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ZnTPY-chelated PbI2 nuclei effectively reduce the activation energy of perovskite crystallization resulting in higher conversion of PbI2 into uniform perovskite crystalline films, which ultimately improves the performance of perovskite solar cells.

The device efficiency of

Montmorillonite (MMT) has been frequently utilized as drug vehicles due to its high specific surface area, excellent cation exchange capacity and biocompatibility. However, the significant flocculation of MMT under physiological condition restricted its application to drug delivery. To conquer this problem, the graft-type PEGylated chitosan (PEG-CS) adducts were synthesized as intercalator to stabilize MMT dispersion. Through electrostatic attraction between the chitosan and MMT, the PEG-CS adducts were adsorbed on MMT surfaces and intercalated into MMT. The resulting PEG-CS/MMT nanosheets possessed PEG-rich surfaces, thus showing outstanding dispersion in serum-containing environment. Moreover, the physicochemical characterization revealed that the increased mass ratio of PEG-CS to MMT led to the microstructure transition of PEG-CS/MMT nanosheets from multilayered to exfoliated structure. Interestingly, the PEG-CS/MMT nanosheets with mass ratio of 8.0 in freeze-dried state exhibited a hierarchical lamellar structure organized by the intercalated MMT bundles and unintercalated PEG-CS domains. Notably, the multilayered PEG-CS/MMT nanosheets showed the capability of loading doxorubicin (DOX) superior to the exfoliated counterparts. Importantly, the DOX@PEG-CS/MMT nanosheets endocytosed by TRAMP-C1 cells liberated the drug progressively within acidic organelles, thereby eliciting cell apoptosis. This work provides a new strategy of achieving the controllable dispersion stability of MMT nanoclays towards application potentials in drug delivery.

Prion protein is composed of a structure-unsolved N-terminal domain and a globular C-terminal domain. Under limited trypsin digestion, mouse recombinant prion protein can be cleaved into two parts at residue Lys105. Here, we termed these two fragments as the N-domain (sequence 23-105) and the C-domain (sequence 106-230). In this study, the structural properties of the N-domain, the C-domain, and the full-length protein were explored using small-angle X-ray scattering, analytical ultracentrifugation, circular dichroism spectroscopy, and the 8-anilino-1-naphthalenesulfonic acid binding assay. The conformation and size of the prion protein were found to change sensitively under the solvent conditions. The positive residues in the sequence 23-99 of the N-domain were found to be responsible for the enhanced flexibility with the salt concentration reduced below 5 mM. The C-domain containing a hydrophobic patch tends to unfold and aggregate during a salt-induced structural collapse. The N-domain collapsed together with the C-domain at pH 5.2, whereas it collapsed independently at pH 4.2. The positively charged cluster (sequence 100-105) in the N-domain contributed to protecting the exposed hydrophobic surface of the C-domain.

Cellulose nanofibers functionalized with multiple aldehyde group were synthesized as the crosslinker to produce composite self-healing hydrogel and shape memory cryogel from chitosan. The hydrogel possessed effective self-healing (∼100% efficiency) and shear-thinning properties. The cryogel had macroporous structure, large water absorption (4300%), and high compressibility. Both hydrogel and cryogel were injectable. In particular, the cryogel (nanocellulose/chitosan 1:6) revealed thermally induced shape memory, the mechanism of which was elucidated by in situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) as changes in orientation of the induced crystalline structure during the shape memory program. The shape memory cryogel with a large size (15 mm × 10 mm × 1.1 mm) injected through a 16 G syringe needle was recoverable in 37 °C water. Moreover, the cryogel was cytocompatible and promoted cell growth. The nanocellulose-chitosan composite hydrogel and cryogel are injectable and degradable biomaterials with adjustable mechanical properties for potential medical applications.

The Brill transition in nylon 6/6 is generally perceived as a fully reversible solid–solid transformation between a low-temperature triclinic lattice (α-phase) and a high-temperature pseudohexagona...

