Structure Peculiarities of Reduced Vanadium–Titanium Oxide Catalysts

The properties of vanadium–titanium oxide catalysts, which contain coherent phase boundaries formed by V₂O₅ and TiO₂ crystallites during reduction by hydrogen at 150–500°C, are examined. The phase boundary is preserved over the entire examined temperature range regardless of the structure of vanadium oxide, which is formed. The state of vanadium ions at the phase boundary is determined. The presence of a phase boundary in the catalyst is responsible for the V₂O₅ V₂O₃ transition without the formation of intermediate structures.     

UCNP–Bi2Se3 Upconverting Nanohybrid for Upconversion Luminescence and CT Imaging and Photothermal Therapy

Non-invasive theranostics that integrate the advantages of multimodality imaging and therapeutics have great potential in the field of biomedicine. Herein, a new nanohybrid based on Bi₂Se₃-conjugated upconversion nanoparticles (UCNPs) has been successfully developed through a simple in situ growth strategy. Under 808 nm near-infrared laser irradiation, the UCNPs can emit bright visible light, whereas the Bi₂Se₃ nanomaterial exhibits efficient photothermal conversion capacity. Moreover, the as-synthesized UCNP–Bi₂Se₃ nanohybrid exhibits efficient cell upconversion luminescence (UCL), reasonable CT imaging, and admirable cancer cell ablation capacity, further emphasizing the efficiency of this strategy for simultaneous UCL imaging and photothermal therapy. The designed theranostic strategy guided by dual-modal imaging endowed with real-time dynamic monitoring, remote controllability, and non-invasiveness makes the UCNP–Bi₂Se₃ nanohybrid an ideal candidate for non-invasive multimodal imaging-guided photothermal therapy for the precise diagnosis and treatment of cancer.     

Recent Advances in Bio-Inspired Versatile Polydopamine Platforms for “Smart” Cancer Photothermal Therapy

Although photothermal therapy(PTT) has been developed for fighting cancers, the degradative, toxic, and metabolic nature of photothermal conversion materials(PCMs) has prevented them from being clinically implemented. Taking advantage of the surface modification strategy of mussel-inspired dopamine chemistry and its excellent photothermal conversion effect, polydopamine(Pdop) represents a versatile PTT platform, providing strategies and methods for the construction of novel Pdop-functionalized P...     

A RuII Polypyridyl Alkyne Complex Based Metal–Organic Frameworks for Combined Photodynamic/Photothermal/Chemotherapy

Despite drug delivery nanoplatforms receiving extensive attention, development of a simple, effective, and multifunctional theranostics nanoplatform still remains a challenge. Herein, a versatile nanoplatform based on a zirconium framework (UiO-66-N₃) was synthesized, which demonstrated a combined photodynamic therapy (PDT), photothermal therapy (PTT), and chemotherapy (CT) for cancer treatment. A Ru^II polypyridyl alkyne complex (Ra) as a photosensitizer was modified into a nanoplatform by click reactions for the first time. When exposed to suitable light irradiation, the as-prepared multifunctional nanoplatform (UiO-Ra-DOX-CuS) not only demonstrated efficient ¹O₂ generation, but also exhibited excellent photothermal conversion ability. In particular, the nanotherapeutic agent presented a dual-stimuli response; either acidic environment or NIR laser irradiation would trigger the drug release. The synergetic efficacy of UiO-Ra-DOX-CuS combined PDT, PTT, and CT, which was evaluated by cell experiments. Moreover, the design could promote the development of Ru^II polypyridyl alkyne complexes based multifunctional nanoparticles and multimodal cancer treatment.     

Increasing Molecular Planarity through Donor/Side-Chain Engineering for Improved NIR-IIa Fluorescence Imaging and NIR-II Photothermal Therapy under 1064 nm

Developing conjugated small molecules (CSM) with intense NIR-II (1000–1700 nm) absorption for phototheranostic is highly desirable but remains a tremendous challenge due to a lack of reliable design guidelines. This study reports a high-performance NIR-II CSM for phototheranostic by tailoring molecular planarity. A series of CSM show bathochromic absorption extended to the NIR-II region upon the increasing thiophene number, but an excessive number of thiophene results in decreased NIR-IIa (1300–1400 nm) brightness and photothermal effects. Further introduction of terminal nonconjugated alkyl chain can enhance NIR-II absorption coefficient, NIR-IIa brightness, and photothermal effects. Mechanism studies ascribe this overall enhancement to molecular planarity stemming from the collective contribution of donor/side-chain engineering. This finding directs the design of NIR-II CSM by rational manipulating molecular planarity to perform 1064 nm mediated phototheranostic at high efficiency.     

