Triggered by the endogenous chemical energy in the tumor microenvironment (TME), chemodynamic therapy (CDT) as an emerging non‐exogenous stimulant therapeutic modality has received increasing ...attention in recent years. The chemodynamic agents can convert internal hydrogen peroxide (H2O2) into the lethal reactive oxygen species (ROS) hydroxyl radicals (•OH) for oncotherapy. Compared with other therapeutic modalities, CDT possesses many notable advantages, such as tumor‐specific, highly selective, fewer systemic side effects, and no need for external stimulation. Nevertheless, mild acid pH, low H2O2 content, and overexpressed reducing substance in TME severely suppressed the CDT efficiency. With the rapid development of nanotechnology, some kinds of nanomaterials have been utilized with improved CDT efficiency. In particular, the excellent photo‐, ultrasound‐, magnetic‐, and other stimuli‐response properties of nanomaterials make it possible for combination cancer therapy of CDT with other therapeutic modalities, and it has shown superior anti‐cancer activity than monotherapies. Therefore, it is necessary to summarize the application of nanomaterial‐based chemodynamic cancer therapy. In this review, the various nanomaterials‐based nanoplatforms for CDT and its combinational therapies are summarized and discussed, aiming to provide inspiration for the design of better‐quality agents to promote the CDT development and lay the foundation for its future conversion to clinical applications.
Chemodynamic therapy (CDT) is an emerging non‐exogenous stimulant therapeutic modality and has drawn increasing attention in recent years. In particular, varieties of nanomaterials have been utilized in CDT with encouraging therapeutic efficiency. The latest progress on CDT‐involved combined therapy is overviewed, aiming to provide inspiration for the design of better‐quality agents and hoping to promote CDT future clinical conversion.
The main goal of the current study was to investigate the membrane fouling mechanism of aerobic granular sludge (AGS) with various AGS sizes. In this regard, AGSs were sieved into 6 levels: 0∼0.5, ...0.5∼0.7, 0.7∼1, 1∼1.2, 1.2∼1.7 mm and larger than 1.7 mm, then filtrated by a small dead-end filtration cell. Interestingly, there appeared a critical AGS size (1∼1.2 mm) for membrane fouling. Above 1.2 mm, flux increased and fouling reduced with size, due to the loose cake layer and high permeability caused by larger AGS. Below 1 mm, for smaller AGS, higher flux and lower fouling appeared, because less extracellular polymeric substance (EPS) formed and adhered onto AGS foulants. In the critical size, membrane fouling was serious to the most extent, on account of the dual role of the compact structure of cake fouling layer and the adhesion of EPS. Moreover, this critical AGS size also possessed the highest cake layer, pore blocking and irreversible fouling, which generally existed in various operational conditions. Besides, the results of SEM, AFM, hydrophilicity and ATR-FTIR also proved that the existence of the maximum membrane fouling at the critical AGS size. This study provides a deep understanding of the membrane fouling mechanisms of AGS in membrane filtration and is beneficial for developing a new membrane fouling mitigation strategy by terms of regulating AGS size.
Display omitted
•Membrane fouling mechanisms of AGS with various AGS sizes were studied.•Interestingly, there appeared a critical AGS size (1–1.2 mm) for membrane fouling.•Above or below critical AGS size, fouling reduced as the size increase or decrease.•For the fouling resistance, pore blocking was higher than cake layer.•The micromorphology of fouled membrane was used to analyze critical AGS size.
Severe dendrite growth and high‐level activity of the lithium metal anode lead to a short life span and poor safety, seriously hindering the practical applications of lithium metal batteries. With a ...trisalt electrolyte design, an F‐/N‐containing inorganics–rich solid electrolyte interphase on a lithium anode is constructed, which is electrochemically and thermally stable over long‐term cycles and safety abuse conditions. As a result, its Coulombic efficiency can be maintained over 98.98% for 400 cycles. An 85.0% capacity can be retained for coin‐type full cells with a 3.14 mAh cm−2 LiNi0.5Co0.2Mn0.3O2 cathode after 200 cycles and 1.0 Ah pouch‐type full cells with a 4.0 mAh cm−2 cathode after 72 cycles. During the thermal runaway tests of a cycled 1.0 Ah pouch cell, the onset and triggering temperatures were increased from 70.8 °C and 117.4 °C to 100.6 °C and 153.1 °C, respectively, indicating a greatly enhanced safety performance. This work gives novel insights into electrolyte and interface design, potentially paving the way for high‐energy‐density, long‐life‐span, and thermally safe lithium metal batteries.
An F‐/N‐containing inorganics‐rich solid electrolyte interphase is constructed, which is electrochemically and thermally stable during the long‐term cycles and safety abuse conditions. More than 6 times longer cycles compared with routine cells are achieved in 1.0 Ah pouch‐type cells. The onset and triggering temperatures during the thermal runaway are increased from 70.8 and 117.4 to 100.6 and 153.1 °C, respectively.
