Transition metal carbides/nitrides (MXenes) exhibit exceptional metallic conductivity and precisely tunable interlayer spacing, serving as promising candidates for overcoming key bottlenecks in next-generation energy storage devices. The performance of these devices remains constrained by several interconnected challenges. Inefficient ion transport arising from tortuous pathways, size mismatch, and polarization impede reaction kinetics. Structural degradation caused by electrode expansion and active material dissolution further reduce performance. Furthermore, interface issues such as corrosion, dendrite growth, and high impedance also severely limit efficiency. In this review, we summarize strategies for constructing composites with dimensional materials from zero-dimension (0D) to three-dimensions (3D). Emphasis is placed on synergistic enhancement mechanisms. We further evaluate the role of MXenes in addressing interfacial challenges like ion deposition, shuttle effect, solid-electrolyte interphase (SEI) formation, and contact resistance. Building on these insights, we discuss solutions for the practical application of MXene-based energy storage devices. This Review summarizes strategies for constructing composites based on MXenes for addressing challenges MXenes face in energy storage applications, such as ion deposition, shuttle effect, solid-electrolyte interphase formation, and contact resistance.
In this work, we have developed a Sanger's reagent-based photocage, LNDA-NBD-Sanger, which releases the caged COX-2 inhibitor, lenalidomide (LNDA), under 400 nm UV irradiation while producing a fluorescent signal from the activated nitrobenzoxadiazole (NBD) derivative, realizing the monitoring of LNDA release in cancer cells and light-controlled anti-cancer therapy.
1-Aminocyclopropane-1-carboxylic acid (ACC) is a nonprotein amino acid commonly found in plants, serving as an ethylene precursor with independent hormone functions that regulate plant growth, development, and stress resistance. Due to its agricultural significance, efforts have focused on boosting its production. In this study, ACC biosynthesis was achieved in E. coli via LaACS (1-aminocyclopropane-1-carboxylate synthase) from Lycoris aurea, which catalyzes S-adenosylmethionine (SAM). To enhance the yield, structural prediction of LaACS using AlphaFold2 and MOE docking identified the mutant LaACSL243A, which exhibited a doubled Vmax (0.018 mM/L/min) and Kcat (12.033 min-1) and 20% higher Kcat/Km (15.88 mM-1 min- 1) than that of the wild type. The intrinsic reasons for the enhanced catalytic efficiency were elucidated through molecular dynamics simulation. Subsequently, through screening of S-adenosylmethionine synthase (SAMS), SAMSa (from Arabidopsis thaliana) was identified as having the highest catalytic activity. Overexpression of the genes encoding SAMSa, MetA (homoserine O-succinyltransferase), and MetH (methionine synthase) successfully increased the ACC yield to 109 mg/L in 50 mL of M9 medium, which is twice that of the unmodified strain. The development of a green, safe, and efficient ACC biosynthetic process is of significant importance for promoting the application of ACC in agricultural science, biology, and medicine.
High fructose intake is an important cause of metabolic disease. Due to the increasing prevalence of metabolic diseases worldwide, the development of an accurate and efficient tool for monitoring fructose in food is urgently needed to control the intake of fructose. Herein, a new fluorescent probe NBD-PQ-B with 7-nitrobenz-2-oxa-1, 3diazole (NBD) as the fluorophore, piperazine (PQ) as the bridging group and phenylboronic acid (B) as the recognition receptor, was synthesized to detect fructose. The fluorescence of NBD-PQ-B increased linearly at 550 nm at an excitation wavelength of 497 nm with increasing fructose concentration from 0.1 to 20 mM. The limit of detection (LOD) of fructose was 40 mu M. The pKa values of NBD-PQ-B and its fructose complexes were 4.1 and 10.0, respectively. In addition, NBD-PQ-B bound to fructose in a few seconds. The present technique was applied to determine the fructose content in beverages, honey, and watermelon with satisfactory results. Finally, the system could not only be applied in an aqueous solution with a spectrophotometer, but also be fabricated as a NBD-PQ-B/polyvinyl oxide (PEO) film by electrospinning for on-site food analysis simply with the assistance of a smartphone.
Precise imaging identification of tumor tissues from normal tissues is still challenging. In this study, a new dual-locked near-infrared fluorescent probe BBQ650-SS-BTZHC-E was developed for the discrimination between cancer cells and normal cells. The probe consists of a hemicyanine fluorophore conjugated to an esterase substrate and a quencher connected via a disulfide bond. The esterase substrate blocks the excited state intramolecular proton transfer (ESIPT) process, while the quenching agent forms a Förster resonance energy transfer (FRET) pair with the fluorophore. The fluorescence activation is dependent on the presence of both esterase and glutathione (GSH), resulting in the “ESIPT on” and “FRET off” states, which represent an “AND” logic. The characterizations showed that the kinetics of fluorescence activation are dependent on the concentrations of the two activators with a high specificity. Fluorescent imaging experiments using BBQ650-SS-BTZHC-E successfully distinguished cancer cells (HeLa, 4T1, RAW264.7) from normal cells (HFL1) with high contrast and specificity, and imaged 4T1 tumor on live mice. This study provides a simple platform for the development of dual-locked fluorescent probes for bio-imaging applications.
