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Arrays of single crystal germanium nanowires were fabricated in a self-assembled manner by a hydrothermal method without any metallic catalyst or templates. SEM, TEM, HRTEM, SAED, EDS, FTIR analyses show that the germanium nanowires are composed of a core of germanium and a very thin GeO2shell, and have a smooth surface and straightforward body, uniform diameters, a rectangular growth sectional view, and a knife edge growth tip. In the growth process, the H橷 OH−play an important assistant role, a role of oxidation-reduction in the growth tip. PL shows that the germanium nanowires have intensive purple light emission at about 360 nm and 396 nm, which may be come from nano-size effect of GeNWs and the neutral oxygen vacancy, respectively. [ABSTRACT FROM AUTHOR]

We report a novel DNA lesion-modified nanotweezer that underwent conformational switching upon ALKBH enzyme-mediated lesion repair. We demonstrated that the DNA lesion-modified nanotweezer enabled specific and rapid monitoring of ALKBH2 and ALKBH3 activities and screening of inhibitors. Importantly, this strategy allowed evaluating ALKBH2-associated drug resistance in cells.

Bacterial biofilms play a crucial role in the emergence of antibiotic resistance and the persistence of chronic infections. The challenge of effectively eradicating bacterial biofilms while ensuring minimal toxicity to normal cells persists. Carbon-based artificial nanoenzymes have attracted considerable attention as emerging nanotheranostic agents, owing to their biocompatibility, cost-effectiveness, and straightforward synthesis. In this study, we have developed a multifunctional carbon dots (CDs) system, specifically CDs functionalized with 1-(3-aminopropyl) imidazole (API), termed CDs-API. This system demonstrates acid-activated antibiofilm activity. The CDs-API were synthesized from chlorogenic acid (ChA), a bioactive compound naturally occurring in coffee, and subsequently functionalized with API to achieve charge-switchable properties under acidic conditions. This distinctive feature enables CDs-API to efficiently penetrate bacterial biofilms and selectively target the colonized bacteria. The enzyme-like activity of CDs-API effectively consumes high levels of glutathione (GSH) within the biofilm, leading to the accumulation of reactive oxygen species (ROS). Consequently, this process degrades the extracellular polymeric substance (EPS) matrix, damages bacterial DNA and protein structures, and disrupts the redox balance, ultimately leading to bacterial cell death. Experimental results demonstrated that CDs-API effectively inhibited the growth of methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa (PAE) while promoting wound healing with minimal damage to healthy tissues. The acid-activated charge-switchable capability of CDs-API provides superior antibacterial efficacy compared to traditional antibiotics, rendering it a promising candidate for the treatment of bacterial biofilm infections., Competing Interests: The authors declare that they have no competing interests., (This journal is © The Royal Society of Chemistry.)

Five new indole diterpenoids, shearinines U-Y (2-6), and the known compound 22,23-dehydro-shearinine A (1) were isolated from cultures of the entomogenous fungus Penicillium sp. Their structures were elucidated primarily by NMR experiments. The absolute configurations of 2-6 were assigned by electronic circular dichroism calculations, respectively. Compounds 1-3 showed moderate cytotoxicity, with IC 50 values of 11.7-26.2 μM., Competing Interests: The authors declare no conflict interest., (This journal is © The Royal Society of Chemistry.)

In this work, three iridium(iii) tetrazolato complexes have been used in antibacterial, biofilm removal and for other bioactivities for the first time. Notably, these iridium(iii) tetrazolato complexes with high antibacterial, especially, Ir-CF 3 TAZ showed the best antimicrobial activity and the most effective hemolytic performance, which may pave the way to explore the value of the complexes for clinical applications in the future., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Nanospaces within enzymes play a crucial role in chemical reactions in biological systems, garnering significant attention from supramolecular chemists. Inspired by the highly efficient catalysis of enzymes, artificial supramolecular hosts have been developed and widely employed in various reactions, paving the way for innovative and selective catalytic processes and offering new insights into enzymatic catalytic mechanisms. In supramolecular macrocycle systems, weak non-covalent interactions are exploited to enhance substrate solubility, increase local concentration, and stabilize the transition state, ultimately accelerating reaction rates and improving product selectivity. In this review, we will focus on the opportunities and challenges associated with the catalysis of chemical reactions by supramolecular macrocycles in the aqueous phase. Key issues to be discussed include limitations in molecular interaction efficiency in aqueous media, product inhibition, and the incompatibility of catalysts or conditions in "one-pot" reactions.

Contamination of heavy metals (HMs) has caused increasing concern due to their ecological toxicities and difficulties in degradation. The transport, retention, and release of HMs in porous media are highly related to their environmental fate and risk to groundwater. Column transport experiments and numerical simulations were conducted to investigate the retention and release behaviors of Cu 2+ , Pb 2+ , Cd 2+ , and Zn 2+ in the presence and absence of kaolin under varying ionic strengths and cation types. The interaction between HMs and soil colloids is critical to these processes, yet it remains poorly understood. In both single and multi-metal systems, the mobility of HMs ranked as Cd 2+ > Zn 2+ > Cu 2+ > Pb 2+ , is influenced by their hydrolysis ability. Multi-metal systems showed higher mobility due to competition for retention sites, and Ca 2+ enhanced transport more than Na + due to greater affinity to the sand surface. Kaolin reduced HM transport by adsorption and led to irreversible retention. Cation exchange (Na + replacing Ca 2+ ) followed by reduced ionic strength promoted HM release due to the remobilization of kaolin associated with HMs. Uniform, nonmonotonic, and exponential retention profiles indicated variations in the spatial distribution of HMs. The Pb 2+ and Cu 2+ were more retained near the column inlet than Cd 2+ and Zn 2+ , indicating limited mobility in the deep subsurface. Numerical simulations well described HM transport, considering the adsorption and desorption of HMs and the solid-water interface. These results enhance understanding of HM fate in terrestrial environments.

