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There is an urgent need to develop phototherapeutic agents with imaging capabilities to assess the treatment process and efficacy in real-time during cancer phototherapy for precision cancer therapy. The safe near-infrared (NIR) fluorescent dyes have garnered significant attention and are desirable for theranostics agents. However, until now, achieving excellent photostability and fluorescence (FL) imaging capability in aggregation-caused quenching (ACQ) dyes remains a big challenge. Here, for the only FDA-approved NIR dye, indocyanine green (ICG), we developed a dual-ferrocene (Fc) chimeric nanonetwork ICG@HFFC based on the rigid-flexible strategy through one-step self-assembly, which uses rigid Fc-modified hyaluronic acid (HA) copolymer (HA-Fc) and flexible octadecylamine (ODA) bonded Fc (Fc-C18) as the delivery system. HA-Fc reserved the ability of HA to target the CD44 receptor of the tumor cell surface, and the dual-Fc region provided a rigid space for securely binding ICG through metal–ligand interaction and π–π conjugation, ensuring excellent photostability. Additionally, the alkyl chain provided flexible confinement for the remaining ICG through hydrophobic forces, preserving its FL. Thereby, a balance is achieved between outstanding photostability and FL imaging capability. In vitrostudies showed improved photobleaching resistance, enhanced FL stability, and increased singlet oxygen (1O2) production efficiency in ICG@HFFC. Further in vivoresults display that ICG@HFFC had good tumor tracing ability and significant tumor inhibition which also exhibited good biocompatibility.. Therefore, ICG@HFFC provides an encouraging strategy to realize simultaneous enhanced tumor tracing and photothermal/photodynamic therapy (PTT/PDT) and offers a novel approach to address the limitations of ACQ dyes.

Solid oxide electrolysis cells (SOECs) provide a promising way for converting renewable energy into chemical fuels. Traditionally, NiO/CGO (nickel-gadolinium doped ceria) cermet has shown its excellent properties in ionic and electronic conductivity under reducing conditions. Herein, we developed a novel 1D NiO/CGO cathode through a cerium metal-organic framework (MOF) derived process. The cathode’s 1D nanostructure integrated with a microchannel scaffold facilitates enhanced mass transport, providing vertically aligned pathways for CO2and H2O diffusion. Additionally, the 1D framework increases the number of interfacial sites and reduces ion diffusion distances, thereby simplifying electron/ion transport. Consequently, this advanced cathode achieved a significant breakthrough in SOEC performance, maintaining efficient CO2and H2O electrolysis at an extraordinary current density of 1.41 A/cm2at 1.5 V and excellent stability over 24 h at 850 °C. The enhanced performance of this newly developed cathode not only achieves a remarkable 100% improvement compared to those of NiO/CGO cathodes with varying geometrical configurations but also surpasses those of commercial NiO/CGO catalysts by an outstanding 40% when tested under identical conditions. The development of the 1D NiO/CGO enhances the efficiency and durability of ceramic cathodes for CO2and H2O co-electrolysis in SOECs and improves the scalability and effectiveness of SOECs in renewable energy applications.

Control over the pore structure of zeolite is very important, so researchers are trying to regulate the pore structure of zeolite through various methods to endow it with better performance in industrial applications. Here, a confined etching route that could selectively increase the microporous structure of zeolite is developed using ethanol/amine buffer solution. Ethanol is introduced into an aqueous amine solution, where it could decrease the migration rate and concentration of hydroxyl ions which can etch the framework atoms of zeolite to fabricate various porous structures, consequently developing a confined etching route that could selectively increase the microporous structure of zeolite, unlike conventional approaches that generally increase mesoporous and macroporous architectures. In addition, ethanol enhances the solubility of amine in water, and a buffer solution (ethanol/amine) is formed, which is able to release hydroxyl ions continuously. Based on the above confined etching route, a micropore-increased beta crystal is synthesized and when used as a carrier in ZnLaY/beta catalysts, it achieves excellent ethanol conversion of 96.04% and butadiene selectivity of 64.22% in 20 h time-on-stream in an ethanol to butadiene reaction.Keywords: Ethanol; Confined etching route; Micropore-increased; Beta zeolite; Ethanol to butadiene.

