High-temperature giant dielectric switching in an organic-inorganic hybrid material.

With the increasing research on giant dielectric materials, there is growing interest in the development of switching materials with giant dielectric properties. In this study, a novel organic-inorganic hybrid material (EtNCHBr)FeCl was synthesized. It was characterized through differential scanning calorimetry (DSC) and temperature-dependent powder X-ray diffraction (PXRD), which determined its phase transition temperature () to be 362 K.

Multi-responsive cascade enzyme-like catalytic nanoassembly for ferroptosis amplification and nanozyme-assisted mild photothermal therapy.

Ferroptosis is greatly restricted by low reactive oxygen species (ROS) generation efficiency, and the inherent self-protection mechanism originating in heat shock proteins (HSPs) seriously impedes the efficiency of photothermal therapy (PTT). Herein, we designed an intelligent strategy utilizing cascade catalytic nanoassemblies (Au@COF@MnO) with triple-enzyme activity for amplifying ferroptosis therapy and improving the efficiency of PTT in tumor. Gold nanozyme was encapsulated within a hollow manganese dioxide (MnO) shell with the help of covalent organic frameworks (COFs).

Enhancing Short-Range Interactions to Broaden the Temperature Range for Coexistence of Antiferroelectricity and Ferroelasticity.

Antiferroelectric (AFE) materials, characterized by double electric hysteresis loops, can be transformed to the ferroelectric (FE) phase under an external electric field, making them promising candidates for electronic energy storage and solid-state refrigeration. Additionally, the field-induced strain in AFE materials is contingent upon the direction of the electric field, rendering it with a switching characteristic. Although AFE materials have made progress in the field of energy storage and negative electrocaloric effect, the coexistence of AFE and ferroelasticity is still rarely reported.

Molecularly Imprinted Polymers for Highly Specific Bioorthogonal Catalysis Inside Cells.

Transition metal catalysts (TMCs) mediated bioorthogonal catalysis expand the chemical possibilities within cells. Developing synthetic TMCs tools that emulate the efficiency and specificity of natural metalloenzymes is a rewarding yet challenging endeavor. Here, we highlight the potential of molecularly imprinted enzyme mimics (MIEs) containing a Cu center and specific substrate binding domain, for conducing dimethylpropargyloxycarbonyl (DmProc) cleavage reactions within cells.

Intermolecular Forces Regulating the Phase-Transition Temperatures in Organic-Inorganic Hybrid Materials.

Organic-inorganic hybrid phase-transition materials have attracted widespread attention in energy storage and sensor applications due to their structural adaptability and facile synthesis. However, increasing the phase-transition temperature () effectively remains a formidable challenge. In this study, we employed a strategy to regulate intermolecular interactions (different types of hydrogen bonds and other weak interactions), utilizing bismuth chloride as an inorganic framework and azetidine, 3,3-difluoro azetidine, and 3-carboxyl azetidine as organic components to synthesize three compounds with different values: [CHN]BiCl (, 234 K), [CHNF]BiCl (, 256 K), and [CHON]BiCl (, 350 K).

Transition Metal Ru(II) Catalysts Immobilized Nanoreactors for Conditional Bioorthogonal Catalysis in Cells.

Employing transition metal catalysts (TMCs) to perform bioorthogonal activation of prodrugs and pro-fluorophores in biological systems, particularly in a conditional fashion, remains a challenge. Here, we used a mesoporous organosilica nanoscaffold (RuMSN), which localizes Ru(II) conjugates on the pore wall, enabling the biorthogonal photoreduction reactions of azide groups. Due to easily adjustable surface charges and pore diameter, this efficiently engineering RuMSN catalyst, with abundant active sites on the inner pore well, could spontaneously repel or attract substrates with different molecular sizes and charges and thus ensure selective bioorthogonal catalysis.

Novel small molecule-based organic nanoparticles for second near-infrared photothermal tumor ablation.