The interaction between dissolved organic matter (DOM) and iron minerals has a significant effect on its stabilization and preservation in the environment. In this study, iron minerals with different crystal forms (crystalline goethite and amorphous ferrihydrite) were selected to investigate the photochemical transformation process for DOM immobilized on iron minerals under simulated sunlight irradiation at the molecular scale with the help of Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results showed that a total of 7148 molecules were detected in alkaline-extractable sedimentary DOM, of which 38.8% and 36.2% were adsorbed by ferrihydrite and goethite, respectively, while there was no selectivity difference between the two iron minerals in terms of DOM adsorption. After simulated sunlight irradiation, the DOM adsorbed by goethite was significantly degraded (58.3%), in which the H/C ratio of the mineral-immobilized DOM increased and the O/C ratio decreased, and the photodegradation primarily involved DOM molecules with high Kendrick mass defect (KMD) values. The results confirmed that the iron mineral types play an important role in the transportation and transformation of DOM, which adds to the understanding of the fate of DOM in natural environments.

The intricate nature of the tumor microenvironment (TME) results in the inefficient delivery of anticancer drugs within tumor tissues, significantly compromising the therapeutic effect of cancer treatment. To address this issue, transdermal drug delivery microneedles (MNs) with high mechanical strength have emerged. Such MNs penetrate the skin barrier, enabling efficient drug delivery to tumor tissues. This approach enhances drug bioavailability, while also mitigating concerns such as liver and kidney toxicity associated with intravenous and oral drug administration. Notably, stimulus responsive MNs designed for drug delivery have the capacity to respond to various biological signals and pathological changes. This adaptability enables them to exert therapeutic effects within the TME, exploiting biochemical variations and tailoring treatment strategies to suit tumor characteristics. The present review surveys recent advancements in responsive MN systems. This comprehensive analysis serves as a valuable reference for the prospective application of smart MN drug delivery systems in cancer therapy.

Hydrogen atom transfer (HAT) processes provide an important strategy for selective C-H functionalization. Compared with the popularity of 1,5-HAT processes, however, net-1,2-HAT reactions have been reported less frequently. Herein, we report a unique visible-light-mediated net-1,2-HAT of amidyl radicals for the synthesis of β-amido ketone derivatives. Single-electron transfer (SET) to N -aryloxy amides generates nitrogen-centered radicals (N˙), which undergo a rare net-1,2-HAT to form carbon-centered radicals (C˙). The C-centered radicals are then captured by silyl enol ethers on the way to β-amido ketones. A series of β-amido ketone derivatives (33 examples, up to 97% yield) were prepared with good functional group tolerance demonstrating the synthetic utility of this method. Mechanistic studies, including EPR, radical trapping experiments, deuterium labeling and KIE measurements, suggest an intramolecular radical net-1,2-HAT pathway., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Oral cancer is a significant global health challenge, with conventional treatments often resulting in substantial side effects and limited effectiveness. Phototherapy, encompassing photodynamic and photothermal therapy, presents a promising alternative by selectively targeting and destroying cancer cells with minimal systemic toxicity. However, issues such as insufficient light penetration and limited tumor specificity have restricted their clinical use. Recent advancements in nanosystems have addressed these challenges by enhancing the solubility, stability, and tumor-targeting capabilities of phototherapy agents. This review delves into the latest advancements in phototherapeutic nanosystems for oral cancer, focusing on the design of innovative nanoformulations and targeted delivery strategies. Additionally, it summarizes recent approaches to enhance the efficacy of photodynamic therapy for oral cancer and examines phototherapy-based combination treatments. These advancements hold the promise of significantly improving treatment outcomes while minimizing side effects in oral cancer therapy.

High-performance n-type organic mixed ionic-electronic conductors (OMIECs) are essential for advancing complementary circuits based on organic electrochemical transistors (OECTs). Despite significant progress, current n-type OMIECs often exhibit lower transconductance and slower response times compared to their p-type counterparts, limiting the development of OECT-based complementary circuits. Optimizing the conjugated backbone and side chain structures of OMIECs is critical for enhancing both ion and electron transport efficiencies while maintaining a delicate balance between the two. In this study, hydrophilic polyethylene glycol (PEG) side chains were incorporated into the highly conductive n-type polymer poly(3,7-dihydrobenzo[1,2- b :4,5- b ']difuran-2,6-dione) (PBFDO) backbone to achieve this goal. The incorporation of PEG chains improved ion accessibility, and by adjusting the PEG content, the electronic and ionic transport properties were fine-tuned, ultimately enhancing the performance of OECTs and related p-n complementary circuits. The n-type OECTs based on PBFDO-PEG50wt% demonstrated exceptional transfer characteristics, including a transient response time ( τ ON ) as low as 72 μs, a high geometry-normalized transconductance exceeding 400 S cm -1 , and an impressive μC * value surpassing 720 F cm -1 V -1 s -1 . Notably, the use of PBFDO-PEG50wt% in a complementary inverter resulted in a voltage gain of 20 V/V, more than five times higher than that achieved with unmodified PBFDO (<4 V/V). These findings highlight the importance of balancing electron and ion transport characteristics in OMIECs to achieve high performance in OECTs and their associated circuits, and they validate PEG decoration as an effective approach.

Our research has demonstrated a significant correlation between the Cu doping concentration in CdZnS and its photocatalytic performance, with CZS-2 exhibiting a 15-fold increase in methane (CH 4 ) production rate compared to pristine CZS, reaching a peak value of 519.2 μL g -1 h -1 . Moreover, CZS-2 demonstrates an unprecedented CH 4 selectivity of 85.3%, surpassing previously reported values for analogous systems. In-depth electrochemical analysis reveals that Cu doping strategically modifies the electronic structure of CZS- x , facilitating efficient charge separation and transfer. This optimization minimizes charge recombination, leading to the selective promotion of CO 2 reduction to CH 4 .

