The complete harmless treatment of aromatic organic compounds in coal chemical wastewater (CCW) has always been a big challenge in water process engineering. This study addresses the issue by designing and preparing a kind of Ce and Al bimetallic catalyst with high oxygen vacancies (OVs) based on SiC carrier. The results showed that CeO2 and Al2O3 were uniformly dispersed on SiC, and the composite material exhibited an ordered cubic structure. The degradation efficiency and enhancement mechanism of the catalyst with ozone oxidation were investigated. When applied to actual CCW with a chemical oxygen demand (COD) concentration exceeding 600 mg/L, the synergy between O-3 and CeO2/Al2O3-SiC increased the degradation efficiency of phenols from 50 % to 99 % and COD from 42 % to 78 % compared to using O-3 alone. CeO2/Al2O3-SiC had a high concentration of oxygen vacancies (OVs = 48.57 %). Further research indicated that oxygen vacancies (OVs) were the main active sites for ozone adsorption and reactive oxygen species (ROSs) generation. Electron paramagnetic resonance (EPR) and quenching experiments also confirmed that O-3, center dot O-2(-1), O-1(2) were the main active oxidation factors, rather than center dot OH. Additionally, even after granulating the catalyst, it still achieved 99 % degradation of phenols. Therefore, this study provides theoretical support for the complete harmless treatment of CCW and has broad prospects for industrial application.

Purpose Exploring the distribution characteristics of immune cells related to the programmed cell death receptor-1 (PD-1) pathway in esophageal cancer(EC) tissue and its relationship with prognosis. Methods Tissue samples of 236 patients with EC after surgery in our hospital from January 2016 to January 2021 were included to explore the correlation between 6 kinds of immunohistochemical indicators and clinical characteristics of patients. The Kaplan-Meier method and LOG-rank test to univariate analyzed the effect of IHC expression level on patient survival, and the clinical prediction model was constructed to evaluate and valate the prediction model. Results The expression levels of PD-1, PD-L1, FOXP3+, and CD25+were positively correlated with tumor infiltration depth and lymph node metastasis (P < 0.05); The expression levels of CD4+and CD8+were negatively correlated with tumor infiltration depth and lymph node metastasis (P < 0.05). Lymph node metastasis, high expression of PD-1, PD-L1, FOXP3+, and CD25+are independent risk factors affecting patient prognosis (P < 0.05). Patients with low expression of PD-1, PD-L1, FOXP3+, CD25+ and high expression of CD4+,CD8+ had better three-year survival rates (P < 0.001). The prediction model constructed based on influencing factors has good discrimination and accuracy. Conclusion The prediction model based on PD-1, PD-L1, FOXP3+, CD25+ expression levels and lymphocytes infiltration has a high predictive validity for the prognosis of patients with EC.

To address the challenges of high energy consumption and low efficiency in recovering phenols and oils from coal chemical wastewater (CCW), this study focused on the design and synthesis of metal-organic frameworks and spherical carbon particle (MOFs/SCP) adsorbents with a high adsorption capacity and ease of desorption. Additionally, a new comprehensive treatment mode named "adsorption-desorption-regeneration-recovery" (ADRR) was developed to efficiently recover phenols and oils from CCW. The results revealed that the ADRR treatment mode maintained high adsorption and desorption efficiencies of MOFs/SCP, which remained consistently above 95 %. Additionally, methanol regeneration reached similar to 90 %, and the recovery efficiency of phenols and oils was similar to 83 %. The analysis of the adsorption behavior model indicated that the adsorption of phenols and oils by MOFs/SCP mainly involved monolayer chemical adsorption characterized by spontaneity, heat absorption, and disorder. The dynamic adsorption model exhibited a strong correlative ability to predict and assess the adsorption capacity, rate, equilibrium, and operating parameters. Finally, structural analyses and molecular dynamics simulations revealed that the micro-interaction mechanisms between MOFs/SCP and phenols and oils mainly depended on the distinctive hydrophobic nature and porous adsorption capabilities of MOFs/SCP. These interactions were mainly facilitated by electrostatic interactions, pi-pi interactions, and hydrogen bonding. The findings of the study are crucial for achieving high-value recovery of phenols and oils from CCW and, promoting the clean and sustainable growth of the coal chemical industry.