Tumor Microenvironment Stimuli-Responsive Fluorescence Imaging and Synergistic Cancer Therapy by Carbon-Dot–Cu2+ Nanoassemblies

A method is developed to fabricate tumor microenvironment (TME) stimuli-responsive nanoplatform for fluorescence (FL) imaging and synergistic cancer therapy via assembling photosensitizer (chlorine e6, Ce6) modified carbon dots (CDs-Ce6) and Cu²⁺. The as-obtained nanoassemblies (named Cu/CC nanoparticles, NPs) exhibit quenched FL and photosensitization due to the aggregation of CDs-Ce6. Their FL imaging and photodynamic therapy (PDT) functions are recovered efficiently once they entering tumor sites by the stimulation of TME. Introducing of Cu²⁺ not only provides extra chemodynamic therapy (CDT) function through reaction with hydrogen peroxide (H₂O₂), but also depletes GSH in tumors by a redox reaction, thus amplifying the intracellular oxidative stress and enhancing the efficacy of reactive oxygen species (ROS) based therapy. Cu/CC NPs can act as a FL imaging guided trimodal synergistic cancer treatment agent by photothermal therapy (PTT), PDT, and thermally amplified CDT.     

Hexafluoropropylene Oxide–Alcohol: A Convenient System for Silica Dissolution

Abstract

A new method of silica dissolution is described. It involves the formation of a stable SiF₄ · n ROH complex (1, 1a) just from SiO₂ and anhydrous alcoholic HF generated in situ from commercially available hexafluoropropene oxide. Alcoholic SiF₄ complexes can be easily converted to different organosilicon compounds of the type SiF₄L₂ and (LH)₂SiF₆ [L = 1,10-phenantroline (2a), 2,2′-dipyridyl (2b), Me₂SO (2c), pyridine (2d), triethanolamine (3a)]. Different silica-containing compounds can be used in this strategy—silicagel, sand, alumosilicates, and even rice husk.

GRAPHICAL ABSTRACT     

A Neutrophil-Inspired Supramolecular Nanogel for Magnetocaloric–Enzymatic Tandem Therapy

Neutrophils can responsively release reactive oxygen species (ROS) to actively combat infections by exogenous stimulus and cascade enzyme catalyzed bio-oxidation. A supramolecular nanogel is now used as an artificial neutrophil by enzymatic interfacial self-assembly of peptides (Fmoc-Tyr(H₂PO₃)-OH) with magnetic nanoparticles (MNPs) and electrostatic loading of chloroperoxidase (CPO). The MNPs within the nanogel can elevate H₂O₂ levels in cancer cells under programmed alternating magnetic field (AMF) similar to the neutrophil activator, and the loaded CPO within protective peptides nanolayer converts the H₂O₂ into singlet oxygen (¹O₂) in a sustained manner for neutrophil-inspired tumor therapy. As a proof of concept study, both the H₂O₂ and ¹O₂ in cancer cells increase stepwise under a programmed alternating magnetic field. An active enzyme dynamic therapy by magnetically stimulated oxygen stress and sustained enzyme bio-oxidation is thus shown with studies on both cells and animals.     

Weather-informed Light–tissue Model–Based Dose Planning for Indoor Daylight Photodynamic Therapy

Daylight activation for photodynamic therapy (PDT) of skin lesions is now widely adopted in many countries as a less painful and equally effective treatment mechanism, as compared to red or blue light activation. However, seasonal daylight availability and transient weather conditions complicate light dose estimations. A method is presented for dose planning without placing a large burden on clinical staff, by limiting spectral measurements to a one-time site assessment, and then using automatically acquired weather reports to track transient conditions. The site assessment tools are used to identify appropriate treatment locations for the annual and daily variations in sunlight exposure for clinical center planning. The spectral information collected from the site assessment can then be integrated with real-time daily electronic weather data. It was shown that a directly measured light exposure has strong correlation (R²: 0.87) with both satellite cloud coverage data and UV index, suggesting that the automated weather indexes can be surrogates for daylight PDT optical dose. These updated inputs can be used in a dose-planning treatment model to estimate photodynamic dose at depth in tissue. A simple standardized method for estimating light dose during daylight-PDT could help improve intersite reproducibility while minimizing treatment times.     

