Injectable pH- and Ultrasound-Responsive Dual-Crosslinked Dextran/Chitosan/TiO2 Nanocomposite Hydrogels for Antibacterial Applications.

Combining exogenous and endogenous antibacterial mechanisms has been demonstrated to enhance therapeutic efficacy significantly. This study constructs an innovative type of exogenous and endogenous antibacterial nanocomposite hydrogels with injectable dual-crosslinked networks and dual-stimuli responsiveness. The primary network establishes imine bonds between the functionalized dextran featuring norbornenes and aldehydes (NorAld-Dex) and the quaternized chitosan (QCS). The imine bonds provide self-healing, injectability, and pH-responsiveness to the hydrogel network. The secondary network is established by integrating thiolated mesoporous silica-coated titanium dioxide nanoparticles (TiO2@MS-SH) into the hydrogel network via an ultrasound-activated thiol-norbornene reaction with NorAld-Dex. The microstructures and properties of NorAld-Dex/QCS/TiO2@MS-SH hydrogels can be fine-tuned by adjusting the sonication time to increase the amount of thiol-norbornene crosslinks in the network. Effective antibacterial performance of NorAld-Dex/QCS/TiO2@MS-SH hydrogels at low pH has been demonstrated with the synergistic effect of the acid-induced dissociation of the hydrogel network, protonated QCS, and the reactive oxygen species (ROS) generated by TiO2@MS-SH nanoparticles under ultrasound irradiation. In summary, NorAld-Dex/QCS/TiO2@MS-SH nanocomposite hydrogel is an advanced dual stimuli-responsive antibacterial platform with customizable microstructures and properties, offering great potential for biomedical applications.

Polar Aromatic Two-dimensional Dion-Jacobson Halide Perovskites for Efficient Photocatalytic H2 Evolution.

Polar materials with spontaneous polarization (Ps) have emerged as highly promising photocatalysts for efficient photocatalytic H2 evolution owing to the Ps-enhanced photogenerated carrier separation. However, traditional inorganic polar materials often suffer from limitations such as wide band gaps and poor carrier transport, which hinders their photocatalytic H2 evolution efficiency. Here, we rationally synthesized a series of isostructural two-dimensional (2D) aromatic Dion-Jacobson (DJ) perovskites, namely (2-(2-Aminoethyl)pyridinium)PbI4 (2-APDPI), (3-(2-Aminoethyl)pyridinium)PbI4 (3-APDPI), and (4-(2-Aminoethyl)pyridinium)PbI4 (4-APDPI), where 2-APDPI and 4-APDPI crystalize in polar space groups with piezoelectric constants (d33) of approximately 40 pm V-1 and 3-APDPI adopts a centrosymmetric structure. Strikingly, owing to the Ps-facilitated separation of photogenerated carriers, polar 2-APDPI and 4-APDPI exhibit a 3.9- and 2.8-fold increase, respectively, in photocatalytic H2 evolution compared to the centrosymmetric 3-APDPI. As a pioneering study, this work provides an efficient approach for exploring new polar photocatalysts and highlights their potential in promoting photocatalytic H2 evolution.

Multi-Functionalization of Single crystals Mediated by Gel-Incorporation: A Bioinspired Strategy.

Biominerals are inherently organic-inorganic crystal composites. Drawing inspiration from this biomineral structure, functionalized single crystals can be synthesized using the gel-grown method, resulting in the incorporation of gel-networks into the host crystals. By incorporating gel-networks, diverse guest materials, such as nanoparticles and dye molecules, can be uniformly and isotropically distributed within the crystals, thereby imparting non-intrinsic optical or magnetic properties to the host crystals. Additionally, gel-incorporation enhances the toughness and stability of the crystals as the incorporated gel-fibers and accompanying guest materials act as bridges to prevent crack propagation. Furthermore, gel-incorporation enables protein crystals to exhibit self-healing properties, which can be attributed to the dynamic bonding interaction between gel-networks and crystals. Notably, recent research has demonstrated that the incorporation of zwitterionic gel-networks enhances the charge effects on crystal morphology evolution as the charged groups become bound to the developing crystal surfaces, and their detachment is impeded by the interconnected gel-networks. Therefore, preparing single crystals with gel-incorporation is a remarkable strategy for synthesizing functionalized crystal materials.