Metal organic framework materials(MOFs) are coordination polymers formed by coordination. Recent studies have found that MOFs are the kind of heterogeneous catalysts with excellent catalytic performance due to their stable active sites in many reactions. In this paper,the ZnCo-MOF bimetallic catalyst material were prepared by the synthetic method of rotational hydrothermal crystallization using ZnO as the zinc source. X-ray diffraction(XRD), Fourier transform infrared spectrum(FTIR),scanning electron microscopy(SEM)and X-ray photoelectron spectro- scopy(XPS)were used to represent the morphology,structure and composition of the catalyst. The prepared catalyst can obtain epoxide with high conversion and high selectivity without adding any initiator or co-reducing agent in the air epoxidation reaction of catalyzed diolefin by microwave heating. The ZnCo-MOF catalyst synthesized by rotational hydrothermal method(110 r/min)has the best activity in the catalytic epoxidation of alpha-pinene and alpha-methylstyrene, which can obtain 86.3% and 99.8%(molar fraction)conversion,respectively,and the selectivity of the correspon- ding epoxides reach 93.8% and 94.3%.

Here, we report the synthesis of spherical bimetal ZnCo-MOF materials by a hydrothermal rotacrystallization method and their catalytic activity on the air epoxidation of mixed biolefins enhanced by microwaves. The structural and chemical properties of the ZnCo-MOF materials were fully characterized by XRD, IR, SEM, TG, XPS, and NH3-TPD. The morphology of the material exhibited a three-dimensional spherical structure. From an NH3-TPD test of the ZnCo-MOF catalyst, it could be concluded that the Zn0.1Co1-MOF-H-150 rpm material had the highest acidic content and the strongest acidity among the catalysts synthesized by different methods, which gave the best performance in the epoxidation of mixed biolefins. The air epoxidation reaction was carried out under atmospheric pressure and microwave conditions, in the absence of any initiator or coreducing agent. Moreover, the Zn0.1Co1-MOF catalyst could be recycled six times without reducing the catalytic activity significantly, which showed the stability of spherical catalyst material under microwaves.

A recyclable [Co(NH3)6]Cl3complex was synthesized to catalyze the epoxidation of α-pinene. With air as the oxidant, [Co(NH3)6]Cl3obtained 97.4% conversion of α-pinene and 98.3% selectivity of epoxide.

Quantum-size metal clusters with multiple delocalized electrons could support collective plasmon excitation, and thus, theoretically, coupling of plasmons in the few-atom limit might exist between assembled metal clusters, while currently few experimental observations about this phenomenon have been reported. Here we examined the optical absorption of DNA-templated Ag nanoclusters (DNA-AgNCs) assembled through DNA hybridization and found their absorption peaks were sensitive to the assembled distances, which share common characteristics with classical plasmon coupling. Dipolar charge distribution, multiple transition contributed optical absorption, and strongly enhanced electric field simulated by time-dependent density functional theory (TDDFT) indicated the origin of the absorption of individual DNA-AgNCs is a plasmon. The consistency of the peak-shifting trend between experimental and simulation results for assembled DNA-AgNCs suggested the possible presence of plasmon coupling. Our data imply the possibility for quantum-size structures to support plasmon coupling and also show that DNA-AgNCs possess the potential to be promising materials for construction of plasmon-coupling devices with ultrasmall size, site-specific and stoichiometric binding abilities, and biocompatibility.