C20H22N2O4, monoclinic, P21/n(no. 14), a= 11.4033(15) Å, b= 14.2998(16) Å, c= 11.6486(16) Å, β= 91.197(8)°, V= 1899.1(4) Å3, Z= 4, Rgt(F) = 0.0513, wRref(F2) = 0.1542, T= 296.2 K.

In the field of recycling CO2, the photocatalytic CO2reduction reaction (CO2RR) is a typical example, and researchers have designed a variety of photocatalysts to improve the conversion rate of CO2over the years. In this paper, two metal–oxygen clusters are designed and formulated as [Co3Zn(OH)6(SO4)]·4H2O (1) and [Ni3Zn(OH)6(SO4)]·4H2O (2). As for compound 1, the main structure is composed of {CoO6} octahedra connected by edge-sharing to form a two-dimensional layer, on which {ZnO4} and {SO4} tetrahedra are supported. More interestingly, compound 1has outstanding photocatalytic activity, which is mainly attributed to the open-framework structure and the cobalt ions as active sites. Upon catalysis for eight hours, its maximum CO generation rate is 9982.13 μmol g–1h–1, with a selectivity of 81.8%. Additionally, compound 1takes on weak antiferromagnetic coupling due to Co(II) ions.

Constructing efficient nanocatalysts for the oxygen reduction reaction (ORR) is crucial for the widespread application of metal–air batteries. Herein, we construct carbon-guarded cobalt-based nanospheres composed of metal nanoparticles encased in a nitrogen doped carbon shell (M@NC NPs, where M stands for metal or alloy) through a bifunctional gas phase heat treatment technique. Compared to monometallic and polymetallic nanospheres, bimetallic nanospheres of Ni/Co@NC NPs exhibit enhanced ORR activity, even comparable to that of the commercial Pt/C catalyst, and have robust catalytic stability. In situRaman spectra analysis during the ORR electrocatalysis reveals a strong interaction between the carbon shell of Ni/Co@NC NPs and the ORR intermediates. Moreover, Ni/Co@NC NPs show superior catalytic capability compared to Pt/C in a battery system, resulting in improved discharging performance in a home-made zinc–air battery, this includes higher peak power density (185.5 mW cm−2), better rate performance, and larger discharging capacity (817 mA h gZn−1). These impressive catalytic performances are attributed to the three-dimensional structure that contains carbon-guarded Ni/Co alloy nanoparticles, the partially graphitized nitrogen-doped carbon shell that is dispersed with Ni/Co active moieties, and the electronic effect of the Ni/Co alloy on the carbon shell. This work provides a general strategy for synthesizing durable carbon-guarded and metal-diversified nanosphere electrocatalysts for efficient energy conversion.

Limited information is available on long-term effects of metal(loid)s pollution incidents. Here, we analyze the distribution characteristics and quantification of elements in the Southwest China Keda mining site, which is one of the most populated sites and enables human health and ecological risk assessments of elemental pollution. The results on modified degree of contamination indicated that the soil and sediment were highly contaminated near Dahu Lake. The health risk of children was almost 2.5 times that of adults in surface water, and 7.1 times in soil, respectively. Moreover, Tl and As were the main health risk contributors in surface water and soil, respectively, and As posed the highest ecological risk both in soil and sediment. These results indicated the potential impact of toxic metal(loid)s on the health of residents and environment. Hence, more scientific attention and proper management need to be paid to this environmental challenge in the future.

Selective functionalization of C–F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted organic molecules using simple and inexpensive trifluoromethyl sources as the starting materials. In this regard, impressive progress has been made on the defluorinative functionalization reactions that proceed viaradical intermediates. Nevertheless, it is still a great challenge to precisely control the defluorination process, due to the continuous decrease of the C–F bond strength after the replacement of one or two fluorine atoms with various functionalities. This review article is aimed to provide a brief overview of recently reported methods used to functionalize C–F bonds of CF3groups viaradical intermediates. An emphasis is placed on the discussion of mechanistic aspects and synthetic applications

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In this paper, we utilize d-dimensional Bell states to construct a multi-party semiquantum private comparison (MSQPC) protocol with two supervisors, which can determine the size relationship of more than two classical users’ private inputs under the control of two supervisors within one round implementation. The two supervisors, i.e., one quantum third party (TP) and one classical TP, are both semi-honest, which means that they can misbehave at their own wishes but are not permitted to conspire with anyone else. Neither quantum entanglement swapping nor unitary operations are required in the proposed MSQPC protocol. The security analysis certifies that the proposed MSQPC protocol can overcome both the outside attacks and the participant attacks.