Conducting polymers can be dynamically switched between being optically metallic (negative real permittivity) and dielectric (positive real permittivity) by varying their redox state. This has enabled nanoantennas with plasmonic resonances that can be reversibly turned on/off, opening for applications in dynamic metaoptics, reflective displays, and smart windows. However, previous reports on conducting polymer plasmonics were limited to p-type polymers. Here, we show that a highly conducting n-type polymer, called poly(benzodifurandione) (PBFDO), can also provide optically metallic properties and be used to make dynamic optical nanoantennas. The doped version of the polymer becomes metallic at wavelengths above around 700 nm, leading to plasmonic extinction peaks for nanodisks made from the material. These peaks can be reversibly switched off and on electrically or chemically by varying the doping level of the polymer. The study extends the field of dynamic polymer plasmonics to n-type materials and broadens the application areas of PBFDO., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

The innovation of advanced high-rate anodes is of great significance for the development of high-power and fast-charging lithium-ion batteries (LIBs). In this work, self-supported Li 4 Ti 5 O 12 @carbon (LTO@C) nanotube arrays as a high-quality anode are fabricated via anodizing and hydrothermal processes. Owing to the structure having a high contact surface area and good stability, as well as the incorporation of carbon, the LTO@C exhibits a remarkable rate capability (a reversible capability of 290 mA h g -1 , 251.9 mA h g -1 , 228.8 mA h g -1 , and 208.7 mA h g -1 at 1C, 5C, 10C, and 20C, respectively) and cycling performance (71.7% capacity retention after 1000 cycles at 10C), which is superior to LTO. These features suggest the promising application of LTO@C in high-power energy storage areas., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

An efficient and metal-free method for the synthesis of 3-aryl pyrido[1,2- a ]indoles from aryne intermediates and 2-pyridinyl-substituted p -QMs was successfully developed under ambient conditions. The reaction offered a novel and practical protocol to access some diverse functional molecules in good to excellent yields. The proposed mechanism indicated that the reaction proceeded via a formal [3 + 2] cycloaddition step.

Magnetic propulsion of nano-/micro-robots is an effective way to treat implant-associated infections by physically destroying biofilm structures to enhance antibiotic killing. However, it is hard to precisely control the propulsion in vivo . Magnetic-nanoparticle coating that can be magnetically pulled off does not need precise control, but the requirement of adhesion stability on an implant surface restricts its magnetic responsiveness. Moreover, whether the coating has been fully pulled-off or not is hard to ensure in real-time in vivo . Herein, composited silk fibroins (SFMA) are optimized to stabilize Fe 3 O 4 nanoparticles on a titanium surface in a dry environment; while in an aqueous environment, the binding force of SFMA on titanium is significantly reduced due to hydrophilic interaction, making the coating magnetically controllable by an externally-used magnet but still stable in the absence of a magnet. The maximum working distance of the magnet can be calculated using magnetomechanical simulation in which the yielding magnetic traction force is strong enough to pull Fe 3 O 4 nanoparticles off the surface. The pulling-off removes the biofilms that formed on the coating and enhances antibiotic killing both in vitro and in a rat sub-cutaneous implant model by up to 100 fold. This work contributes to the practical knowledge of magnetic propulsion for biofilm treatment.

Bovine serum albumin-stabilized Au nanoclusters (BSA-Au NCs) have emerged as promising contenders for imaging agents and highly sensitive fluorescence sensors due to their biocompatibility and strong photoluminescence. Optimizing the synthesis conditions of BSA-Au NCs is crucial for enhancing fluorescence imaging and other nanocluster applications. In this study, for the first time, we systematically investigated the effects of BSA concentration and Au 3+ on both particle size and optical characteristics of BSA-Au NCs. When the two components achieved a suitable concentration ratio, it was beneficial to form BSA-Au NCs with a high quantum yield (QY = 74.30%) and good fluorescence stability. In contrast, an inappropriate concentration ratio would lead to the formation of gold nanoparticles (Au NPs), and their internal filtration effect (IFE) would attenuate the fluorescence emission of BSA-Au NCs. The BSA-Au NCs were then employed as efficient fluorescence sensors for detecting Hg 2+ . Furthermore, the growth mechanism of BSA-Au NCs was elucidated by monitoring fluorescence changes during different incubation times. The BSA-Au NCs with a high quantum yield introduce a novel synthetic concept for sensitive fluorescent probes and expanding versatile applications of BSA-Au NCs in catalysis, chemical sensing and biomedicine., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Organic π-conjugated polycyclic hydrocarbons (PHs) with an open-shell diradical character are attracting increasing interest due to their promising applications in organic electronics and spintronics. However, most of the open-shell PHs synthesized thus far are based on planar π-conjugated molecules. Herein, we report the synthesis and characterization of two new quinodimethane-embedded expanded helicenes H1 and H2. The helical structures of both molecules were revealed using X-ray crystallographic analysis. It was elucidated in detailed experimental and theoretical studies that they possess an open-shell singlet biradical structure in the ground state and show a small energy gap and amphoteric redox behavior. Both compounds can also be easily oxidized or reduced into relatively stable charged species. The dianions of H1 and H2 exhibit similar electronic structures to the respective isoelectronic structures of their all-benzenoid helical analogues according to NMR measurements and theoretical calculations. Moreover, the structures of the dication and dianion of H2 were identified by X-ray crystallographic analysis, revealing the effect of electron transfer on their backbones and aromaticity. This study thus opens up new avenues for both helical polycyclic π-systems and diradicaloids., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The discovery of negative differential conductance (NDC) in a single molecule and mechanism controlling this phenomenon are important for molecular electronics. We investigated the electronic properties of a typical radical molecule 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (CTPO) on an Au(111) surface using low-temperature scanning tunneling microscopy (STM) and inelastic electron tunneling spectroscopy. Large NDC was observed in single CTPO molecules at the boundary of the crystal monolayer. The origin of observed NDC is revealed as the inelastic electron-phonon scattering during tunneling, and the strong spatial variation of the NDC over the single molecule illustrates the nature of the localized radical group. In addition, the NDC can be transformed into a positive differential conductance peak by tuning coupling strengths between different tunneling channels. An empirical multi-channel model has been developed to describe the competition between the valley-shaped NDC and peak-shaped positive differential conductance. The unique electronic property and giant conductance change observed in this radical molecule is valuable for designing novel molecular devices in the future., Competing Interests: The authors declare no conflicts of interests., (This journal is © The Royal Society of Chemistry.)