Principles of Self-Repairing Ability of Tripodal Ligand-Stabilized Hybrid Cobalt Hydroxide Nanosheets for Alkaline Water Electrolysis.

Self-repairing catalysts are promising new materials for achieving long lifetime of alkaline water electrolyzers powered by renewable energy. Catalytic nanoparticles dispersed in an electrolyte were deposited on the anode to repair a catalyst layer by electrolysis. A hybrid cobalt hydroxide nanosheet modified with tris(hydroxymethyl)aminomethane on the surface (Co-ns) was used as a catalyst. Assuming a pseudo-first-order process, the rate constant of an electrochemical deposition was linearly correlated with the electrode potential during electrolysis. Thus, it is expected that the repair of the catalyst is automatically controlled by changes in the oxygen evolution reaction (OER) overpotential. The essential step of the electrochemical deposition was the anodic oxidation of Co2+ to Co3+ . Surface modification of Co-ns protects Co2+ against the autooxidation of Co2+ caused by the dissolved oxygen. The redox properties and organic modification of Co-ns make them well-suited for the self-repairing of anode catalysts.

Electrochemically Activated Expanded Graphite with Tailor-Made Pores for Magnesium-Organocation Hybrid Batteries.

Persisting limitations of lithium-ion batteries (LIBs) in terms of safety, energy and power density, natural resources, and the price call for expeditious research to develop the "beyond Li-ion" technologies. In this regard, magnesium-organocation hybrid batteries (MOHB) hold the potential to address the above issues associated with LIBs by utilizing abundant and inexpensive elements of magnesium and carbon for the anode and cathode, respectively. Moreover, magnesium metal anode is highly energy-dense yet less susceptible to the dendrite formation, enabling safer operation compared to lithium metal anodes. In this study, we targeted to increase the capacity and rate capability of porous carbon cathode of MOHB by generating tailor-made pores, which were provided by the interlayer accommodation of solvated organic cations with controlled sizes during the electrochemical activation of expanded graphite. Our electrochemically activated expanded graphite can be used as an efficient cathode in MOHB with enhanced kinetics, specific capacitance, and cycle life.

Morphological Evolution of Calcite Grown in Zwitterionic Hydrogels: Charge Effects Enhanced by Gel-Incorporation.

The incorporation of charged biomacromolecules is widely found in biomineralization. To investigate the significance of this biological strategy for mineralization control, gelatin-incorporated calcite crystals grown from gelatin hydrogels with different charge concentrations along the gel networks are examined. It is found that the bound charged groups on gelatin networks (amino cations, gelatin-NH3 + and carboxylic anions, gelatin-COO- ) play crucial roles in controlling the single-crystallinity and the crystal morphology. And the charge effects are greatly enhanced by the gel-incorporation because the incorporated gel networks force the bound charged groups on them to attach to crystallization fronts. In contrast, ammonium ions (NH4 + ) and acetate ions (Ac- ) dissolve in the crystallization media do not exhibit the similar charge effects because the balance of attachment/detachment make them more difficult to be incorporated. Employing the revealed charge effects, the calcite crystal composites with different morphologies can be flexibly prepared.

An Activatable Hybrid Organic-Inorganic Nanocomposite as Early Evaluation System of Therapy Effect.

Delays in evaluating cancer response to radiotherapy (RT) usually reduce therapy effect or miss the right time for treatment optimization. Hence, exploring timely and accurate methods enabling one to gain insights of RT response are highly desirable. In this study, we have developed an apoptosis enzyme (caspase-3) activated nanoprobe for early evaluation of RT efficacy. The nanoprobe bridged the nanogapped gold nanoparticles (AuNNPs) and the second near-infrared window (NIR-II) fluorescent (FL) molecules (IR-1048) through a caspase-3 specific peptide sequence (DEVD) (AuNNP@DEVD-IR1048). After X-ray irradiation, caspase-3 was activated to cut DEVD, turning on both NIR-II FL and PA imaging signals. The increased NIR-II FL/PA signals exhibited a positive correlation with the content of caspase-3. Moreover, the amount of the activated caspase-3 was negatively correlated with the tumor size. The results underscore the role of the caspase-3 activated by X-ray irradiation in bridging the imaging signals variation and tumor inhibition rate. Overall, activatable NIR-II FL/PA imaging was successfully used to timely predict and evaluate the RT efficacy. The evaluation system based on biomarker-triggered living imaging has the capacity to guide treatment decisions for numerous cancer types.