cis-Diol-containing metabolites are widely distributed in living organisms, and they participate in the regulation of various important biological activities. The profiling of cis-diol-containing metabolites could help us in fully understanding their functions. In this work, based on the characteristic isotope pattern of boron, we employed a boronic acid reagent as the isotope tag to establish a sensitive and selective liquid chromatography–high-resolution mass spectrometry method for the screening and annotation of cis-diol-containing metabolites in biological samples. Boronic acid reagent 2-methyl-4-phenylaminomethylphenylboronic acid was used to label the cis-diol-containing metabolites in biological samples to improve the selectivity and MS sensitivity of cis-diol-containing metabolites. Based on the characteristic 0.996 Da mass difference of precursor ions and the peak intensity ratio of 1:4 originating from 10B and 11B natural isotopes, the potential cis-diol-containing metabolites were rapidly screened from biological samples. Potential cis-diol-containing metabolites were annotated by database searching and analysis of fragmentation patterns obtained by multistage MS (MSn) via collision-induced dissociation. Importantly, the cis-diol position could be readily resolved by the MS3spectrum. With this method, a total of 45 cis-diol-containing metabolites were discovered in rice, including monoglycerides, polyhydroxy fatty acids, fatty alcohols, and so forth. Furthermore, the established method showed superiority in avoiding false-positive results in profiling cis-diol-containing metabolites.

•The framework of mobilities and health is used to explain the multi-dimensional health consequences of frequent business travel.•Perceptions of health impacts vary among respondents with different travel pattern and personal situations.•With longer experiences, travelers are more aware about the potential health cost but health impairment has been accumulated.•Public glamorization of business travel needs to be changed.

Ammonia is one of the most important industrial intermediates due to the mass-demand for the production of various chemicals. Since the development of the Haber–Bosch process, most ammonia production has been conducted using Fe-, Co-, and Ru-based catalysts. Meanwhile, the low-cost and earth-abundant elements, such as Ni, typically show much inferior activity due to their weak nitrogen adsorption energy. Here, we show that LaNi5, a representative hydrogen-absorbing material, offers stable and high ammonia production through surface decomposition to a unique Ni–LaN core–shell structure. The reaction rate is as high as 4500 μmol·g–1·h–1, which is much higher than those of other reported Co and Ni intermetallic catalysts and comparable to those of reported Ru-based intermetallic catalysts. TEM observations demonstrated that the nanosized Ni–LaN core–shell structures were self-organized during ammonia synthesis and generated a Ni–LaN active nanostructure, accounting for the high and stable catalytic performance in ammonia synthesis. Since the Ni–LaN active structure allows for the transition metal–nitride composite to generate ammonia universally, these discoveries show that hydrogen-storage materials can be a promising playground for designing brand-new ammonia synthesis catalysts without including expensive rare metals.

Ammonia is one of the most important feedstocks for the production of fertilizer and as a potential energy carrier. Nitride compounds such as LaN have recently attracted considerable attention due to their nitrogen vacancy sites that can activate N2for ammonia synthesis. Here, we propose a general rule for the design of nitride-based catalysts for ammonia synthesis, in which the nitrogen vacancy formation energy (ENV) dominates the catalytic performance. The relatively low ENV(ca. 1.3 eV) of CeN means it can serve as an efficient and stable catalyst upon Ni loading. The catalytic activity of Ni/CeN reached 6.5 mmol·g–1·h–1with an effluent NH3concentration (ENH3) of 0.45 vol %, reaching the thermodynamic equilibrium (ENH3= 0.45 vol %) at 400 °C and 0.1 MPa, thereby circumventing the bottleneck for N2activation on Ni metal with an extremely weak nitrogen binding energy. The activity far exceeds those for other Co- and Ni-based catalysts, and is even comparable to those for Ru-based catalysts. It was determined that CeN itself can produce ammonia without Ni-loading at almost the same activation energy. Kinetic analysis and isotope experiments combined with density functional theory (DFT) calculations indicate that the nitrogen vacancies in CeN can activate both N2and H2during the reaction, which accounts for the much higher catalytic performance than other reported nonloaded catalysts for ammonia synthesis.