Second near-infrared (NIR-II,1000 ∼ 1700 nm) therapeutic window presents an increased tissue penetration and elevated maximal permissible exposure in the application of photothermal therapy (PTT). However, the lack of NIR-II photothermal conversion agents (PCAs) limit their further development. In this work, we rationally designed and successfully developed three novel indolium-like heptamethine cyanine dyes (NFs) by installing N,N-diethylamino on the terminal ends of a conjugated polyene backbone and replacing the middle chlorine atom with o-mercapto benzoic acid and p-mercapto benzoic acid.

Isolation, synthesis and identification of degraded impurities in Letermovir.

Letermovir is a cytomegalovirus inhibitor for cytomegalovirus infection a hematopoietic-cell transplantation. In the degradation test of Letermovir, five new impurities were detected at levels of ND ∼ 2.21 % (by oxide, thermal or photolytic).

Tumor-Targeting Near-Infrared Dimeric Heptamethine Cyanine Photosensitizers with an Aromatic Diphenol Linker for Imaging-Guided Cancer Phototherapy.

Phototherapy is considered a promising alternative to conventional tumor treatments due to its noninvasive modality and effective therapeutic effect. However, designing a photosensitizer with satisfactory therapeutic effect and high security remains a considerable challenge. Herein, a series of dimeric heptamethine cyanine photosensitizers with an aromatic diphenol linker at the meso position is developed to improve the photothermal conversion efficiency (PCE).

Design, synthesis, and characterization of a new hybrid organic-inorganic perovskite with a high- dielectric transition.

Phase change materials (PCMs) have drawn increasing attention for their promising applications in thermal switches, data communication, and energy storage. Because of the complexity of the interactions between molecules, it is still a challenge to design PCMs with a desired high phase transition temperature (). In this study, a one-dimensional hybrid perovskite of (TEACCl)PbBr (1, TEACCl = EtNCHCl) was successfully designed and synthesized with a = 390 K.

Novel pharmaceutical salts of cephalexin with organic counterions: structural analysis and properties.

Three novel pharmaceutical salts of cephalexin (CPX) with 2,6-dihydroxybenzoic acid (DHBA), 5-chlorosalicylic acid (CSA) and 5-sulfosalicylic acid (SSA), which were obtained and thoroughly explored by various analytical techniques, were found to be crystallized invariably in hydrated forms. It is the proton transfer from carboxylic or sulfonic counterions to the CPX molecules that results in the salt formation. Crystal structure analyses reveal that the N-H⋯O and O-H⋯O hydrogen bonding interactions among the CPX, acidic guest molecules and water molecules play a crucial role in the packing motifs of crystal stabilization.

Three near-infrared and lysosome-targeting probes for photodynamic therapy (PDT).

Lysosome, an organelle which contains a number of hydrolases and hydrogen ions, plays a crucial role in cellular survival and apoptosis. If selectively destroy lysosomes membrane, inner hydrolases and hydrogen ions will leak and induce cell death. In this work, three lysosome-targeting fluorescent probes (HCL 1-3, heptamethine cyanine lysosomal-targeting probe) were designed, synthesized and developed for photodynamic therapy.

Dual-responsive and NIR-driven free radical nanoamplifier with glutathione depletion for enhanced tumor-specific photothermal/thermodynamic/chemodynamic synergistic Therapy.

The efficacy of free radical-based therapeutic strategies is severely hindered by nonspecific accumulation, premature release and glutathione (GSH) scavenging effects. Herein, a tumor microenvironment-responsive MPDA/AIPH@Cu-TA@HA (abbreviated as MACTH) nanoplatform was constructed by coating Cu and tannic acid (TA) on the surface of azo initiator (AIPH)-loaded mesoporous polydopamine (MPDA) nanoparticles and further modifying them with hyaluronic acid (HA) to achieve tumor-specific photothermal/thermodynamic/chemodynamic synergistic therapy (PTT/TDT/CDT). Once accumulated and internalized into cancer cells through CD44 receptor-mediated active targeting and endocytosis, the HA shell of MACTH would be preliminarily degraded by hyaluronidase (HAase) to expose the Cu-TA metal-phenolic networks, which would further dissociate in response to an acidic lysosomal environment, leading to HAase/pH dual-responsive release of Cu and AIPH.