Driven by the "double carbon" strategy, petroleum coke short-term demand is growing rapidly as a negative electrode material for artificial graphite. The analysis of petroleum coke physicochemical properties has always been an important part of its research, encompassing significant indicators such as ash content, volatile matter and calorific value. A strategy based on laser-induced breakdown spectroscopy (LIBS) in combination with chemometrics is proposed to realize the rapid and accurate quantification of the above properties. LIBS spectra of 46 petroleum coke samples were collected, and an original random forest (RF) calibration model was constructed by optimizing the pretreatment parameters. The RF calibration model was further optimized based on variable importance measures (VIM) and variable importance in projection (VIP) methods. After variable selection, the elemental spectral lines related to ash content, volatile matter and calorific value modeling were screened out, thus initially exploring the correlation between these properties and elements. Under the optimized spectral pretreatment method, VI threshold and model parameters, the mean relative error (MRE P ) of the prediction set of ash content, volatile matter and calorific value were 0.0881, 0.0527 and 0.006, the root mean square error (RMSE P ) of the prediction set of ash content, volatile matter and calorific value were 0.0471%, 0.6178% and 0.2697 MJ kg -1 , respectively, and the determination coefficient ( R P 2 ) of the prediction set was 0.9187, 0.9820 and 0.9510, respectively. The combination of LIBS technology and chemometric methods can provide powerful technical means for the analysis and evaluation of the physicochemical properties of petroleum coke., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Efficient and affordable nucleic acid detection methods play a pivotal role in various applications. Herein, we developed an immobilization-free and label-free strategy to construct a photoelectrochemical nucleic acid biosensing platform based on interactions between silver nanoparticles and DNA. First, CRISPR-Cas12a exhibited a trans-cleavage effect on adenine nucleotide sequences upon recognizing the target DNA. The resulting adenine nucleotide sequences of varying lengths then engaged in interactions with silver nanoparticles, leading to a solution characterized by distinct light transmittance. Subsequently, the solution was positioned between the light source and the photoelectrode, strategically impacting the photon absorption step within the photoelectrochemical process. Consequently, the detection of nucleic acid was accomplished through the analysis of the resultant photocurrent signal. The developed platform exhibits a detection limit of 0.06 nM (S/N = 3) with commendable selectivity. The innovative use of adenine nucleotide sequences as cost-effective probes interacting with silver nanoparticles eliminates the need for complex interfacial immobilization processes, significantly simplifying the fabrication of DNA sensors. The outcomes of our research present a promising pathway for advancing the development of economically feasible miniature DNA sensors.

Semicarbazide (SEM) is a metabolite of antibiotic nitrofurazone and a food contaminant in food production, showing potential carcinogenic, mutagenic, teratogenic, and toxic effects on human health. It is urgent to develop a highly efficient and sensitive assay for visual detection of SEM. In this paper, a pyrrolopyrrole cyanine fluorescent probe (PPCy-1) was reported for visualization and quantitative analysis of SEM through a chromophore reaction sensing mechanism for the first time. The probe towards SEM exhibited a fast response (10 min), a low detection limit (0.18 μM), high selectivity, and distinct dual ratiometric fluorescence turn-on and colorimetric modes. Its practicability was further verified by detecting SEM in meat, water, and honey samples with satisfactory recovery values. More importantly, a smartphone-assisted portable testing platform was constructed based on a PPCy-1-immobilized test paper or a polyamide thin film with a color scanning APP for real-time and on-site detection of SEM. This work provides low-cost, convenient, and rapid assays for visual SEM detection, which have potential applications in food safety monitoring.

In order to investigate the structure of FeAl mesoscopic crystals segregating in liquid state alloys, we have determined their equilibrium structures (Wulff shape) based on the Wulff cluster model. For non-stoichiometric surface terminations, the chemical environment is taken into account through the chemical potential of the constituents. In this case, different cluster shapes change as a function of the chemical environment. In order to model the growth process in more detail, we propose a quasi-static growth model based on the sequential addition of (sub-)monolayers in the most favorable surface directions. Thus, a sequence of different Wulff shapes results in the growth process, as illustrated for the FeAl intermetallic compound. This model is proved preliminarily by calculating the concentration trend of Al/Fe atoms on both Al-terminated and Fe-terminated surfaces, and by simulating the most stable layer adsorbed on these two surfaces. This model might be helpful in analyzing the growth processes including nucleation barriers during nucleation processes theoretically., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Identifying the cellular targets of bioactive small molecules within tissues has been a major concern in drug discovery and chemical biology research. Compared to cell line models, tissues consist of multiple cell types and complicated microenvironments. Therefore, elucidating the distribution and heterogeneity of targets across various cells in tissues would enhance the mechanistic understanding of drug or toxin action in real-life scenarios. Here, we present a novel multi-omics integration pipeline called Single-cell TargEt Profiling (STEP) that enables the global profiling of protein targets in mammalian tissues with single-cell resolution. This pipeline integrates single-cell transcriptome datasets with tissue-level protein target profiling using chemoproteomics. Taking well-established classic drugs such as aspirin, aristolochic acid, and cisplatin as examples, we confirmed the specificity and precision of cellular drug-target profiles and their associated molecular pathways in tissues using the STEP analysis. Our findings provide more informative insights into the action modes of bioactive molecules compared to in vitro models. Collectively, STEP represents a novel strategy for profiling cellular-specific targets and functional processes with unprecedented resolution., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A yellow-emitting cationic iridium(III) complex [(dfppy) 2 Ir(TBD)]PF 6 (TBD: N 4 , N 4' -bis(3-(triethoxysilyl)propyl)-[2,2'-bipyridine]-4,4'-dicarboxamide; dfppy: 2-(2,4-difluorophenyl)pyridine) containing hydrolysable alkoxysilanes was synthesized. Then, a series of silica-based hybrid nanospheres with diameters of around 400 nm was prepared via the hydrolysis of this complex together with tetraethyl orthosilicate (TEOS, a silica source). When the amount of the complex used was 5.0 wt%, hybrid nanospheres showed the best photoluminescence (PL) properties, relative to the PL quantum yield of pure solid [(dfppy) 2 Ir(TBD)]PF 6 (12.7%), that of hybrid nanospheres increased to 26.2%. Moreover, the thermal decomposition temperature ( T d ) of pure solid [(dfppy) 2 Ir(TBD)]PF 6 was 331 °C, the T d of the complex in hybrid nanospheres increased to 447 °C. However, the yellow light emission was almost unchanged and was still located at 500-750 nm with a maximum wavelength ( λ em,max ) of 577 nm. Under the excitation of blue-emitting chips ( λ em,max ≈ 455 nm), cold/neutral/warm white light-emitting diodes (WLEDs) with good luminous quality can all be fabricated using these hybrid nanospheres as phosphors in epoxy resin at different blending concentrations. Compared with two or three iridium(III) complexes being contained in silica-based particles as phosphors as described in literatures, in this study, silica-based hybrid nanospheres covalently containing only one yellow-emitting cationic iridium(III) complex as phosphors provide a more effective and simpler method for preparation high-performance WLEDs.