► Cellulose nanocrystals and nanofibrils isolated from rice straw yielded up to 20%. ► Isolation by acid hydrolysis, blending and TEMPO oxidation was compared. ► Nanocellulose showed distinctly ...different sizes and surfaces. ► Nanocellulose had cellulose Iβ crystalline structure with crystallinity up to 91%. ► Nanocellulose self assembled into 153–440nm fibers upon rapid freezing and drying.
Cellulose nanocrystals (CNCs) and nanofibrils (CNFs) have been isolated from pure rice straw cellulose via sulfuric acid hydrolysis, mechanical blending and TEMPO-mediated oxidation to 16.9%, 12% and 19.7% yields, respectively. Sulfuric acid hydrolysis produced highly crystalline (up to 90.7% CrI) rod-like (3.96–6.74nm wide, 116.6–166nm long) CNCs with similarly negative surface charges (−67 to −57mV) and sulfate contents but decreasing yields and dimensions with longer hydrolysis time. Mechanical defibrillated CNFs were 82.5% crystalline and bimodally distributed in sizes (2.7nm wide and 100–200nm long; 8.5nm wide and micrometers long). TEMPO mediated oxidation liberated the most uniform, finest (1.7nm) and micrometer long, but least crystalline (64.4% CrI) CNFs. These nanocellulose self-assembled into submicron (153–440nm wide) fibers of highly crystalline (up to 90.9% CrI) cellulose Iβ structure upon rapid freezing (−196°C) and freeze-drying. The self-assembling behaviors were analyzed based on nanocellulose dimensions, specific surfaces and surface chemistries.
Abstract
Metadiscourse has received considerable attention in recent years as a way of understanding the rhetorical negotiations involved in academic writing. But while a useful tool in revealing ...something of the dynamic interactions which underlie persuasive claim making, it has little to say about the role of nouns in this process. We address this gap by exploring the rhetorical functions of what we call metadiscursive nouns (such as fact, analysis, belief) and by mapping them onto a model of metadiscourse. The study examines ‘metadiscursive noun + post-nominal clause’ patterns, one of the most frequent structures containing such nouns, in a corpus of 120 research articles across six disciplines. Developing a rhetorically based classification and exploring the interactive and interactional use of metadiscursive nouns, we show that they are another key element of metadiscourse, offering writers a way of organizing discourse into a cohesive flow of information and of constructing a stance towards it. These interactions are further shown to realize the epistemological assumptions and rhetorical practices of particular disciplines.
Two mixed‐metal gallium iodate fluorides, namely, α‐ and β‐Ba2GaF4(IO3)2(IO3) (1 and 2), have been designed by the aliovalent substitutions of α‐ and β‐Ba2VO2F2(IO3)2(IO3) (3 and 4) involving one ...cationic and two anionic sites. Both 1 and 2 display large second‐harmonic generation responses (≈6×KH2PO4 (KDP)), large energy band gaps (4.61 and 4.35 eV), wide transmittance ranges (≈0.27–12.5 μm), and high relevant laser‐induced damage thresholds (29.7× and 28.3×AgGaS2, respectively), which indicates that 1 and 2 are potential second‐order nonlinear optical materials in the ultraviolet to mid‐infrared. Our studies propose that three‐site aliovalent substitution is a facile route for the discovery of good NLO materials.
Trading places: Two new nonlinear optical materials, α‐ and β‐Ba2GaF4(IO3)2(IO3) (1 and 2), were designed via three‐site aliovalent substitution of VO4F2 in α‐ and β‐Ba2VO2F2(IO3)2(IO3) by GaO2F4. The new materials display large second‐harmonic generation responses (≈6×KH2PO4 (KDP)), wide energy band gaps (4.61 and 4.35 eV), and high laser damage thresholds (29.7× and 28.3× relative to that of AgGaS2).
Successful research writers construct texts by taking a novel point of view toward the issues they discuss while anticipating readers’ imagined reactions to those views. This intersubjective ...positioning is encompassed by the term stance and, in various guises, has been a topic of interest to researchers of written communication and applied linguists for the past three decades. Recognizing that academic writing is less objective and “author evacuated” than Geertz and others once supposed, analysts have sought to identify the ways that writers use language to acknowledge and construct social relations as they negotiate agreement of their interpretations of data with readers. Despite prolonged and widespread curiosity concerning the notion of stance, however, together with an interest in the gradual evolution of research genres more generally, very little is known of how it has changed in recent years and whether such changes have occurred uniformly across disciplines. In this article we set out to explore these issues. Drawing on a corpus of 2.2 million words taken from the top five journals in each of four disciplines at three distinct time periods, we seek to determine whether authorial projection has changed in academic writing over the past 50 years.