To date, it was difficult to develop catalytic systems for activating O-2 in the absence of initiator and sacrificial co-reductant for high-efficiency epoxidation of olefins under mild conditions. Herein, different compositions of ZnCo-MOF have been prepared via a dry-gel crystallization method, which were used to catalyze the epoxidation of alpha-pinene with air at 90 degrees C. Zn0.1Co1-MOF-D2-24 performed the best catalysis activity to give 95.5 % alpha-pinene conversion and 96.7 % epoxide selectivity. The epoxidation results showed that Zn and Co could effectively activate air to epoxidize alpha-pinene in high efficiency. This bimetal catalytic effect was assigned to the contribution of interacted lattice Zn and Co ions embedded into crystalline MOF framework with similar electronic structure and ion radius, which avoided the use of organic peroxide initiators and other co-reducing agents. Under anhydrous conditions, Zn0.1Co1-MOF-D2-24 showed stable catalytic activity in the epoxidation of alpha-pinene with air by at least six recycles.

Benzimidazole and metal cobalt salts were employed in the synthesis of Co-ZIF-9 by solvothermal crystallization. Highly active catalysts for selective hydrogenation of carbonyl compounds were developed. The optimal nanocatalyst Co-ZIF-350 manifested remarkable activity and selectivity for the hydrogenation of cyclohexanone under mild conditions. Catalytic conversion of cyclohexanone reached the highest over the catalyst of Co-ZIF-9-pyrolyzed at 350 degrees C for 2 h, in which the conversion of cyclohexanone was 100 % and the selectivity of cyclohexanol was > 99 % at 50 degrees C. A wide scope of ketones/aromatic aldehydes could be selectively reduced to the corresponding alcohols with high yields. Importantly, the nanocatalyst Co-ZIF-350 presented good tolerance of substrates with various functional groups under mild conditions.

The lack of blood-brain barrier (BBB) penetrating ability has hindered the delivery of many therapeutic agents for tauopathy treatment. In this study, we report the synthesis of a circular bifunctional aptamer to enhance the in vivo BBB penetration for better tauopathy therapy. The circular aptamer consists of one reported transferrin receptor (TfR) aptamer to facilitate TfR-aptamer recognition-induced transcytosis across BBB endothelial cells, and one Tau protein aptamer that we recently selected to inhibit Tau phosphorylation and other tauopathy-related pathological events in the brain. This novel circular Tau-TfR bifunctional aptamer displays significantly improved plasma stability and brain exposure, as well as the ability to disrupt tauopathy and improve traumatic brain injury (TBI)-induced cognitive/memory deficits in vivo, providing important proof-of-principle evidence that circular Tau-TfR aptamer can be further developed into diagnostic and therapeutic candidates for tauopathies.

Lipid-oligonucleotide conjugates (LONs) are powerful molecular-engineering materials for various applications ranging from biosensors to biomedicine. Their unique amphiphilic structures enable the self-assembly and the conveyance of information with high fidelity. In particular, LONs present remarkable potential in measuring cellular mechanical forces and monitoring cell behaviors. LONs are also essential sensing tools for intracellular imaging and have been employed in developing cell-surface-anchored DNA nanostructures for biomimetic-engineering studies. When incorporating therapeutic oligonucleotides or small-molecule drugs, LONs hold promise for targeted therapy. Moreover, LONs mediate the controllable assembly and fusion of vesicles based on DNA-strand displacements, contributing to nanoreactor construction and macromolecule delivery. In this review, we will summarize the general synthesis strategies of LONs, provide some characterization analysis and emphasize recent advances in bioanalytical and biomedical applications. We will also consider the relevant challenges and suggest future directions for building better functional LONs in nanotechnology and materials-science applications.

Functional nucleic acids (FNAs) are garnering tremendous interest owing to their high modularity and unique bioactivity. Three-dimensional FNAs have been developed to overcome the issues of nuclease degradation and limited cell uptake. We have developed a new facile approach to the synthesis of multiple three-dimensional FNA nanostructures by harnessing photo-polymerization-induced self-assembly. Sgc8 aptamer and CpG oligonucleotide were modified as macro chain-transfer reagents to mediate in situ polymerization and self-assembly. Diverse structures, including micelles, rods, and short worms, afford these two FNAs afford these two FNAs with higher nuclease resistance in serum serum, greater cellular uptake efficiency, and increased bioactivity.