There have been several studies on the catalytic activity of the hydrogen evolution reaction (HER) using ultralow loading of Pt catalysts or even Pt single atom catalysts. However, Pt single atom deposited on the surface of the carbon or metal oxide material has some drawbacks, such as high possibility of Pt desorption from the supported material in the electrolyte. Besides, from the reaction mechanism perspective, each Pt atom in this type of catalyst is too far to achieve high HER efficiency via the Tafel reaction pathway. In this work, gold nanodendrites (Au NDs) with high facet surface were chosen as the supported materials for studying the relation between the low loading amount of Pt atoms and the reaction mechanism of the HER activity. The atomic deposition of Pt atoms on the surface of Au NDs can be controlled effectively using a constant-current synthetic method. It was found that the HER electrocatalytic activity of ultralow Pt loading catalyst, with Pt atoms to total surface atoms of Au NDs (O-Pt on Au NDs) of 5.5%, could achieve high efficiency via the Tafel reaction pathway, showing a low overpotential of ∼18 mV at a current density of 10 mA cm−2 and a small Tafel slope of ∼31 mV dec−1, which is close to that of commercial Pt/C with 20 wt% Pt. As confirmed by Inductively Coupled Plasma Mass Spectrometry(ICP-MS), the Pt loading amount of O-Pt on Au NDs was ∼3.8 ± 0.2 μg cm−2 on a physical area of carbon fiber paper. The turnover frequency (TOF) of O-Pt on Au NDs was found to be 40.1 ± 2.5 H2 per s at 50 mV. This work provides a feasible approach to control the atomic deposition of Pt on a specific substrate as an active catalyst for various catalytic applications.

A recent report on the azo coupling of 4-nitrobenzo-15-crown-ether (4NB15C) and 4-nitrothiophenol (4NTP) indicated that the reaction barrier could be reduced greatly with surface plasmonic effects on silver dendritic nanostructures in aqueous solution. Accordingly, an azo coupling reaction mechanism was proposed based on one or two SERS peaks. Toward a profound understanding of this azo coupling reaction mechanism, it is crucial to scrutinize the origin of the full SERS spectrum. Here, we construct a molecular model consisting of 4NTP and 4NB15C on an Ag7 cluster that simulates a silver dendritic nanostructure, and investigate the SERS spectra of the azo coupling of these two molecules. We propose five different adsorption sites and 13 different orientations of 4NTP on the Ag7 cluster and optimize the geometries of the five configurations. With each optimized configuration of 4NTP adsorbed on Ag7, we further consider the azo coupling product with a 4NB15C molecule and simulate the corresponding Raman spectra. Comparing the measured Raman spectra and model analysis, we conclude that the azo coupling reaction depends decisively on a parallel molecular orientation of the adsorbed 4NTP relative to the facets of Ag7, the orientation of which further directs the subsequent reaction for the product of 4NB15C–4NTP.

Rationally utilizing and developing synthetic units is of particular significance for the design of high-performance non-fullerene small-molecule acceptors (SMAs). Here, a thieno[3,2-b]pyrrole synthetic unit was employed to develop a set of SMAs (ThPy1, ThPy2, ThPy3 and ThPy4) by changing the number or the position of the pyrrole ring in the central core based on a standard SMA of IT-4Cl, compared to which the four thieno[3,2-b]pyrrole-based acceptors exhibit bathochromic absorption and upshifted frontier orbital energy level due to the strong electron-donating ability of pyrrole. As a result, the polymer solar cells (PSCs) of the four thieno[3,2-b]pyrrole-based acceptors yield higher open-circuit voltage and lower energy loss relative to those of the IT-4Cl-based device. What is more, the ThPy3-based device achieves a power conversion efficiency (PCE) (15.3%) and an outstanding fill factor (FF) (0.771) that are superior to the IT-4Cl-based device (PCE = 12.6%, FF = 0.758). The ThPy4-based device realizes the lowest energy loss and the smallest optical band gap, and the ternary PSC device based on PM6:BTP-eC9:ThPy4 exhibits a PCE of 18.43% and a FF of 0.802. Overall, this work sheds light on the great potential of thieno[3,2-b]pyrrole-based SMAs in realizing low energy loss and high PCE. Four heteroheptacene-based acceptors using thieno[3,2-b]pyrrole building block were developed for the first time, and all the four acceptors-based devices realized high performance and low energy loss. Funding Agencies|National Key Research and Development Program of China - Ministry of Science and Technology [2019YFA0705900]; Basic and Applied Research Major Programme of Guangdong Province [2019B030302007]; National Natural Science Foundation of China [91433202]; Shenzhen Technology and Innovation Commission through Shenzhen Fundamental Research Program [JCYJ20200109140801751]; Hong Kong Innovation and Technology Commission [ITC-CNERC14SC01]; Foshan-HKUST [FSUST19-CAT0202]; Hong Kong Research Grants Council (RIF project) [R6021-18]; Hong Kong Research Grants Council (CRF project) [C6023-19G]; Hong Kong Research Grants Council (GRF project) [16310019, 16310020]