To date, ionic conducting hydrogel attracts tremendous attention as an alternative to the conventional rigid metallic conductors in fabricating flexible devices, owing to their intrinsic ...characteristics. However, simultaneous realization of high stiffness, toughness, ionic conductivity, and freezing tolerance through a simple approach is still a challenge. Here, a novel highly stretchable (up to 660%), strong (up to 2.1 MPa), tough (5.25 MJ m−3), and transparent (up to 90%) ionic conductive (3.2 S m−1) organohydrogel is facilely fabricated, through sol–gel transition of polyvinyl alcohol and cellulose nanofibrils (CNFs) in dimethyl sulfoxide‐water solvent system. The ionic conductive organohydrogel presents superior freezing tolerance, remaining flexible and conductive (1.1 S m−1) even at −70 °C, as compared to the other reported anti‐freezing ionic conductive (organo)hydrogel. Notably, this material design demonstrates synergistic effect of CNFs in boosting both mechanical properties and ionic conductivity, tackling a long‐standing dilemma among strength, toughness, and ionic conductivity for the ionic conducting hydrogel. In addition, the organohydrogel displays high sensitivity toward both tensile and compressive deformation and based on which multi‐functional sensors are assembled to detect human body movement with high sensitivity, stability, and durability. This novel organohydrogel is envisioned to function as a versatile platform for multi‐functional sensors in the future.
A polyvinyl alcohol/cellulose nanofibril organohydrogel with simultaneously improved strength, toughness, and ionic conductivity is rationally designed. The organohydrogel shows outstanding freezing tolerance while maintains high ionic conductivity (1.1 S m−1) at −70 °C due to the presence of high dielectric dimethyl sulfoxide‐water binary solvent. The organohydrogel demonstrates great promise in serving as multi‐functional sensors under extreme conditions.
Exploring advanced strategies in alleviating the thermal runaway of lithium‐metal batteries (LMBs) is critically essential. Herein, a novel electrolyte system with thermoresponsive characteristics is ...designed to largely enhance the thermal safety of 1.0 Ah LMBs. Specifically, vinyl carbonate (VC) with azodiisobutyronitrile is introduced as a thermoresponsive solvent to boost the thermal stability of both the solid electrolyte interphase (SEI) and electrolyte. First, abundant poly(VC) is formed in SEI with thermoresponsive electrolyte, which is more thermally stable against lithium hexafluorophosphate compared to the inorganic components widely acquired in routine electrolyte. This increases the critical temperature for thermal safety (the beginning temperature of obvious self‐heating) from 71.5 to 137.4 °C. The remained VC solvents can be polymerized into poly(VC) as the battery temperature abnormally increases. The poly(VC) can not only afford as a barrier to prevent the direct contact between electrodes, but also immobilize the free liquid solvents, thereby reducing the exothermic reactions between electrodes and electrolytes. Consequently, the internal‐short‐circuit temperature and “ignition point” temperature (the starting temperature of thermal runaway) of LMBs are largely increased from 126.3 and 100.3 °C to 176.5 and 203.6 °C. This work provides novel insights for pursuing thermally stable LMBs with the addition of various thermoresponsive solvents in commercial electrolytes.
A thermoresponsive electrolyte is introduced into a working cell to relieve the exothermic reactions between electrodes and electrolytes, the internal short circuit. The critical temperature for thermal safety, “ignition point” of battery, and internal‐short‐circuit temperature of batteries with thermoresponsive electrolyte increase from 71.5, 100.3, and 126.3 °C to 137.4, 203.6, and 176.5 °C compared with routine electrolyte.
The catalytic hydrogenation of aromatic nitro compounds containing multiple functional groups into amino compounds with high conversion rates, selectivity, and stability under mild conditions is a ...great challenge. Herein, a well defined catalyst (Co@NC) is prepared through the pyrolysis of the Co-centered metal-organic framework (MOF) at the optimized temperature. The as-synthesized catalyst exhibits a high conversion rate and selectivity for the hydrogenation of 12 aromatic nitro compounds with different competing groups into desired amino compounds with hydrazine hydrate under mild conditions (80 °C, 30 min, and 1 atm). The catalyst also shows excellent stability and can be reused over 20 times without considerably losing its activity. It is found that the Co-Nx site is the main active site for catalytic hydrogenation, and the Mott-Schottky effect between the surface Co NPs and N-doped carbon can further promote the hydrogenation reaction. EXAFS, TEM, XPS, and Raman analyses confirm that cobalt nanoparticles (NPs) are properly encapsulated by the N-doped carbon matrix at the optimized temperature, and the Co species maintain a high spin state after the catalysis, which may be responsible for the high performance of Co@NC. This work demonstrates not only a highly efficient catalyst for hydrogenation under mild conditions, but also provides insight into the active sites in Co-based catalysts for hydrogenation.
The defined catalyst (Co@NC) is prepared through the pyrolysis of the Co-centered metal-organic framework (MOF), in which Co active species (Co-Nx, surface Co NPs) and particle size play important roles in the catalytic hydrogenation of aromatic nitro compounds.
PDF