Carrier-Free Delivery of Precise Drug–Chemogene Conjugates for Synergistic Treatment of Drug-Resistant Cancer

Combinatorial antitumor therapies using different combinations of drugs and genes are emerging as promising ways to overcome drug resistance, which is a major cause for the failure of cancer treatment. However, dramatic pharmacokinetic differences of drugs greatly impede their combined use in cancer therapy, raising the demand for drug delivery systems (DDSs) for tumor treatment. By employing fluorescent dithiomaleimide (DTM) as a linker, we conjugate two paclitaxel (PTX) molecules with a floxuridine (FdU)-integrated antisense oligonucleotide (termed chemogene) to form a drug–chemogene conjugate. This PTX–chemogene conjugate can self-assemble into a spherical nucleic acid (SNA)-like micellular nanoparticle as a carrier-free DDS, which knocks down the expression of P-glycoprotein and subsequently releases FdU and PTX to exert a synergistic antitumor effect and greatly inhibit tumor growth.     

Electrochemical Sensor for Detection of p-Nitrophenol Based on Nickel Oxide Nanoparticles/α-Cyclodextrin Functionalized Reduced Graphene Oxide

p-Nitrophenol (p−NP) is a high priority toxic pollutant and that has harmful effects on human, animals and plants. Thus, the detection and determination of p−NP present in the environment is an urgent as well as highly important requisite. The present article, therefore focused on the construction of a novel electrochemical sensor based on NiO nanoparticles/α-cyclodextrin functionalized reduced graphene oxide modified glassy carbon electrode (NiO−NPs-α-CD-rGO-GCE) for the selective and sensitive detection of p−NP. UV-vis, high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction pattern (SAED) and X-ray diffraction (XRD) analysis confirms the formation of highly pure NiO nanoparticles. Field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), and cyclic voltammetry (CV) were used to characterize the step-wise electrode modification process. DPV was carried out to quantify p−NP within the concentration range of 1−10 μM and found the detection limit of 0.12 nM on the basis of the signal-to-noise ratio S/N=3. The electrode can able to detect different isomers of nitrophenols. Interferences of other pollutants such as phenol, p-aminophenol, o- and m- nitrophenol, 4-chlorophenol, 2,6-dichlorophenol and ions like K⁺, Cd²⁺, Cl⁻, SO₄²⁻ did not affect the sensing of p−NP. The newly developed sensor exhibited diffusion controlled kinetics and had excellent sensitivity, selectivity and reproducibility for the detection of p−NP. The electrode showed good recoveries in real sample analysis.     

Formation of Active Structures in Monolith Copper–Manganese Oxide Catalysts for Air-Heating Devices

Impregnation catalysts based on CuO, MnO_x, and CuO–MnO_x with different Cu/Mn ratios supported on ceramic monoliths of alumina and silica are studied by BET, mercury porosimetry, X-ray diffraction analysis, transmission and scanning electron microscopy, temperature-programmed reduction with H₂, diffuse reflectance electron spectroscopy, and differential dissolution. It is found that, in the butane oxidation reaction, CuO–MnO_x catalysts exert a synergistic effect, which is attributed to the formation of highly defective phases of complex oxides of the nonstoichiometric spinel type with a large number of interparticle boundaries in the near-surface layers of the support.     

Synthesis and Examination of Electrolytic Sodium–Vanadium Oxide Compounds Intended for Cathodes of Lithium Batteries: The Mechanism of Formation of Electrolytic Bronze β-NaxV2O5

To determine the mechanism responsible for the formation of electrolytic sodium–vanadium oxide bronze e-Na _x V₂O₅, synthesized earlier from acid vanadyl sulfate electrolyte, -bronze i-Na _x V₂O₅is synthesized by exposing electrolytic oxide e-V₂O₅in the same sodium-containing electrolyte under open-circuit conditions, with a subsequent annealing of the sample. It is established that the two modifications of -bronze (e-Na _x V₂O₅and i-Na _x V₂O₅) are identical and that electrolytic precursors of -bronze Na _x V₂O₅form via an ion-exchange mechanism.     