Hierarchically porous carbon materials with interconnected frameworks of macro- and mesopores are desirable for electrochemical applications in biosensors, electrocatalysis, and supercapacitors. In this study, we report a facile synthetic route to fabricate hierarchically porous carbon materials by controlled macro- and mesophase separation of a mixture of polystyrene

After randomly incorporating 2–21 mol % of 3-methylstyrene (3MS) or 4-methylstyrene (4MS) into the syndiotactic polystyrene (sPS) backbone, the effects of the comonomer units on the equilibrium mel...

Structure-based stabilization of protein–protein interactions (PPIs) is a promising strategy for drug discovery. However, this approach has mainly focused on the stabilization of native PPIs, and non-native PPIs have received little consideration. Here, we identified a non-native interaction interface on the three-dimensional dimeric structure of the N-terminal domain of the MERS-CoV nucleocapsid protein (MERS-CoV N-NTD). The interface formed a conserved hydrophobic cavity suitable for targeted drug screening. By considering the hydrophobic complementarity during the virtual screening step, we identified 5-benzyloxygramine as a new N protein PPI orthosteric stabilizer that exhibits both antiviral and N-NTD protein-stabilizing activities. X-ray crystallography and small-angle X-ray scattering showed that 5-benzyloxygramine stabilizes the N-NTD dimers through simultaneous hydrophobic interactions with both partners, resulting in abnormal N protein oligomerization that was further confirmed in the cell. This unique approach based on the identification and stabilization of non-native PPIs of N protein could be applied toward drug discovery against CoV diseases.

The formation of helical assemblies from achiral supramacromolecules has been a highly mysterious process, but is of interest for the generation of a variety of structures and properties. Herein, novel hierarchical superhelices are developed from self-assembly of achiral dendron-jacketed block copolymers (DJBCPs). The presence of focal asymmetry in both the stereochemistry of the dendrons (donors) and interactive binding sites of the copolymer chains (acceptors) plays a pivotal role in generating a spontaneous symmetry breaking through tailored donor–acceptor matching via hydrogen bonding. The focal asymmetry, on a scale of several nanometers, propagates to helical twists of the achiral DJBCP hierarchical assemblies over hundreds of nanometers, such that the primary molecular asymmetry sequentially triggers a secondary helical conformation of the dendron-jacketed blocks, then tertiary supramolecular helical assemblies and eventually quaternary superhelices. The helical twisting power of the superhelices is tunable using the dendron grafting ratio, indicating that the magnitude of helical twisting can be quantitatively adjusted from local to entire structures.

Aptamer selection against novel infections is a complicated and time-consuming approach. Synergy can be achieved by using computational methods together with experimental procedures. This study aims to develop a reliable methodology for a rational aptamer in silico et vitro design. The new approach combines multiple steps: (1) Molecular design, based on screening in a DNA aptamer library and directed mutagenesis to fit the protein tertiary structure; (2) 3D molecular modeling of the target; (3) Molecular docking of an aptamer with the protein; (4) Molecular dynamics (MD) simulations of the complexes; (5) Quantum-mechanical (QM) evaluation of the interactions between aptamer and target with further analysis; (6) Experimental verification at each cycle for structure and binding affinity by using small-angle X-ray scattering, cytometry, and fluorescence polarization. By using a new iterative design procedure, structure- and interaction-based drug design (SIBDD), a highly specific aptamer to the receptor-binding domain of the SARS-CoV-2 spike protein, was developed and validated. The SIBDD approach enhances speed of the high-affinity aptamers development from scratch, using a target protein structure. The method could be used to improve existing aptamers for stronger binding. This approach brings to an advanced level the development of novel affinity probes, functional nucleic acids. It offers a blueprint for the straightforward design of targeting molecules for new pathogen agents and emerging variants.