Glutathione-triggered nanoplatform for chemodynamic/metal-ion therapy.

The integration of metal-ion therapy and hydroxyl radical (˙OH)-mediated chemodynamic therapy (CDT) holds great potential for anticancer treatment with high specificity and efficiency. Herein, Ag nanoparticles (Ag NPs) were enveloped with Cu-based metal-organic frameworks (MOFs) and further decorated with hyaluronic acid (HA) to construct a glutathione (GSH)-activated nanoplatform (Ag@HKU-HA) for specific chemodynamic/metal-ion therapy. The obtained nanoplatform could avoid the premature leakage of Ag in circulation, but realize the release of Ag at the tumor site owing to the degradation of external MOFs triggered by Cu-reduced glutathione.

A polydopamine-gated biodegradable cascade nanoreactor for pH-triggered and photothermal-enhanced tumor-specific nanocatalytic therapy.

Despite the great potential of cascade catalytic reactions in tumor treatment, uncontrolled catalytic activities lead to inevitable off-target toxicity to normal tissues, which greatly hampers their clinical conversion. Herein, an intelligent cascade nanoreactor (hMnO-Au@PDA, hMAP) was constructed by depositing glucose oxidase (GOx)-mimicking ultrasmall gold nanoparticles (Au NPs) into honeycomb-shaped manganese oxide (hMnO) nanostructures and then coating them with polydopamine (PDA) to achieve pH-responsive and photothermal-enhanced nanocatalytic therapy. Upon exposure to the mild acidic tumor microenvironment (TME), the PDA gatekeeper would collapse, and the inner hMnO could simultaneously deplete glutathione (GSH) and generate Mn, while a considerable amount of HO produced from the oxidation of glucose by GOx-mimicking Au NPs could accelerate the Mn-mediated Fenton-like reaction, yielding sufficient highly toxic ˙OH.

Bromhexine and its fumarate salt: Crystal structures, Hirshfeld surfaces and dissolution study.

Bromhexine is an expectorant drug repurposing as a TMPRSS2 inhibitor, which has also been proposed for potential treatment in COVID-19 infection. Multicomponent crystal strategy has been applied in bromhexine to improve its poor solubility, which limits its bioavailability and efficacy. A new bromhexine crystal and its fumarate salt crystal have been successfully obtained by slow evaporation technique.

Small-Molecule-Selective Organosilica Nanoreactors for Copper-Catalyzed Azide-Alkyne Cycloaddition Reactions in Cellular and Living Systems.

We reported the synthesis of a tris(triazolylmethyl)amine (TTA)-bridged organosilane, functioning as Cu(I)-stabilizing ligands, and the installation of this building block into the backbone of mesoporous organosilica nanoparticles (TTASi) by a sol-gel way. Upon coordinating with Cu(I), the mesoporous Cu-TTASi, with a restricted metal active center inside the pore, functions as a molecular-sieve-typed nanoreactor to efficiently perform Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reactions on small-molecule substrates but fails to work on macromolecules larger than the pore diameter. As a proof of concept, we witnessed the advantages of selective nanoreactors in screening protein substrates for small molecules.

Dual catalytic cascaded nanoplatform for photo/chemodynamic/starvation synergistic therapy.

In this study, manganese dioxide (MnO) was attached to prussian blue (PB) by a one-pot method to prepare PBMO. Then, the GOD was loaded onto PBMO through the electrostatic interaction of hyaluronic acid (HA) to form tumor-targeted nanoplatform (PBMO-GH). Hydrogen peroxide (HO) and gluconic acid were produced through the GOD-catalyzed enzymatic reaction.

One-for-all intelligent core-shell nanoparticles for tumor-specific photothermal-chemodynamic synergistic therapy.

Reasonable management of the one-for-all nanoplatform can facilitate improved cancer therapy. Here, the metal-organic frameworks (MOFs) based on iron(iii) carboxylate material (MIL-101-NH) were in situ decorated on stabilized polydopamine nanoparticles (PDANPs), which subsequently loaded glucose oxidase (GOx) via hyaluronic acid (HA) coating to structure the one-for-all intelligent core-shell nanoparticles (HG-MIL@PDANPs). Because of the inner PDANPs, the HG-MIL@PDANPs could realize near-infrared (NIR)-controllable site-specific photothermal therapy (PTT).