The extraction of lead-212 ( 212 Pb) from radioactive thorium (Th) waste is immensely important, as it serves to mitigate environmental risks associated with radioactive waste and provides a vital source for medical isotopes. To economically extract 212 Pb from thorium, we synthesized a novel extractant known as 2,13-disulfonyldiethylamine dibenzo-18-crown-6 (DSADB18C6). We assessed its performance in isolating Pb(II) by employing stable lead and optimizing the parameters of the extraction system. The results showcased an exceptional ability to extract Pb(II) efficiently. Within 10 minutes, using 20 mmol of DSADB18C6 and under conditions of 10 mg L -1 lead concentration (HNO 3 = 0.5 mol L -1 ), the extraction efficiency reached up to 96.1%. Even after four rounds of stripping with 0.4 mol L -1 ammonium citrate, the efficiency remained at 90.2%. Moreover, the extraction stoichiometry and thermodynamics revealed that DSADB18C6 exhibited superior extraction performance compared to the commercial extractant 4',4'',(5'')-di-( tert -butyldicyclohexano)-18-crown-6 (DtBuDC18C6), in line with the density functional theory (DFT) calculation result. Furthermore, we successfully separated 212 Pb from the thorium nitrate solution, maintaining radioactive equilibrium with its progeny. Gamma-spectroscopy confirmed a recovery yield of extraction exceeding 85.7%. This study presents a viable approach, underscoring the potential of DSADB18C6 as a promising extractant for the effective separation of 212 Pb from radioactive thorium sources.

NH 2 -UiO-66(Ti) and NH 2 -MIL-125(Ti) were successfully prepared by using post-synthesis exchange (PSE) and hydrothermal methods, and then these frameworks were tested for photocatalytic hydrogen peroxide production in pure water under visible light. NH 2 -MIL-125(Ti) exhibits superior activity compared to NH 2 -UiO-66(Ti) due to its shorter Ti-O bond. In addition, NH 2 -MIL-125-D (defective) demonstrates a high photocatalytic yield of hydrogen peroxide owing to the presence of defect-rich titanium rich sites.

Infectious bone defects are characterized by the partial loss or destruction of bone tissue resulting from bacterial contaminations subsequent to diseases or external injuries. Traditional bone transplantation and clinical methods are insufficient in meeting the treatment demands for such diseases. As a result, researchers have increasingly focused on the development of more sophisticated biomaterials for improved therapeutic outcomes in recent years. This review endeavors to investigate specific reparative materials utilized for the treatment of infectious bone defects, particularly those present in the maxillofacial region, with a focus on biomaterials capable of releasing therapeutic substances, functional contact biomaterials, and novel physical therapy materials. These biomaterials operate via heightened antibacterial or osteogenic properties in order to eliminate bacteria and/or stimulate bone cells regeneration in the defect, ultimately fostering the reconstitution of maxillofacial bone tissue. Based upon some successful applications of new concept materials in bone repair of other parts, we also explore their future prospects and potential uses in maxillofacial bone repair later in this review. We highlight that the exploration of advanced biomaterials holds promise in establishing a solid foundation for the development of more biocompatible, effective, and personalized treatments for reconstructing infectious maxillofacial defects.

Efficient and durable electrocatalysts for the oxygen evolution reaction (OER) play an important role in the use of hydrogen energy. Rutile RuO 2 , despite being considered as an advanced electrocatalyst for the OER, performs poorly in stability due to its easy oxidative dissolution at very positive (oxidizing) potentials. Herein, we report a type of Co-doped RuO 2 nanoparticle for boosting OER catalytic activity and stability in alkaline solutions. The replacement of Ru by Co atoms with a lower ionic valence and smaller electronegativity can promote the generation of O vacancies and increase the electron density around Ru, thus enhancing the adsorption of oxygen species and inhibiting the peroxidative dissolution of RuO 2 during the OER process. It was found that Ru 0.95 Co 0.05 O y exhibited excellent OER performance with overpotentials as low as 217 mV at 10 mA cm -2 and 290 mV at 100 mA cm -2 in 1 M KOH, as well as outstanding stability in continuous testing for 50 h at a current density of 100 mA cm -2 , and nearly no significant degradation after the accelerated durability test of 2000 cycles.