The large non-radiative recombination is the main factor that limits state-of-the-art organic solar cells (OSCs). In this work, two novel structurally similar oligomers (named 5BDTBDD and 5BDDBDT) with D-A-D-A-D and A-D-A-D-A configuration are synthesized for high-performance ternary OSCs with low energy loss. As third components, these PM6 analogue oligomers effectively suppress the non-radiative recombination in OSCs. Although the highest occupied molecular orbital (HOMO) levels of 5BDTBDD and 5BDDBDT are higher than that of PM6, the oligomers enabled ultra-high electroluminescence quantum efficiency (EQE

Structure and composition of the unilamellar vesicles (ULV) formed with catanionic surfactant of sodium dodecylsulfate (SDS) and cetyltrimethylammonium bromide (CTAB) are revealed using small-angle X-ray and neutron scattering (SAXS and SANS) and freeze-fracture-replication transmission electron microscopy (FFR-TEM). Imaging and scattering results consistently indicate a globular shape of the ULV, having a core size of 48 nm and a bilayer thickness of 32 A; the bilayer comprises a central aliphatic shell of 24 A, sandwiched by two headgroup shells, each of ca. 4 A thickness. From the zero-angle scattering intensity ratio of the SAXS and SANS data, a SDS/CTAB composition ratio of 3:4 for the ULV bilayer is deduced. Poly(oxyethylene-b-oxypropylene-b-oxyethylene) (P123), a triblock copolymer, is found to intervene into the ULV bilayer of the catanionic surfactant in solution, leading to successively enlarged complex ULV, as P123 concentration in the solution increases. The ULV of SDS/CTAB is saturated with P123-loading after a critical concertation of 0.067 mM P123; thereafter, formation and proliferation of constant-sized, P123-based core-shell micelles are observed with increase of P123 concentration. A structural model of P123-embedded ULV of the catanionic surfactant is proposed. These results suggest a capacity and limits of using the catanionic ULV as molecule carriers.

Electron donors and acceptors in organic solar cells (OSCs) shall strike a favorable vertical phase separation that acceptors and donors have sufficient contact and gradient accumulation near the cathodes and anodes, respectively. Random mixing of donors/acceptors at surface will result in charge accumulation and severe recombination for low carrier-mobility organic materials. However, it is challenging to tune the vertical distribution in bulk-heterojunction films as they are usually made from a well-mixed donor/acceptor solution. Here, for the first time, it presents with solid evidence that the commonly used 1-chloronaphthalene (CN) additive can tune the donor/acceptor vertical distribution and establish the mechanism. Different from the previous understanding that ascribed the efficiency enhancement brought by CN to the improved molecular stacking/crystallization, it is revealed that the induced vertical distribution is the dominant factor leading to the significantly increased performance. Importantly, the vertical distribution tunability is effective in various hot nonfullerene OSC systems and creates more channels for the collection of dissociated carriers at corresponding organic/electrode interfaces, which contributes the high efficiency of 18.29%. This study of the material vertical distribution and its correlation with molecular stacking offers methods for additives selection and provides insights for the understanding and construction of high-performance OSCs.

For undulator hard X-ray beamlines of a wide energy range, the beam intensity control is often needed to regulate the photon flux impinging on delicate detectors. Despite the capability of state-of-the-art X-ray pixel detectors being greatly advanced recently, the frontier undulator beamlines in synchrotron facilities often carry outstanding photon fluxes that are sometimes too high for certain measurements. Here, we report a developed protocol that allows intensity attenuation of an X-ray beam in the 4-23 keV energy range with flexible attenuation factors; a prototype is installed and tested on the 13A biological small-angle X-ray scattering beamline of the 3 GeV Taiwan Photon Source (TPS) of the National Synchrotron Radiation Research Center, Hsinchu, Taiwan. The intensity attenuation system is modified from a commercially available pneumatically actuated, vacuum-type precision X-ray attenuator of ADC ABS-300; the system provides beam attenuation factors covering 8 orders of intensity attenuation for an X-ray beam in 4-23 keV. This was achieved with selected combinations of 10 sets of metal foils comprising different thicknesses of Al, Ti, Cu, and Ta foils. A user-friendly protocol is established to automatically compare a subscribed attenuation factor with all the possible attenuation factors from the 1024 combinations of the 10 sets of foils in the X-ray energy used, and determine a set of the metal foils having a best-matched attenuation factor. Calculation of beam intensity attenuations with the selected foils is coded with Python and integrated into the Experimental Physics and Industrial Control System (EPICS). The input of an attenuation factor is done through a graphical display of the attenuator system based on the Control System Studio (CSS). The developed X-ray beam attenuation system provides a convenient and intuitive beam intensity control and has the potential to be adopted in future beamlines.