Smart Porous Core-Shell Cuprous Oxide Nanocatalyst with High Biocompatibility for Acid-Triggered Chemo/Chemodynamic Synergistic Therapy.

The rational integration of chemotherapy and hydroxyl radical (·OH)-mediated chemodynamic therapy (CDT) holds great potential for cancer treatment. Herein, a smart biocompatible nanocatalyst based on porous core-shell cuprous oxide nanocrystals (Cu O-PEG (polyethylene glycol) NCs) is reported for acid-triggered chemo/chemodynamic synergistic therapy. The in situ formed high density of hydrophilic PEG outside greatly improves the stability and compatibility of NCs.

Enhanced antitumor effect via amplified oxidative stress by near-infrared light-responsive and folate-targeted nanoplatform.

The efficiency of producing hydroxyl radicals (·OH) from hydrogen peroxide (HO) catalyzed by different iron compounds have been explored extensively. Exclusively, ferrocenecarboxylic acid (FCA) showed the best catalyzed activity for ·OH generation. Then, we designed and prepared near-infrared (NIR) light-responsive and folate-targeted nanoplatform, which co-delivered FCA, cisplatin and indocyanine green (ICG) for improving antitumor therapy through amplified oxidative stress.

A pH-activated autocatalytic nanoreactor for self-boosting Fenton-like chemodynamic therapy.

The emergence of hydroxyl radical (˙OH)-mediated chemodynamic therapy (CDT) by the Fenton or Fenton-like reaction holds great potential for improving anticancer efficacy. Herein, an activatable autocatalytic nanoreactor (HT@GOx-DMONs) was developed for self-boosting Fenton-like CDT via decorating Cu-based metal-organic frameworks (MOFs) on glucose oxidase (GOx)-loaded dendritic mesoporous organosilica nanoparticles (DMONs) for the first time. The obtained nanoreactor could prevent the premature leakage of Cu and GOx in neutral physiological environments conducted by the gatekeeper of growing carboxylate MOF (HKUST-1), but the explosive release of agents was realized due to the activated degradation of external HKUST-1 in acidic condition of endo/lysosomes, which thereby endowed this nanoreactor with the performance of pH-triggered ˙OH generation driven by Cu-mediated autocatalytic Fenton-like reaction.

Mesoporous Silica-Coated Silver Nanoframes as Drug-Delivery Vehicles for Chemo/Starvation/Metal Ion Multimodality Therapy.

Cutting off the energy supply by glucose oxidase (GOx) to starve cancer cells has been a feasible and efficient oncotherapy strategy. The employment of GOx can effectively starve tumor cells by aerobic hydrolysis of glucose hopefully strengthening the abnormality (including the decrease in pH, the increase of hypoxia, and toxic hydrogen peroxide) in the tumor microenvironment (TME). On this basis, we designed and fabricated a GOx-conjugated yolk-shell Ag@mSiO nanoframe with Ag NPs and GOx-conjugated mesoporous silica as the yolk and the shell, respectively, to make full use of changes the GOx induces in TME.

Dendritic Mesoporous Organosilica Nanoparticles: A pH-Triggered Autocatalytic Fenton Reaction System with Self-supplied HO for Generation of High Levels of Reactive Oxygen Species.

Dendritic mesoporous silica nanoparticles represent a new biomedical application platform due to their special central radial pore structure for the loading of drugs and functional modification. Herein, we report functionalized dendritic mesoporous organosilica nanoparticles (DMONs), a pH-triggered Fenton reaction generator (TA/Fe@GOD@DMONs), incorporating natural glucose oxidase (GOD) in the DMONs with tannic acid (TA) grafted using Fe on the surface, that have been designed and constructed for efficient tumor ablation with self-supplied HO and accelerated conversion of Fe/Fe by TA. In view of the deficiency of endogenous HO, the self-supply through the TA/Fe@GOD@DMONs platform represented a high-yielding source of peroxygen.