Polyacrylamide gel (PAG) is extensively used as a matrix for biomolecular analysis and fractionation. However, the traditional polymerization catalyst system N , N , N ', N '-tetramethylethylenediamine (TEMED)/ammonium persulphate (APS) of PAG presents non-negligible toxicity. Herein, we utilized the green and efficient bio-enzyme horseradish peroxidase (HRP) to catalyze the gel polymerization of polyacrylamide. At the same time, the efficacy of this gel system in separating nucleic acids and proteins was confirmed by applying the gel system in electrophoresis. This study aims to explore a higher biosafety polyacrylamide gel polymerization catalytic system which can be applied to electrophoresis technology. Furthermore, in order to differentiate between the bio-enzymatic catalytic system and the traditional toxic catalytic system during polymerization, aggregation-induced luminescence (AIE) of bovine serum albumin-stabilized gold nanoclusters (BSA-Au NCs) was used to monitor the polymerization reaction of the system. The results indicated that the fluorescence intensity of the polymeric system containing BSA-Au NCs increased with the polymerization of the monomers. Subsequently, we assessed whether certain components of nucleic acid electrophoresis and protein electrophoresis such as sodiumdodecylsulfate (SDS) and TBE buffer (Tris-boric acid, EDTA, pH 8.3) would affect the polymerization of the polyacrylamide gels catalyzed by the biological enzymes. The experimental conditions were also optimized to explore the optimal concentration of the ternary system of HRP, H 2 O 2 and ACAC. Our results suggested that the bioenzyme-catalyzed system could be a feasible alternative to the TEMED/APS-catalyzed system, which also could provide new insights into the methods of monitoring the polymerization system., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Inflammatory cytokines that are secreted into the spinal trigeminal nucleus caudalis (Sp5C) may augment inflammation and cause pain associated with temporomandibular joint disorders (TMD). In a two-step process, we attached triphenylphosphonium (TPP) to the surface of a cubic liposome metal-organic framework (MOF) loaded with ruthenium (Ru) nanozyme. The design targeted mitochondria and was designated Mito-Ru MOF. This structure scavenges free radicals and reactive oxygen species (ROS) and alleviates oxidative stress. The present study aimed to investigate the effects and mechanisms by which Mito-Ru MOF ameliorates TMD pain. Intra-temporomandibular joint (TMJ) injections of complete Freund's adjuvant (CFA) induced inflammatory pain for ≥10 d in the skin areas innervated by the trigeminal nerve. Tumor necrosis factor-alpha (TNF-α), nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB), long non-coding RNA nuclear paraspeckle assembly transcript 1 (lncRNA NEAT1), and ROS also have been proved to be significantly upregulated in the Sp5C of TMD mice. Moreover, a single Mito-Ru MOF treatment alleviated TMD pain for 3 d and downregulated TNF-α, NF-κB, lncRNA NEAT1, and ROS. NF-κB knockdown downregulated NEAT1 in the TMD mice. Hence, Mito-Ru MOF inhibited the production of ROS and alleviated CFA-induced TMD pain via the TNF-α/NF-κB/NEAT1 pathway. Therefore, Mito-Ru MOF could effectively treat the pain related to TMD and other conditions associated with severe acute inflammatory activation.

We report here a dual-nanopore biosensor based on modulation of surface charge density coupled with a microwell array chip for in situ monitoring of ROS secretion from single MCF-7 cells.

Normal prostate tissues generally exhibit a higher level of zinc to maintain their special "citrate-producing" metabolism, while its level dramatically decreases during prostate tumorigenesis. Despite the significant antitumor effects, the intracellular accumulation of zinc in prostate cancer cells also promotes the expression of ZNT1, which in turn results in the efflux of zinc and attenuated cytotoxicity against cancer cells. To solve the dilemma, we developed a 2-[3-(1,3-dicarboxypropyl)ureido]pentanedioic acid (DUPA)-decorated zeolitic imidazolate framework-8 (ZIF8), which is able to load plasmid DNA encoding the Cas9 editor and single-guide RNA to form Cas9@ZIF8-DUPA nanocomplexes. The intracellular delivery of Cas9@ZIF8-DUPA simultaneously increases the level of zinc and inhibits the ZNT-1 function by disrupting the SLC30A1 gene to prevent the efflux of zinc in prostate cancer cells. Due to the high affinity between DUPA and the prostate-specific membrane antigen, Cas9@ZIF8-DUPA nanocomplexes exhibit excellent prostate tumor-targeting ability. The internalization and degradation of Cas9@ZIF8-DUPA not only release free zinc and Cas9 editors, but also reduce zinc efflux through Cas9-mediated genome editing that disables the function of ZNT1. As a result, Cas9@ZIF8-DUPA nanocomplexes exhibit significant antitumor activity and extended survival in the mouse model bearing prostate tumors. The current platform offers an alternative therapeutic strategy and holds tremendous translational potential as an anticancer nanomedicine for prostate cancer treatment.

A new sensor has been developed to detect miRNA-15 using nanoelectrodes and a hairpin DNA-based electrochemical amplification technique. By utilizing a complex DNA cylinder connected with hairpin DNA1, the sensor is able to absorb more methylene blue (MB) than simple double-stranded DNA. Another hairpin DNA2 is modified on an Au nanoelectrode surface and, when miRNA-15 is introduced, it triggers a chain reaction. This reaction unlocks two hairpins alternatively to polymerize into a complex structure that attaches more MB. The miRNA-15 is then replaced by DNA1 due to strand displacement reactions and continues to react with the next DNA2 to achieve circular amplification. The electrochemical signal from MB oxidation has a linear relationship with the miRNA-15 concentrations, making it possible to detect miRNA-15. Moreover, this method can be readily adapted for the detection of various other miRNA species. The newly devised nanosensor holds promising applications for the in vivo detection of miRNA-15 within biological systems, which is achieved by leveraging the advantageous characteristics of nanoelectrodes, including their low resistance-capacitance time constant, rapid mass transfer kinetics, and small diameter.

The construction of platinum complexes with high steric hindrance is expected to suppress triple-triplet annihilation and π-π stacking to achieve high-performance organic light-emitting diodes (OLEDs) with low efficiency roll-off. Herein, two large steric hindrance platinum complexes ( N -CzPhPtacac and N -CzCF 3 PhPtacac) were prepared by taking advantage of steric hindrance between the phenyl group on carbazole and the functional group (phenyl and trifluoromethyl substituted phenyl) at the 3-position of a pyridine moiety. Due to the similar electron cloud distribution and gap difference between the HOMO and LUMO, the two complexes showed similar orange-red emission peaks at 590 and 596 nm with high PL quantum yields of 90% and 92% and short excited state lifetimes of 2.77 and 3.08 μs in doped films, respectively. Consequently, OLEDs based on N -CzPhPtacac and N -CzCF 3 PhPtacac showed maximum external quantum efficiency (EQE max ) values of 15.4% and 18.9%, respectively. Importantly, benefitting from the more stretched spatial configuration from the -CF 3 effect, the corresponding OLED exhibited a lower efficiency roll-off, with an EQE of 18.1% at 1000 cd m -2 .