Rationally utilizing and developing synthetic units is of particular significance for the design of high-performance non-fullerene small-molecule acceptors (SMAs). Here, a thieno[3

Microporous round cake-like (diameter: 900 ± 100 nm) MIL-125(Ti) carrier with a central metal (Ti) exhibiting bio-affinity and possessing a great potential to be used as drug release platform, has been synthesized in the present study. The thermal and pH responsiveness of drug delivery systems (DDS) are the most important parameters for drug release and can be provided through polymer coating techniques. The Pluronic F127 (F127) and chitosan (CH) monomers were inserted into the crystal lattice of MIL-125(Ti) carrier during the de novo synthesis process, which were subsequently loaded with doxorubicin (DOX). The results reveal particle size changes (ranged between 30 and 50 %) from the original size of the MIL-125(Ti) carrier in response to temperature and pH when the carrier reaches acid environment. The drug release profiles have been completed through self-design device, which provides for the real-time release in the DOX amounts via UV-Vis spectra. The kinetics analysis was used to evaluate the R

Sub-monolayer Pt-modified Au dendrites (Au-Ds) were successfully synthesized and characterized using several techniques. The resulting Pt-modified Au-Ds effectively combined component catalytic properties and plasmonic optical properties. Results obtained from comprehensive kinetics experiments revealed that Pt-modified Au-Ds serve as an ideal photoelectocatalyst for the formic acid oxidation reaction (FAOR). Electro- and photoelectrocatalytic FAOR was carried out via the same dehydrogenation pathway on a high-efficiency Pt-modified Au-D surface with a low activation energy of 35.4 kJ mol−1. The contribution from the photo-enhanced electrocatalytic effect reached 68% in the Tafel region. Photoelectrocatalysis and the photo-thermal effect synchronously boosted the FAOR on Pt-modified Au-Ds under illumination. Chronoamperometry results indicated that Pt-modified Au-Ds exhibit excellent stability and long-term durability for the FAOR.

In this study, small-angle X-ray scattering (SAXS) is successfully employed to investigate the structure of the DPPC/diC7PC disc-shaped bicelles incorporated with different amounts of C16-PEG2000-Ceramide lipids. The incorporation of the C16-PEG2000-Ceramide lipids could provide an antifouling capability to the bicelle for biomedical applications. However, traditionally it is believed that most of the incorporated PEGlylated lipids should lie in the rim of the disc-shaped bicelle. In this study, high sensitivity SAXS reveals the distribution of the added C16-PEG2000-Ceramide lipids in both the planar region and in the rim of the bicelle. The PEG brushes of C16-PEG2000-Ceramide lipids form a second shell outside the lipid headgroup shell of the bicelle. A double shell disc bicelle model is used in analyzing the SAXS data. The lipid density of C16-PEG2000-Ceramide in the rim is found to be about 1.7 times the C16-PEG2000-Ceramide lipid density in the planar region for all three C16-PEG2000-Ceramide concentrations, 1, 2, and 3 mM. Moreover, the bicelle core radius can be predicted well using the actual molecular ratio of lipids in the planar region to the lipids in the rim of the bicelles in the model calculation.

The diblock copolymer polystyrene-block-poly(N-methyl 4-vinylpyridine iodide) (PS-b-P4VPQ) with the molecular weight of PS 3.5 × 103 g/mol and P4VPQ 11.6 × 103 g/mol forms core-shell polymer micelles in aqueous solution. The cationic brush shell of the polymer micelle can be used to accommodate hydrophilic drugs and biomolecules, such as DNA, for biomedical applications. It is essential to understand how biomolecules are adsorbed within the brush layer. Here we investigated the interaction of the cationic brush of the polymer micelle with DNA by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). It is found when adding only relatively small amounts of on average 30 base pairs (bp) DNA, at 19.6 and 39.2 μM for 0.1 mM PS-b-P4VPQ, most of the polymer micelle/DNA complexes remain well dispersed. The brush layer of the polymer micelles are slightly swelled due to the adsorption of DNA within the brush layer. When the DNA concentration is increased to 58.8 μM or higher, the polymer micelle/DNA complexes form closely packed agglomerates. At high DNA concentrations, some adsorbed DNA will start to build up at the edge or surface of the brush layer which could induce aggregation of the polymer micelle/DNA complexes. This means that it is possible to prepare mostly dispersed polymer/DNA complexes by keeping the DNA concentration below the aggregation concentration. The well dispersed polymer micelle/DNA complexes are advantageous for many DNA related biomedical applications.