Photoactivatable subcellular organelles imaging offers the desirable spatiotemporal resolution in studying the complex biological processes. Developing proper and simple photoremovable protecting groups (PPGs) is the key for constructing such imaging probes. In this study, we designed and synthesized three Sanger's reagent caged fluorescent probes for specific photoactivated organelle imaging. We showed the photoactivated fluorescence recovery of the probes. The photolysis mechanism was verified by mass spectra (MS) analysis, and the highly efficient photolysis process was monitored by high performance liquid chromatography (HPLC). The probes successfully imaged their respective targeted organelle, including mitochondria, lysosomes, and endoplasmic reticulum (ER), in a photoactivated manner, and exhibited high co-localization coefficients when compared to commercially available probes. Given the high reactivity and efficient photodissociation capability of Sanger's reagent with amino groups, our examples demonstrate the potential of Sanger's reagent as a novel general PPG for constructing photoactivatable fluorescent probes.
Phloroglucinol (PG) is an extremely expensive pharmaceutical intermediate, which requires high purity for subsequent applications. Thus, there is a pressing need to selectively separate it from the complex production system. In this work, the optimal functional monomer N-Vinylimidazole (VIM) that possesses the strongest affinity with PG among 11 phenolic monomers was quantitively selected by DFT calculation. The key factors influencing the adsorption capacity (Qe) and imprinting effect (α) were systematically researched including the molar ratio of the template molecule (PG) to the functional monomer (VIM), the molar ratio of functional monomer to cross-linker (EGDMA), the types of solvent and the reaction time. And the physicochemical property and morphology of the obtained VIM-MIP with the best adsorption performance were explored by a series of characterization methods. The adsorption tests were carried out, indicating that the VIM-MIP exhibited large adsorption capability (Qe=81.34 mg/g), which exceeded 78.97% of existing optimal absorbents for PG. What’s more, the adsorption data for PG fit in with the Freundlich model (R2>0.99). More notably, the excellent PG selectivity of the VIM-MIP was confirmed by competitive adsorption experiments under binary systems (relative selectivity coefficient, 2.014), which was attributed to the existence of imprinted cavities. The molecular simulation, X-ray photoelectron spectroscopy (XPS) analysis and Zeta potential analysis were employed to reveal the adsorption mechanism, indicating the hydrogen bond was the main driving force.
Real-time imaging and monitoring of biothiols in living cells are essential for understanding pathophysiological processes. However, the design of the fluorescent probe that has accurate and repeatable real-time monitoring capabilities for these targets is highly challenging. In this study, we prepared a fluorescent sensor, Lc-NBD-Cu(II), which contains a N1, N1, N2-tris-(pyridin-2-ylmethyl) ethane-1,2-diamine as a Cu(II) chelating unit and a 7-nitrobenz-2-oxa-1,3-diazole fluorophore to detect Cysteine (Cys). Emission changes promoted by addition of Cys to this probe are distinctive and correspond to a range of processes including Cys induced loss of Cu(II) from Lc-NBD-Cu(II) to form Lc-NBD, Cu(I) oxidation to reform Cu(II), Cys oxidation to form Cys-Cys, Cu(II) binding to Lc-NBD to reform Lc-NBD-Cu(II), and competitive binding of Cu(II) to Cys-Cys. The study also shows that Lc-NBD-Cu(II) maintains high stability during the sensing process and that it can be utilized over a number of detection cycles. Finally, the findings show that Lc-NBD-Cu(II) can be utilized to repetitively sense Cys in living HeLa cells.
A core-shell biacid catalyst WO3@mSiO(2)-SO3H was prepared. Through the core-shell structure, an interface with internal and external spatial relationship was formed, which was used to synergistic catalyze the preparation of furfural from xylose. And the conversion of xylose was as high as 98.7% and the furfural yield was 70.1% at 170 degrees C for 4 h in water-toluene mixture (1:2 v/v%). The research provided a case for the preparation of furfural from xylose catalyzed by sulfonated core-shell catalyst and provided more application prospects for core-shell catalysts in biomass conversion.