The selection of metal centers can endow donor-metal-accepter (D-M-A) type MOFs with progressive framework dimensions. 3D Cd-based MOFs with intramolecular charge transfer caused by D-M-A exhibit a satisfactory photothermal conversion efficiency of 35.7%, with the temperature rapidly rising from 25 °C to 201 °C in 7 s under 808 nm laser irradiation.

Neodymium is mainly obtained by electrolysis of a molten LiF-NdF 3 -Nd 2 O 3 system. LiF-NdF 3 is a basic system, and the phase diagram of this system provides important information in the production of electrolytic neodymium. An accurate LiF-NdF 3 binary phase diagram helps in the selection of the appropriate molten salt component in production and optimizing the production process, which is of great significance to improve the electrolysis efficiency and reduce the production cost. To obtain an accurate phase diagram of the LiF-NdF 3 binary system, liquidus and solidus temperatures were experimentally determined in the LiF-NdF 3 binary system by differential scanning calorimetry. The experimental results were used to construct the phase diagram and develop a new database for the LiF-NdF 3 system using the FactSage software. The sub-regular solution model was used to describe the excess Gibbs free energy of the liquid phase, and the thermodynamic optimization calculation was carried out for the binary system. The binary interaction coefficients 0 L = -39 966 + 17.68 T , 1 L = -7667 + 26.1 T , and 2 L = -6000 were used to describe the system's excess Gibbs free energy. The results show that the eutectic point of the system is 68.4% LiF-31.6% NdF 3 at 731.5 °C. The effects of industrial and high purity NdF 3 and the presence of Nd 2 O 3 on the liquidus temperature of the LiF-NdF 3 system were also investigated, high liquidus temperatures have been observed in tests using industrial NdF 3 and NdF 3 feedstock that contains a specific quantity of Nd 2 O 3 ., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Luminescent Au nanoparticles (AuNPs) and their organic/inorganic nanohybrids are of interest due to their favorable properties and promising biomedical applications. However, most existing AuNP-based hybrid nanostructures cannot satisfy high efficiency in synthesis, deep tissue penetration, and long blood circulation simultaneously, thus cannot be employed in dynamic monitoring of biomedical applications. In this paper, using Pluronic F127 as a template, we report a robust approach for one-pot synthesis of AuNP-based organic/inorganic nanohybrids (AuNHs) with bright luminescence in the second near-infrared (NIR-II) window, tunable shape, and controllable surface polyethylene glycol (PEG) density. The nanohybrids could be controlled from a necklace-like shape with a dense brush PEG configuration to a spherical structure with a brush PEG coating, which greatly impacts the in vivo biological behavior. Compared to spherical AuNHs, the necklace-shaped AuNHs present a higher quantum yield and longer blood circulation, which are superior to most of the individual AuNPs. With these outstanding features, the necklace-shaped AuNHs could achieve real-time, dynamic visualization of vascular dysfunction, capable of directing the precise administration of thrombolytics (a medicine for the breakdown of blood clots). These findings could provide a powerful guide for designing novel NIR-II nanoprobes toward in vivo dynamic information visualization., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A novel cyclic ion chromatography (IC) system was developed for the simultaneous determination of trace disinfection by-products (DBPs) in drinking water. Five DBPs (chlorite, bromate, chlorate, dichloroacetic acid, and trichloroacetic acid) were sensitively determined by large-volume direct injection, and the interferences of dominant inorganic anions present in water were eliminated online through the cyclic determination of the target analytes. Under optimized conditions, the obtained limits of detection (LODs) were in the range of 0.18-1.91 μg L -1 based on a signal-to-noise ratio (S/N) of 3 and an injection volume of 1.0 mL. The RSDs for peak area and retention time were in the range of 0.13-1.03% and 1.24-4.29%, respectively. Satisfactory recoveries between 92.3% and 106.4% were obtained by adding three concentration gradients of standards to the drinking water samples. The proposed method has advantages such as high sensitivity, facile automation, and no sample pretreatment, and might be a promising approach for routine analysis., Competing Interests: The authors declare that they have no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Sofalcone (Sof), a synthetic analog of sophoradin, is a type of natural phenol derived from the traditional medicinal herb Sophora subprostrata , with potent anti-inflammatory activity. However, the mechanisms of action of Sof for treating intestinal-associated inflammation are not well known. In this work, we identified high mobility group box 1 (HMGB1) as the key covalent target of Sof for the anti-inflammatory activity in the human colonic epithelial cells through quantitative chemoproteomics profiling.

A wearable sweat sensor, which could continuously monitor biomolecules related to the human physiological state, is emerging as a promising piece of health surveillance equipment. However, current sensors cannot simultaneously achieve a detection performance that equates to that of traditional sensors and satisfactory mechanical strength. Herein, a wearable sweat sensor with excellent detection performance and mechanical stability is designed and fabricated. Based on the integration of laser-induced graphene electrodes and a screen printing technique, this wearable sweat sensor could realize both the separate and simultaneous detection of uric acid (UA), tyrosine (Tyr), and ascorbic acid (AA) with high sensitivity. Good UA sensing performance in artificial sweat could be maintained even after 20 000 bends. In addition, the sensor can operate well in the wearing state or in a complex bovine whole blood sample. For the detection of human sweat, the changes in UA concentration after a purine-rich meal are continuously monitored and the results are in accordance with the corresponding serum UA detection results tested with a commercial serum UA meter. These results suggest its application potential in health monitoring for both gout patients and healthy humans.