Rationale: A cascade, or domino, reaction consists of two, or more, consecutive reactions such that subsequent reactions occur only if some chemical functionality has first been established in the prior step.However, while construction of predesigned and desired molecular domino reactors in a tailored manner is a valuable endeavor, it is still challenging.Methods: To address this challenge, we herein report an aptamer-based photodynamic domino reactor built through automated modular synthesis.The engineering of this reactor takes advantage of the well-established solid-phase synthesis platform to incorporate a photosensitizer into G-quadruplex/ hemin DNAzyme at the molecular level.Results: As a proof of concept, our photodynamic domino reactor, termed AS1411/heminpyrochlorophyll A, achieves in vivo photodynamic domino reaction for efficient cancer treatment by using a high concentration of hydrogen peroxide (H2O2) in the tumor microenvironment (TME) to produce O2, followed by consecutive generation of singlet oxygen ( 1 O2) using the pre-produced O2.More specifically, phosphoramidite PA (pyrochlorophyll A) is coupled to aptamer AS1411 to form AS1411-PA ApDC able to simultaneously perform in vivo targeted imaging and photodynamic therapy (PDT).The insertion of hemin into the AS1411 G-quadruplex was demonstrated to alleviate tumor hypoxia by decomposition of H2O2 to produce O2.This was followed by the generation of 1 O2 by PA to trigger cascading amplified PDT.Conclusion: Therefore, this study provides a general strategy for building an aptamer-based molecular domino reactor through automated modular synthesis.By proof of concept, we further demonstrate a novel method of achieving enhanced PDT, as well as alleviating TME hypoxia at the molecular level.

A method for synthesizing Co-MOF by rapidly rotating hydrothermal crystallization is proposed. When the rotation speed was 150 rpm, only 2 h was needed to synthesize Co-MOF-150-2 with high catalytic activity and stability.

The use of aptamers in bioanalytical and biomedical applications exploits their ability to recognize cell surface protein receptors. Targeted therapeutics and theranostics come to mind in this regard. However, protein receptors occur on both cancer and normal cells; as such, aptamers are now taxed with identifying high vs. low levels of protein expression. Inspired by the flexible template mechanism and elegant control of natural nucleic acid-based structures, we report an allosteric regulation strategy for constructing a structure-switching aptamer for enhanced target cell recognition by engineering aptamers with DNA intercalated motifs (i-motifs) responsive to the microenvironment, such as pH. Structure-switching sensitivity can be readily tuned by manipulating i-motif sequences. However, structure-switching sensitivity is difficult to estimate, making it equally difficult to effectively screen modified aptamers with the desired sensitivity. To address this problem, we selected a fluorescent probe capable of detecting G-quadruplex in complicated biological media.

Compared with conventional chemotherapy and radiotherapy, targeted molecular therapy, e.g., antibody-drug conjugates or aptamer-drug conjugates, can specifically identify overexpressed natural receptors on the cancer cell, perform targeted release of anticancer drugs, and achieve targeted killing of tumor cells. However, many natural receptors are also expressed on non-cancer cells, thereby diverting the targeting molecules to healthy cells. By generating artificial cell surface receptors specific to diseased cells, aptamer-drug conjugates can identify these artificial receptors, improve therapeutic efficacy, and decrease the minimum effective dosage. In this study, we use high K+ and high H2O2 of the tumor microenvironment (TME) to produce polydopamine only on living cancer cell membrane. Owing to the significant reactivity of polydopamine with amino groups, e.g., the amino group of proteins, polydopamine can deposit on tumor cells and act as “artificial receptors” for targeted delivery of anticancer drugs with amino groups, in other words, amino-containing drugs and protein drugs.