Carbon monoxide (CO) is a colorless and odorless gas often used as a fuel and as an important raw material for the synthesis of basic organic compounds in the chemical industry. CO affects respiration and organ coordination in organisms, and is fatal at high concentration. Due to the wide range of industrial applications and biological effects of CO, its research has received considerable attention from researchers. In this study, we designed and synthesized a chemiluminescent sensor CL-CO, which can recognize CO in the presence of palladium chloride (PdCl2), based on the Schaap’s adamantylidene-dioxetane system and allyl ether as the recognition site. In both liquid and solid states, CL-CO can recognize CO gas with high sensitivity and selectivity. This work provides a convenient tool for studying CO gas, and a new application for exploring the adamantylidene-dioxetane system.
Biological thiols are crucial in biological processes. Therefore, a probe capable of targeting and imaging biothiols in living cells, as well as rapidly labelling the thiols in proteins, is desirable and imperative. Herein, we designed and synthesized FRB-T containing alpha, fl-unsaturated ketones to recognize thiols for detecting biothiols and selectively labelling the sulfhydryl-containing proteins. The probe initially exhibited weak fluorescence and then performed 1, 4-Michael addition reaction between its alpha, fl-unsaturated ketone and thiols, along with the spiro ring-opening, leading to remarkable fluorescence enhancement and colour changes. The specificity of FRB-T towards thiols was high, and its detection limits were 70 nM for cysteine (Cys) and 1.51 mu g/mL for ovalbumin (OVA). Furthermore, FRB-T has also been successfully applied to biothiols imaging in Hela cells, and rapid labelling of the sulfhydryl-containing proteins without washing step.
Developing ultraviolet (UV) sensors that can visualize UV light in the environment for productive life has been widely practiced. A challenging problem that arises in this domain is the quantitative analysis of UV light. In this study, we identified a novel naphthalimide derivative, NDGF, which can undergo decomposition to various degrees when irradiated by UV light with different intensities, so as to produce corresponding fluorescence intensities. Moreover, NDGF was prepared as a UV-responsive film NDGF-PEO which also has outstanding competence in the quantification of UV intensity. The surprising thing is that this novel UV-responsive decomposition mechanism of NDGF has been demonstrated and has great potential to open new doors for the development of naphthalimide-based photocages and novel UV quantitative sensors.
A rapid and convenient strategy to monitor the productivity of biomanufacturing is essential for the research in optimizing relevant bioprocesses. In this work, we have developed a fluorescein-derived probe (FL-DT) that reacts rapidly with thiol groups via 1,4-Michael addition reaction of the sulfhydryl to unsaturated ketone and releases fluorescence. FL-DT specifically forms fluorescent adduct with two adjacent thiols in a protein of interest (POI), making the probe a reliable tool for protein quantification. The production of xylanase fused with a short di-Cys tag was then successfully monitored and quantified with FL-DT in Escherichia coli system under different protein expression conditions, providing useful information for optimizing the bioprocess. Our work provides a convenient and efficient strategy for POI labeling and monitoring bioproduction.
为检测微弱的射电信号,要求望远镜接收机噪声性能良好.低噪声放大器(Low Noise Amplifier, LNA)作为接收机前端关键电路,其噪声系数和增益决定了整机的噪声性能.设计了一款1.2–2.2 GHz的低噪声放大器,电路采用两级级联结构,第2级通过引入负反馈,在改善增益平坦度和拓宽带宽的同时减小噪声,级间经过后级输入阻抗优化后仅需一个隔直电容.并引入有损输出匹配网络,实现高增益、低噪声、良好回波损耗和较为平坦的宽带LNA设计.测试结果表明,在1.2–2.2 GHz频段增益30–33 dB,噪声温度平均值为47 K,输出1 d B压缩点大于11.3 dBm.测试性能良好,可用于该频段接收机系统中.
The photocage is a light sensitive substance for photo-controlled release, which is formed by combining the target substance with photosensitive group and other functional groups through physical and chemical methods.Under the irradiation of the specified band, the photocage releases the target substance.It is widely concerned because it can realize space-time control, which means that the time and place of release are controllable.The advantages of simple operation, easy control, strong modification ability and small body damage make it widely used in chemistry, biology, materials science and medicine.In this paper, we introduced and discussed the research progress of photocages in photo-controlled release of metal ions, gases, fluorescent substances, amino acids, peptides, enzymes, proteins, drugs and other target substances in recent 10 years.