Photoassisted Selective Steam and Dry Reforming of Methane to Syngas Catalyzed by Rhodium–Vanadium Bimetallic Oxide Cluster Anions at Room Temperature

Photoassisted steam reforming and dry (CO₂) reforming of methane (SRM and DRM) at room temperature with high syngas selectivity have been achieved in the gas-phase catalysis for the first time. The catalysts used are bimetallic rhodium–vanadium oxide cluster anions of Rh₂VO_1–3⁻. Both the oxidation of methane and reduction of H₂O/CO₂ can take place efficiently in the dark while the pivotal step to govern syngas selectivity is photo-excitation of the reaction intermediates Rh₂VO_2,3CH₂⁻ to specific electronically excited states that can selectively produce CO and H₂. Electronic excitation over Rh₂VO_2,3CH₂⁻ to control the syngas selectivity is further confirmed from the comparison with the thermal excitation of Rh₂VO_2,3CH₂⁻, which leads to diversity of products. The atomic-level mechanism obtained from the well-controlled cluster reactions provides insight into the process of selective syngas production from the photocatalytic SRM and DRM reactions over supported metal oxide catalysts.     

Microemulsions in Sodium Dodecyl Sulfate–1-Butanol–Extractant–Kerosene–Water Systems for Extracting Nonferrous Metals from Oxide Raw Materials

Russian Journal of Applied Chemistry - Areas of existence and properties of extractant-containing microemulsions in sodium dodecyl...     

Development and Elucidation of a Pd-Based Cyclization–Oxygenation Sequence for Natural Product Synthesis

Pd-catalyzed sequences involving oxidative addition, cyclization, and termination through intermolecular nucleophile capture have tremendous utility. Indeed, they can generate a plethora of different polycyclic structures possessing a diverse range of functionality. However, one area of deficiency for Pd⁰/Pd^II variants is the ability to conclude them with oxygen-based species. Inspired by the recent discovery of one such reaction in the course of a total synthesis program, we delineate herein that it has significant strength, both in terms of substrate scope as well as the terminating oxygen nucleophile. As a result, the reaction proved critical in achieving total syntheses of two oxygenated natural products, one of which was prone to over-oxidation. Finally, a mechanistic proposal that accounts for its success is provided.     

Heterostructured Inter-Doped Ruthenium–Cobalt Oxide Hollow Nanosheet Arrays for Highly Efficient Overall Water Splitting

The development of transition-metal-oxides (TMOs)-based bifunctional catalysts toward efficient overall water splitting through delicate control of composition and structure is a challenging task. Herein, the rational design and controllable fabrication of unique heterostructured inter-doped ruthenium–cobalt oxide [(Ru–Co)O_x] hollow nanosheet arrays on carbon cloth is reported. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru–Co)O_x nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, the catalyst showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm⁻² and a small Tafel slope of 23.5 mV dec⁻¹, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm⁻². As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm⁻² for alkaline overall water splitting.     

Nd3+-Sensitized Upconversion Metal–Organic Frameworks for Mitochondria-Targeted Amplified Photodynamic Therapy

Herein, we report the design and synthesis of a mitochondria-specific, 808 nm NIR light-activated photodynamic therapy (PDT) system based on the combination of metal–organic frameworks (MOFs) and upconversion photochemistry with an organelle-targeting strategy. The system was synthesized through the growth of a porphyrinic MOF on Nd³⁺-sensitized upconversion nanoparticles to achieve Janus nanostructures with further asymmetric functionalization of the surface of the MOF domain. The PDT nanoplatform allows for photosensitizing with 808 nm NIR light, which could effectively avoid the laser-irradiation-induced overheating effect. Furthermore, mitochondria-targeting could amplify PDT efficacy through the depolarization of the mitochondrial membrane and the initiation of intrinsic apoptotic pathway. This work sheds light on the hybrid engineering of MOFs to combat their current limitations for PDT.     

Synthesis of a Gold–Metal Oxide Core–Satellite Nanostructure for In Situ SERS Study of CuO-Catalyzed Photooxidation

This work reports on an assembling–calcining method for preparing gold–metal oxide core–satellite nanostructures, which enable surface-enhanced Raman spectroscopic detection of chemical reactions on metal oxide nanoparticles. By using the nanostructure, we study the photooxidation of Si−H catalyzed by CuO nanoparticles. As evidenced by the in situ spectroscopic results, oxygen vacancies of CuO are found to be very active sites for oxygen activation, and hydroxide radicals (*OH) adsorbed at the catalytic sites are likely to be the reactive intermediates that trigger the conversion from silanes into the corresponding silanols. According to our finding, oxygen vacancy-rich CuO catalysts are confirmed to be of both high activity and selectivity in photooxidation of various silanes.