flash strategy using high voltage for the rapid fabrication of carbon-supported ADMCs within 1 min is reported. Continuous plasma arc results in nitrogen-doped carbon ultrathin nanosheets, while an intermittent spark pulse constructs carbon hollow nanospheres via blasting effect, and both structures are decorated with atomically dispersed cobalt. The latter catalyst shows a half-wave potential of 0.887 V versus RHE (47 mV higher than commercial Pt/C) in an oxygen reduction reaction (ORR) in alkaline media. The authors' work paves the way to rapid synthesis of carbon-supported ADMCs at both low cost and mass production.

Investigation on the luminescence behavior of terbium acetylsalicylate/bilirubin system via 2D-COS approaches.

Terbium acetylsalicylate has been prepared, and the ethanol solution of the complex exhibits strong luminescence under the excitation of ultraviolet radiation. When a small amount of bilirubin solution is introduced into the solution containing a high concentration of terbium acetylsalicylate, a remarkable diminution of the luminescence of the terbium complex was observed. Investigations on the behavior and life-time of luminescence indicate that the quenching is not caused by forming a stable non-luminescent product via a reaction between terbium acetylsalicylate and bilirubin. A π-π interaction between the chromophore of bilirubin and the aromatic moiety of ligand was revealed via the pattern of cross peaks in the 2D asynchronous spectrum generated using the DAOSD (double asynchronous orthogonal sample design) approach. Such an interaction paves a route for energy transfer in the quenching process. The combination of a high concentration of the terbium complex and a long life-time of luminescence in the lanthanide complex/bilirubin system forms a special scenario: a bilirubin molecule by diffusion may visit and deactivate dozens of excited terbium complexes within the half-life period of the lanthanide complex. This is why a small amount of bilirubin can bring about the significant reduction of luminescence on the solution containing a high concentration of the terbium complex.

Amplifying the excited state chirality through self-assembly and subsequent enhancement via plasmonic silver nanowires.

The development of circularly polarized luminescent materials with a large luminescence dissymmetry factor (glum) is continuing to be a big challenge. Here, we present a general approach for amplifying circular polarization of circularly polarized luminescence (CPL) through intergrating molecular self-assembly and surface plasmon resonance (SPR). Molecular self-assembly could amplify the CPL performance. Subsequently, the composites built of nanoassemblies and achiral silver nanowires (AgNWs) show intense CPL activity with an amplified glum value. By applying an external magnetic field, the CPL activity of the nanoassemblies/AgNWs composites has been significantly enhanced, confirming a plasmon-enhanced circular polarization. Our design strategy based on SPR-enhanced circular polarization of the chiral emissive systems suggests that combining plasmonic nanomaterials with chiral organic materials could aid in the development of novel CPL active nanomaterials.

Room-Temperature Synthesis of Single Iron Site by Electrofiltration for Photoreduction of CO2 into Tunable Syngas.

Developing a convenient and effective method to prepare single-atom catalysts at mild synthetic conditions remains a challenging task. Herein, a voltage-gauged electrofiltration method was demonstrated to synthesize single-atom site catalysts at room temperature. Under regulation of the graphene oxide membrane, a bulk Fe plate was directly converted into Fe single atoms, and the diffusion rate of Fe ions was greatly reduced, resulting in an ultralow concentration of Fe2+ around the working electrode, which successfully prevented the growing of nuclei and aggregating of metal atoms. Monatomic Fe atoms are homogeneously anchored on the as-prepared nitrogen-doped carbon. Owing to the fast photoelectron injection from photosensitizers to atomically dispersed Fe sites through the highly conductive supported N-C, the Fe-SAs/N-C exhibits an outstanding photocatalytic activity toward CO2 aqueous reduction into syngas with a tunable CO/H2 ratio under visible light irradiation. The gas evolution rates for CO and H2 are 4500 and 4950 µmol g-1 h-1, respectively, and the tunable CO/H2 ratio is from 0.3 to 8.8. This article presents an efficient strategy to develop the single-atom site catalysts and bridges the gap between heterogeneous and homogeneous catalysts toward photocatalytic CO2 aqueous reduction into syngas.

Nanoimprint Lithography-Directed Self-Assembly of Bimetallic Iron-M (M=Palladium, Platinum) Complexes for Magnetic Patterning.

Self-assembly of d8 metal polypyridine systems is a well-established approach for the creation of 1D organometallic assemblies but there are still challenges for the large-scale construction of nanostructured patterns from these building blocks. We describe herein the use of high-throughput nanoimprint lithography (NIL) to direct the self-assembly of the bimetallic complexes [4'-ferrocenyl-(2,2':6',2''-terpyridine)M(OAc)]+ (OAc)- (M=Pd or Pt; OAc=acetate). Uniform nanorods are fabricated from the molecular self-organization and evidenced by morphological characterization. More importantly, when top-down NIL is coupled with the bottom-up self-assembly of the organometallic building blocks, regular arrays of nanorods can be accessed and the patterns can be controlled by changing the lithographic stamp, where the mold imposes a confinement effect on the nanorod growth. In addition, patterns consisting of the products formed after pyrolysis are studied. The resulting arrays of ferromagnetic FeM alloy nanorods suggest promising potential for the scalable production of ordered magnetic arrays and fabrication of magnetic bit-patterned media.