Joint Venture of Metal Cluster and Amphiphilic Cationic Minidendron Resulting in Near Infrared Emissive Lamellar Ionic Liquid Crystals.

Inorganic red-NIR emissive materials are particularly relevant in many fields like optoelectronic, bioimaging or solar cells. Benefiting from their emission in devices implies their integration in easy-to-handle materials like liquid crystals, whose long-range ordering and self-healing abilities could be exploited and influence emission. Herein, we present red-NIR emissive hybrid materials obtained with phosphorescent octahedral molybdenum cluster anions electrostatically associated with amphiphilic guanidinium minidendrons. Polarized optical microscopy and X-ray analysis show that while the minidendron chloride salts self-organize into columnar phases, their association with the dianionic metal cluster leads to layered phases. Steady-state and time-resolved emission investigations demonstrate the influence of the minidendron alkyl chain length on the phosphorescence of the metal cluster core.

Organo-Polyoxometalate-Based Hydrogen-Bond Catalysis.

Several urea-inserted organo-polyoxometalates (POMs) derived from polyoxotungstovanadate [P2 V3 W15 O61 ]9- were prepared. The insertion of the carbonyl into the polyoxometallic framework activates the urea toward Hydrogen-bond catalysis. This was shown on the Friedel-Crafts arylation of trans-ß-nitrostyrene. Modelling shows that the most stable form of the organo-POMs features a cis-trans arrangement of the two N-H bonds, but that the likely catalytically active trans-trans form is accessible at room temperature. Finally, it is possible that the oxo substituents next to the vanadium atoms may help the approach of the nucleophile via H-bonding.

An Organic-Inorganic Perovskitoid with Zwitterion Cysteamine Linker and its Crystal-Crystal Transformation to Ruddlesden-Popper Phase.

We demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous.

Luminescent PMMA Films and PMMA@SiO2 Nanoparticles with Embedded Ln3+ Complexes for Highly Sensitive Optical Thermometers in the Physiological Temperature Range*.

In recent years, luminescent materials doped with Ln3+ ions have attracted much attention for their application as optical thermometers based on both downshifting and upconversion processes. This study presents research done on the development of highly sensitive optical thermometers in the physiological temperature range based on poly(methyl methacrylate) (PMMA) films doped with two series of visible Ln3+ complexes (Ln3+ =Tb3+ , Eu3+ , and Sm3+ ) and SiO2 nanoparticles (NPs) coated with these PMMA films. The best performing PMMA film doped with Tb3+ and Eu3+ complexes was the PMMA[TbEuL1 tppo]1 film (L1 =4,4,4-trifluoro-1-phenyl-1,3-butadionate; tppo=triphenylphosphine oxide), which showed good temperature sensing of Sr =4.21 % K-1 at 313 K, whereas for the PMMA films doped with Tb3+ and Sm3+ complexes the best performing was the PMMA[TbSmL2 tppo]3 film (L2 =4,4,4-trifluoro-1-(4-chlorophenyl)-1,3-butadionate), with Sr =3.64 % K-1 at 313 K. Additionally, SiO2 NPs coated with the best performing films from each of the series of PMMA films (Tb-Eu and Tb-Sm) and their temperature-sensing properties were studied in water, showing excellent performance in the physiological temperature range (PMMA[TbEuL1 tppo]1@SiO2 : Sr =3.84 % °C at 20 °C; PMMA[TbSmL2 tppo]3@SiO2 : Sr =3.27 % °C at 20 °C) and the toxicity of these nanoparticles on human cells was studied, showing that they were nontoxic.

Two Polyoxometalate-Based Hybrid Compounds Modified by Iron Schiff Base Complexes: Syntheses, Crystal structures, Cyclic Voltametric Studies and Nonlinear Optical Properties.