The sluggish oxygen evolution reaction (OER) and costly noble-metal oxide catalysts hinder the vast usage of environmentally friendly water splitting for hydrogen production. Elemental doping by partial replacing of parent metal elements with elements of higher electronegativity is considered to be one of the most efficient strategies to promote the electrocatalytic OER performance. In this work, we synthesize an efficient hierarchical highly wrinkled NiFeCu phosphide nanosheet on nanodendrite Ni3S2/NiF substrates through partial replacement of Cu instead of Ni and Fe in NiFeP@Ni3S2/NiF by using a facile electrodeposition method. The NiFeCuP@Ni3S2/NiF electrocatalyst needs only 230, 282, and 351 mV to reach 10, 50, and 100 mA × cm–2, respectively. Notably, this electrocatalyst shows one of the lowest OER overpotentials at 10 mA/cm–2for metal phosphides and endured the OER at 20 mA × cm–2for 18 h with negligible voltage elevation. The X-ray photoelectron spectroscopy (XPS), double-layer capacitance (Cdl) plots, and electrochemical impedance spectroscopy show that the partial Cu doping in NiFeP@Ni3S2/NiF not only can change the electron density around Ni and Fe but also can increase the electrochemically active surface area and conductivity of electrocatalysts.

Ammonia (NH3) is pivotal to the fertilizer industry and one of the most commonly produced chemicals1. The direct use of atmospheric nitrogen (N2) had been challenging, owing to its large bond energy (945 kilojoules per mole)2,3, until the development of the Haber–Bosch process. Subsequently, many strategies have been explored to reduce the activation barrier of the N≡N bond and make the process more efficient. These include using alkali and alkaline earth metal oxides as promoters to boost the performance of traditional iron- and ruthenium-based catalysts4–6via electron transfer from the promoters to the antibonding bonds of N2through transition metals7,8. An electride support further lowers the activation barrier because its low work function and high electron density enhance electron transfer to transition metals9,10. This strategy has facilitated ammonia synthesis from N2dissociation11and enabled catalytic operation under mild conditions; however, it requires the use of ruthenium, which is expensive. Alternatively, it has been shown that nitrides containing surface nitrogen vacancies can activate N2(refs. 12–15). Here we report that nickel-loaded lanthanum nitride (LaN) enables stable and highly efficient ammonia synthesis, owing to a dual-site mechanism that avoids commonly encountered scaling relations. Kinetic and isotope-labelling experiments, as well as density functional theory calculations, confirm that nitrogen vacancies are generated on LaN with low formation energy, and efficiently bind and activate N2. In addition, the nickel metal loaded onto the nitride dissociates H2. The use of distinct sites for activating the two reactants, and the synergy between them, results in the nickel-loaded LaN catalyst exhibiting an activity that far exceeds that of more conventional cobalt- and nickel-based catalysts, and that is comparable to that of ruthenium-based catalysts. Our results illustrate the potential of using vacancy sites in reaction cycles, and introduce a design concept for catalysts for ammonia synthesis, using naturally abundant elements.

Objective: To investigate perceptions and acceptability of, and attitudes towards, acupuncture for post-acute stroke and rehabilitation care by exploring the views of different stakeholders.Methods: Three electronic surveys were conducted to gauge the breadth of knowledge and acceptance of acupuncture in post-acute stroke and rehabilitation care among three stakeholder groups: (1) traditional acupuncturists registered with the British Acupuncture Council (BAcC); (2) National Health Service (NHS) professionals attending the 2017 UK Stroke Forum conference; and (3) the UK network of Stroke Club co-ordinators.Results: Of 278 NHS respondents, 31% were doctors. Over half (52%) of all NHS respondents reported they had insufficient knowledge about acupuncture, its effectiveness (23%) or how to refer (21%). Only 12% had previously referred stroke patients for acupuncture but 46% thought that there was role for acupuncture in post-acute stroke care (50% were unsure). Two thirds of BAcC acupuncturist respondents had treated at least one stroke patient, with 70.1% having treated 1–5 stroke patients and 71% having provided treatment in the last year, most commonly for motor impairment (88.2%). Of 99 Stroke Club coordinators who responded, only seven had ever been asked about acupuncture by patients, but most felt there would be interest.Conclusion: Interest in the provision of acupuncture for post-acute stroke care was expressed by both NHS practitioners and acupuncturists. Further research is required on the acceptability of acupuncture to patients as well as evidence of its clinical and cost effectiveness.