The nicotinamide adenine dinucleotide derivatives (NADPH, NADP(+), NADH, and NAD(+)) are important redox cofactors that involve in many biological activities, and their concentration levels are associated with a variety of diseases. In this work, an imidazolium functionalized polydiacetylenes sensing system (IM-PDAs) is reported to selectively detect the reduced form of nicotinamide adenine dinucleotide phosphate (NADPH). Depending on the electrostatic attraction between the positively charged imidazolium heads and the negatively charged phosphate groups, the sensing system exhibits colorimetric and fluorescent responses when exposed to NADPH and its oxidized form (NADP(+)); while the system does not respond to the less negatively charged NADH and NAD(+) at the concentration range tested in this study. Owing to the positively charged nicotinamide of NADP(+), the detection sensitivity of IM-PDAs towards NADP(+) is much lower than that towards NADPH, successfully differentiating NADPH from the rest three cofactors. Furthermore, IM-PDAs loaded paper-based sensor is constructed and demonstrates the potentials of IM-PDAs based sensing device for practical applications in NADPH detection.
A ratiometric probe (HBT-HBZ) bearing 2-hydrazino benzothiazole and 3-(benzo[d]thiazol-2-yl)-2-hydroxy-5-methylbenzaldehyde for sensing hypochlorous acid (HClO) with high selectivity and sensitivity is reported in this article. The fluorescence intensity ratios (I-470nm/I-572nm) of the probe with different concentrations of analyte showed excellent selectivity and a linear response to minor changes in HClO. The detection limit of 24 nmol/L suggests that the sensor is very sensitive to HClO. According to the series of performed experiments, HBT-HBZ has practical applications, such as the detection of HClO residues in tap water, which has been rarely reported. In addition, confocal laser microscopy experiments confirmed that HBT-HBZ can selectively recognize HClO in HeLa cells. A ratiometric probe (HBT-HBZ) for sensing HClO with high selectivity and sensitivity is reported in this article. The probe exhibited high selectivity for HClO among other ROS, RNS and anions. In addition, HBT-HBZ has some practical applications such as the analysis of the HClO content in tap water. Furthermore, confocal fluorescence microscopy imaging showed that HBT-HBZ can be applied for detecting HClO in living cells. (C) 2020 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Novel supramolecular vesicles based on host-guest systems were coassembled from carboxylate-substituted pillar[6] arene (CPA[6]) and disulfide-linked benzimidazolium amphiphiles, and the microstructures of the CPA-based supramolecular vesicles were clearly elaborated. The supramolecular vesicles showed controlled drug release in response to five stimuli, with glutathione, pH, CO2, Zn2+ ions, and hexanediamine, leading to cleavage of the disulfide bonds, protonation of the carboxylate groups, metal chelation, and competitive binding. This is the first case of a smart pillararene-based supramolecular vesicle being integrated with five stimuli-responsive functions to meet the diverse requirements of controlled drug release. Importantly, each of the five stimuli is closely related to microenvironments of tumors and diseases of the human body. The smart stimuli-responsive supramolecular vesicles have promising applications in drug therapy of tumors and relevant diseases.
Controlled hierarchical self-assembly of synthetic molecules into chiral nanoarchitectures to mimic those biological chiral structures is of great importance. Here, a low-molecular-weight organogelator containing a benzimidazole moiety conjugated with an amphiphilic l-glutamic amide has been designed and its self-assembly into various hierarchical chiral nanostructures is investigated. Upon gel formation in organic solvents, 1D chiral nanostructure such as nanofiber and nanotube are obtained depending on the solvents. In the presence of transition and rare earth metal ions, hierarchical chiral nanostructures are formed. Specifically, the addition of TbCl3 , EuCl3 , and AgNO3 leads to nanofiber structures, while the addition of Cu(NO3 )2 , Tb(NO3 )3 , or Eu(NO3 )3 provides the microflower structures and microtubular flower structures, respectively. While Eu(III) and Tb(III)-containing microtubular flowers keep the chirality, the Cu(II)-coordinated microflowers lose chirality. More interestingly, the nanofibers formed by the gelator coordinated with Eu(III) or Tb(III) ions show not only the supramolecular chirality but also the circularly polarized luminescence.
Gold nanoshells have strongly tunable localized surface plasmon resonance and therefore attract considerable interest for numerous applications. Here, we present a facile one-pot seedless approach to rapidly and controllably prepare gold nanoshells. According to this approach, the continuous and uniform gold nanoshells were obtained directly by adding NaBH4, PVP, NaOH and ascorbic acid ( AA) into the mixture solution of HAuCl4 and polyelectrolyte modified polystyrene ( PS) colloidal spheres, sequentially. The obtained gold nanoshells showed structure-dependent localized surface plasmon resonance and their absorption wavelengths red-shifted as the gold nanoshells grew from incomplete to continuous gold layers. In terms of the photothermal conversion property, gold nanoshells could effectively convert 808 nm laser to heat and the temperature increase depended highly on the structure of gold nanoshells.