Two new polyoxometalate (POM)-based hybrid compounds modified by a Schiff base, [Fe(DAPSC)(H2 O)2 ]2 [HPMo2 V Mo10 VI O40 ] ⋅ 5H2 O (1) and [Fe(DAPSC)(H2 O)]2 [HPV3 IV Mo4 V Mo7 VI O42 ] ⋅ 6H2 O (2), (DAPSC=2,6-diacetylpyridine bis-(semicarbazone)), have been successfully constructed from typical Keggin POMs, iron ions, and DAPSC ligands under hydrothermal condition. Structural analysis demonstrates that the Fe-Schiff base ligand units are free from polyacid anions in compound 1. While in compound 2, the Fe-Schiff base ligand units are bridged with polyacid anions via Fe-O bonds to emerge a stable double-supported skeleton. Noticeably, owing to the introduction of vanadium in H5 PMo10 V2 O40 ⋅ 32.5H2 O, a divanadium-capped configuration is shaped in compound 2. Besides, the third-order nonlinear optical (NLO) properties of two compounds were explored. It should be noted that both compounds 1 and 2 have two-photon absorption properties, which indicates that the two compounds are potential nonlinear optical materials.

Postsynthetic-Modified PANI/MOF Composites with Tunable Thermoelectric and Photoelectric Properties.

A 3D Co-based metal-organic framework (Co-MOF) with two kinds of large pores filled by free Co2+ ions and ligands was synthesized and characterized. To expand the MOF structure and conductivity, the free Co2+ ions and ligands were exchanged by conductive ionic liquid EtpyBr and photosensitive AgNO3 through single crystal-to-single crystal transformation, which produced structure-changed 3D MOFs Co-MOF-Br and Co-Ag-MOF, which were characterized by single-crystal X-ray diffraction. Incorporating small quantities of doped polyaniline (PANI) with redox activity into the pores could further tune the stability and conductivity of the three MOFs. The PANI/MOFs all show outstanding electrical conductivity (≈10-2  S cm-1 ), and PANI/Co-MOF-Br has the largest p-type Seebeck coefficient of 66.6 µV K-1 . PANI/Co-MOF-Br and PANI/Co-Ag-MOF have 4 and 15 times higher photocurrent density compared with PANI/Co-MOF, respectively. This work sheds light on the design of advanced electrically conductive 3D MOFs.

Ligand-Directed Approach in Polyoxometalate Synthesis: Formation of a New Divacant Lacunary Polyoxomolybdate [γ-PMo10 O36 ]7.

Polyoxometalates (POMs) have received increasing attention over the last decades for extending their application and properties that originate from novel structures. For the synthesis of a variety of POM structures, multivacant lacunary POMs are key precursors, which are typically synthesized by empirically controlling the complex equilibrium in aqueous solvents. Unfortunately, despite the excellent catalytic and electrochemical properties of "polyoxomolybdates", only one multivacant lacunary species, i.e., [A-α-PMo9 O34 ]9- , has been identified and isolated because multivacant lacunary polyoxomolybdates are typically unstable. Here we report a ligand-directed approach for the selective formation of an unprecedented lacunary polyoxomolybdate in organic solvents. By structure transformation of a pyridine-coordinated [A-α-PMo9 O34 ]9- , a new γ-Keggin-type divacant lacunary polyoxomolybdate [γ-PMo10 O36 ]7- was obtained, which can be further used as a precursor for synthesizing a POM-organic hybrid.

Enhancing Magnetic Cooperativity in Fe(II) Triazole-based Spin-crossover Nanoparticles by Pluronic Matrix Confinement.

Polymeric one-dimensional (1D) triazole-based FeII spin crossover nanoparticles have been entrapped in pluronic P123 matrix, forming nanorods in which the interaction between host (P123) and guest (FeII complex) promoted high reproducibility of the spin crossover process, significant shifts of the transition temperatures (T↑=370 K, T↓=338 K for the P123 entrapped material vs the literature values of T↑=358 K, T↓=341 K for the neat/polymer free system) and larger magnetic hysteresis width.