Photodynamic therapy (PDT) is an effective and noninvasive therapeutic strategy employing light-triggered singlet oxygen (SO) and reactive oxygen species (ROS) to kill lesional cells. However, for effective in vivo delivery of PDT agent into the cancer cells, various biological obstacles including blood circulation and condense extracellular matrix (ECM) in the tumor microenvironment (TME) need to be overcome. Furthermore, the enormous challenge in design of smart drug delivery systems is meeting the difference, even contradictory required functions, in different steps of the complicated delivery process. To this end, we present that TME-activatable circular pyrochlorophyll A (PA)-aptamer-PEG (PA-Apt-CHO-PEG) nanostructures, which combine the advantages of PEG and aptamer, would be able to realize efficient in vivo imaging and PDT. Upon intravenous (i.v.) injection, PA-Apt-CHO-PEG shows "stealth-like" long circulation in blood compartments without specific recognition capacity, but once inside solid tumor, PA-Apt-CHO-PEG nanostructures are cleaved and then form PA-Apt Aptamer-drug conjugations (ApDCs) in situ, allowing deep penetration into the solid tumor and specific recognition of cancer cells, both merits, considering anticipated future clinical translation of ApDCs.

Novel materials from self-assembled nanocrystals hold great promise for applications ranging from inorganic catalysis to bio-imaging. However, because of the inherent anisotropic properties, it is challenging to assemble one-dimensional (1D) nanorods into higher-order structures (e.g. 2D sheets or 3D networks) without any support. Here, we have developed a facile strategy for the direct self-assembly of 1D nanorods into free-standing 2D nanorafts with lateral dimensions up to several micrometers. As a general approach, 2D nanorafts with diverse compositions, e.g. MgF2, WO2, CdS, ZnS, and ZnSe nanorafts, have been fabricated from the assembly of their 1D building blocks. More importantly, these nanorafts show high stability even when dispersed in different solvents, making them suitable for various applications. Because of their high porosity and strong adsorption capability, MgF2 nanorafts were investigated to illustrate the collective advantages generated from the assembly platform. Moreover, flexibility in the composition and structure of the building blocks demonstrated in this work will lead to next generation materials with rich functionalities.

Photoresponsive materials are emerging as ideal carriers for precise controlled drug delivery owing to their high spatiotemporal selectivity. However, drawbacks such as slow release kinetics, inherent toxicity, and lack of targeting ability hinder their translation into clinical use. We herein constructed a new DNA aptamer-grafted photoresponsive hyperbranched polymer, which can self-assemble into nanoparticles, thereby achieving biocompatibility and target specificity, as well as light-controllable release behavior. Upon UV-irradiation, rapid release induced by disassembly was observed for Nile Red-loaded nanoparticles. Further in vitro cell studies confirmed this delivery system’s specific binding and internalization performance arising from the DNA aptamer corona. The DOX-loaded nanoassembly exhibited selective phototriggered cytotoxicity towards cancer cells, indicating its promising therapeutic effect as a “smart” drug delivery system.

Over the past decade, the field of polymer-oligonucleotide nanomaterials has flourished because of the development of synthetic techniques, particularly living polymerization technologies, which provide access to polymers with well-defined architectures, precise molecular weights, and terminal or side-chain functionalities. Various "living" polymerization methods have empowered chemists with the ability to prepare functional polymer-oligonucleotide conjugates yielding a library of architectures, including linear diblock, comb, star, hyperbranched star, and gel morphologies. Since oligonucleotides are hydrophilic and synthetic polymers can be tailored with hydrophobicity, these amphiphilic polymer-oligonucleotide conjugates are capable of self-assembling into nanostructures with different shapes, leading to many high-value-added biomedical applications, such as drug delivery systems, gene regulation, and 3D-bioprinting. This review aims to highlight the main living polymerization approaches to polymer-oligonucleotide conjugates, including ring-opening metathesis polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation transfer polymerization (RAFT), and ring-opening polymerization of cyclic esters and N-carboxyanhydride. The self-assembly properties and resulting applications of polymer-DNA hybrid materials are highlighted as well.