Dental caries is a biofilm-induced bacterial infectious oral disease, where the early attachment of proteins and pathogenic bacteria to tooth surfaces has been known as the main cause of biofilm formation. Typically, dental caries is commonly accompanied by mineral depletion of enamels, thus causing dental demineralization. Multifunctional materials are highly attractive candidates for treating dental caries. Herein, we successfully synthesized diblock copolymers poly(ethylene glycol)- b -poly(aspartic acid) (PEG-PAsp) and modified them with alendronate sodium (ALN) to serve as bioactive bifunctional coatings (PEG-PAsp-ALN) on teeth. The PEG segments are employed for inhibiting proteins and bacterial adhesion. In addition, due to the presence of both PAsp and ALN, a synergistically strong binding capacity could be achieved with the tooth surface, thus promoting rapid and thorough remineralization in situ , while maintaining excellent safety. The combination treatment can significantly suppress the biofilm formation, which is beneficial for alleviating the demineralization of enamels caused by bacteria, and further, facilitate remineralization in situ . This approach thus demonstrates the potential of the copolymer PEG-PAsp-ALN coating as a multifunctional protecting layer on the tooth surface for high-efficiency prevention and treatment of dental caries.

Photodynamic therapy (PDT) with an oxygen-dependent character is a noninvasive therapeutic method for cancer treatment. However, its clinical therapeutic effect is greatly restricted by tumor hypoxia. What's more, both PDT-mediated oxygen consumption and microvascular damage aggravate tumor hypoxia, thus, further impeding therapeutic outcomes. Compared to type II PDT with high oxygen dependence and high oxygen consumption, type I PDT with less oxygen consumption exhibits great potential to overcome the vicious hypoxic plight in solid tumors. Type I photosensitizers (PSs) are significantly important for determining the therapeutic efficacy of PDT, which performs an electron transfer photochemical reaction with the surrounding oxygen/substrates to generate highly cytotoxic free radicals such as superoxide radicals (˙O 2 - ) as type I ROS. In particular, the primary precursor (˙O 2 - ) would progressively undergo a superoxide dismutase (SOD)-mediated disproportionation reaction and a Haber-Weiss/Fenton reaction, yielding higher cytotoxic species (˙OH) with better anticancer effects. As a result, developing high-performance type I PSs to treat hypoxic tumors has become more and more important and urgent. Herein, the latest progress of organic type I PSs (such as AIE-active cationic/neutral PSs, cationic/neutral PSs, polymer-based PSs and supramolecular self-assembled PSs) for monotherapy or synergistic therapeutic modalities is summarized. The molecular design principles and strategies (donor-acceptor system, anion-π + incorporation, polymerization and cationization) are highlighted. Furthermore, the future challenges and prospects of type I PSs in hypoxia-overcoming PDT are proposed.

Rare earth ores are complex in composition and diverse in mineral composition, requiring high technical requirements for the selection of rare earth ores. It is of great significance to explore the on-site rapid detection and analysis methods of rare earth elements in rare earth ores. Laser induced breakdown spectroscopy (LIBS) is an important tool to detect rare earth ores, which can be used for in situ analyses without complicated sample preparation. In this study, a rapid quantitative analysis method for rare earth elements Lu and Y in rare earth ores was established by LIBS combined with an iPLS-VIP hybrid variable selection strategy and partial least squares (PLS) method. First, the LIBS spectra of 25 samples were studied using laser induced breakdown spectrometry. Second, taking the spectrum processed by wavelet transform (WT) as the input variables, PLS calibration models based on interval partial least squares (iPLS), variable importance projection (VIP) and iPLS-VIP hybrid variable selection were constructed to quantitatively analyze rare earth elements Lu and Y, respectively. The results show that the WT-iPLS-VIP-PLS calibration model has better prediction performance for rare earth elements Lu and Y, and the optimal coefficient of determination ( R 2 ) of Lu and Y were 0.9897 and 0.9833, the root mean square error (RMSE) were 0.8150 μg g -1 and 97.1047 μg g -1 , and the mean relative error (MRE) were 0.0754 and 0.0766, respectively. It shows that LIBS technology combined with the iPLS-VIP and PLS calibration model provides a new method for in situ quantitative analysis of rare earth elements in rare earth ores., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Molybdenum trioxide (MoO 3 ) is emerging as a hugely competitive cathode material for aqueous zinc ion batteries (ZIBs) for its high theoretical capacity and electrochemical activity. Nevertheless, owing to its undesirable electronic transport capability and poor structural stability, the practical capacity and cycling performance of MoO 3 are yet unsatisfactory, which greatly blocks its commercial use. In this work, we report an effective approach to first synthesise nanosized MoO 3- x materials to provide more active specific surface areas, while improving the capacity and cycle life of MoO 3 by introducing low valence Mo and coated polypyrrole (PPy). MoO 3 nanoparticles with low-valence-state Mo and PPy coating (denoted as MoO 3- x @PPy) are synthesized via a solvothermal method and subsequent electrodeposition process. The as-prepared MoO 3- x @PPy cathode delivers a high reversible capacity of 212.4 mA h g -1 at 1 A g -1 with good cycling life (more than 75% capacity retention after 500 cycles). In contrast, the original commercial MoO 3 sample only obtains a capacity of 99.3 mA h g -1 at 1 A g -1 , and a cycling stability of 10% capacity retention over 500 cycles. Additionally, the fabricated Zn//MoO 3- x @PPy battery obtains a maximum energy density of 233.6 W h kg -1 and a power density of 11.2 kW kg -1 . Our results provide an efficient and practical approach to enhance commercial MoO 3 materials as high-performance cathodes for AZIBs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A novel geldanamycin derivative LZY3016 was synthesized as an antitumor agent. Compound LZY3016 exhibited potent anti-proliferation activity toward MDA-MB-231 (IC 50 = 0.06 μM), which was more effective than positive drug 17-AAG. In vivo hepatotoxicity assay displayed that serum AST/ALT levels in LZY3016-treated mice were both significantly less than those in the geldanamycin (GA) group. LZY3016 showed potent antitumor activity in an MDA-MB-231 xenograft mouse model, suggesting LZY3016 is an up-and-coming antitumor candidate. The theoretical binding mode between LZY3016 and Hsp90 was obtained by molecular dynamics simulation., Competing Interests: We declare that we have no conflict of interest., (This journal is © The Royal Society of Chemistry.)