Immobilization of Ethynyl-π-Extended Electron Acceptors with Amino-Terminated SAMs by Catalyst-Free Click Reaction.

Surface modification of SiO2 using a catalyst-free quantitative reaction between an amine and an ethynyl-π-extended naphthalenediimide was investigated. A post-reaction method, in which the catalyst-free reaction was performed at the surface after the formation of amino-terminated self-assembled monolayers (SAMs), resulted in dense, uniform modification of the SiO2 surface with the naphthalenediimide molecules. Both X-ray reflectivity and angle-resolved X-ray photoemission spectroscopy showed consistent results for the layer thickness and density. In contrast, a pre-reaction method, in which an amino-silane and the ethynyl-π-extended naphthalenediimide reacted first and then formed a SAM, afforded a sparse SAM on the SiO2 surface, probably due to the steric hindrance of the naphthalenediimide moieties. The in situ decoration of the SiO2 surface by a catalyst-free quantitative reaction offers a facile route for modifying surface properties with various π-conjugated molecules suitable for many applications.

Multicomponent Organic Metal Halide Hybrid with White Emissions.

Zero-dimensional (0D) organic metal halide hybrids, in which organic and metal halide ions cocrystallize to form neutral species, are a promising platform for the development of multifunctional crystalline materials. Herein we report the design, synthesis, and characterization of a ternary 0D organic metal halide hybrid, (HMTA)4 PbMn0.69 Sn0.31 Br8 , in which the organic cation N-benzylhexamethylenetetrammonium (HMTA+ , C13 H19 N4 + ) cocrystallizes with PbBr4 2- , MnBr4 2- , and SnBr4 2- . The wide band gap of the organic cation and distinct optical characteristics of the three metal bromide anions enabled the single-crystalline "host-guest" system to exhibit emissions from multiple "guest" metal halide species simultaneously. The combination of these emissions led to near-perfect white emission with a photoluminescence quantum efficiency of around 73 %. Owing to distinct excitations of the three metal halide species, warm- to cool-white emissions could be generated by controlling the excitation wavelength.

Recent Advances and Optoelectronic Applications of Lead-Free Halide Double Perovskites.

Organic-inorganic metal halide perovskites (most notably CH3 NH3 PbI3 ) have demonstrated remarkable physical attributes for photovoltaic and diverse optoelectronic applications, whereas concerns about toxicity owing to the use of lead in the chemical composition still motivate further exploration of new, nontoxic candidates. Lead-free halide double perovskites (HDPs), designed by the rational chemical substitution of Pb2+ with other nontoxic candidate elements, have recently attracted interest as a fascinating alternative to their Pb-based counterparts. Herein, recent advances in crystal structures, physical properties, and versatile optoelectronic applications of lead-free HDPs, such as solar cells, photodetectors, X-ray detectors, and light-emitting diodes, are reviewed. Perspectives to improve the physical and photoelectric properties of existing HDP materials are also discussed and will favor future development of new, lead-free HDP candidates.

Piezoelectric Energy Harvesting from a Ferroelectric Hybrid Salt [Ph3 MeP]4 [Ni(NCS)6 ] Embedded in a Polymer Matrix.

Organic-inorganic hybrid ferroelectrics are an exciting class of molecular materials with promising applications in the area of energy and electronics. The synthesis, ferroelectric and piezoelectric energy harvesting behavior of a 3d metal ion-containing A4 BX6 type organic-inorganic hybrid salt [Ph3 MeP]4 [Ni(NCS)6 ] (1) is now presented. P-E hysteresis loop studies on 1 show a remnant ferroelectric polarization value of 18.71 µC cm-2 , at room temperature. Composite thermoplastic polyurethane (TPU) devices with 5, 10, 15 and 20 wt % compositions of 1 were prepared and employed for piezoelectric energy harvesting studies. A maximum output voltage of 19.29 V and a calculated power density value of 2.51 mW cm-3 were observed for the 15 wt % 1-TPU device. The capacitor charging experiments on the 15 wt % 1-TPU composite device shows an excellent energy storage performance with the highest stored energies and measured charges of 198.8 µJ and 600 µC, respectively.