Screening of Transition Metal Supported on Black Phosphorus as Electrocatalysts for CO2 Reduction.

The electrocatalytic CO2 reduction (CO2RR) is an effective and economical strategy to eliminate CO2 through conversion into value-added chemicals and fuels. However, exploring and screening suitable 2D material-based single-atom catalysts (SACs) for CO2 reduction are still a great challenge. In this study, 27 (3d, 4d, and 5d, except Tc and Hg) transition metal (TM) atom-doped black phosphorus (TM@BP) electrocatalysts were systematically investigated for CO2RR by density functional theory calculations. According to the stability of SACs and their effectiveness in activating the CO2 molecule, three promising catalysts, Zr@BP, Nb@BP, and Ru@BP, were successfully screened out, exhibiting outstanding catalytic activity for the production of carbon monoxide (CO), methyl alcohol (CH3OH), and methane (CH4) with limiting potentials of -0.79, -0.49, and -0.60 V, respectively. A catalytic relationship between the d-band centers of SACs and the limiting potential of CO2RR was used to estimate the catalytic activity of catalysts. Furthermore, Nb@BP has high selectivity for CO2RR to CH3OH compared to H2 formation, while the hydrogen evolution reaction significantly impacts the synthesis of CO and CH4 on Zr@BP and Ru@BP. Nitrogen atom doping in BP is beneficial for enhancing the selectivity of CO2RR, but it is detrimental to the activity of CO2RR. This study offers theoretical guidance for synthesizing highly efficient CO2RR electrocatalysts and further enhances structural modulation methods for layered 2D materials.

Niobium Modification of CeO2 Tuning Electron Density of Nickel-Ceria Interfacial Sites for Enhanced CO2 Methanation.

CO2 methanation has attracted considerable attention as a promising strategy for recycling CO2 and generating valuable methane. This study presents a niobium-doped CeO2-supported Ni catalyst (Ni/NbCe), which demonstrates remarkable performance in terms of CO2 conversion and CH4 selectivity, even when operating at a low temperature of 250 °C. Structural analysis reveals the incorporation of Nb species into the CeO2 lattice, resulting in the formation of a Nb-Ce-O solid solution. Compared with the Ni/CeO2 catalyst, this solid solution demonstrates an improved spatial distribution. To comprehend the impact of the Nb-Ce-O solid solution on refining the electronic properties of the Ni-Ce interfacial sites, facilitating H2 activation, and accelerating the hydrogenation of CO2* into HCOO*, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis and density functional theory (DFT) calculations were conducted. These investigations shed light on the mechanism through which the activity of CO2 methanation is enhanced, which differs from the commonly observed CO* pathway triggered by oxygen vacancies (OV). Consequently, this study provides a comprehensive understanding of the intricate interplay between the electronic properties of the catalyst's active sites and the reaction pathway in CO2 methanation over Ni-based catalysts.

Theoretical study of transition metal-doped ß12 borophene as a new single-atom catalyst for carbon dioxide electroreduction.

The electrocatalytic carbon dioxide reduction reaction (CO2RR) presents a viable and cost-effective approach for the elimination of CO2 by transforming it into valuable products. Nevertheless, this process is impeded by the absence of exceptionally active and stable catalysts. Herein, a new type of electrocatalyst of transition metal (TM)-doped ß12-borophene (TM@ß12-BM) is investigated via density functional theory (DFT) calculations. Through comprehensive screening, two promising single-atom catalysts (SACs), Sc@ß12-BM and Y@ß12-BM, are successfully identified, exhibiting high stability, catalytic activity and selectivity for the CO2RR. The C1 products methane (CH4) and methanol (CH3OH) are synthesized with limiting potentials (UL) of -0.78 V and -0.56 V on Sc@ß12-BM and Y@ß12-BM, respectively. Meanwhile, CO2 is more favourable for reduction into the C2 product ethanol (CH3CH2OH) compared to ethylene (C2H4) via C-C coupling on these two SACs. More importantly, the dynamic barriers of the key C-C coupling step are 0.53 eV and 0.73 eV for the "slow-growth" sampling approach in the explicit water molecule model. Furthermore, Sc@ß12-BM and Y@ß12-BM exhibit higher selectivity for producing C1 compounds (CH4 and CH3OH) than C2 (CH3CH2OH) in the CO2RR. Compared with Sc@ß12-BM, Y@ß12-BM demonstrates superior inhibition of the competitive hydrogen evolution reaction (HER) in the liquid phase. These results not only demonstrate the great potential of SACs for direct reduction of CO2 to C1 and C2, but also help in rationally designing high-performance SACs.

Regulation of the Coordination Structures of Transition Metals on Nitrogen-Doped Carbon Nanotubes for Electrochemical CO2 Reduction.

The electrochemical carbon dioxide reduction reaction (CO2RR) has been extensively studied due to its potential to reduce the globally accelerating CO2 emission and produce value-added chemicals and fuels. Despite great efforts to optimize the catalyst activity and selectivity, the development of robust design criteria for screening the catalysts and understanding the role of water and potassium for CO2 activation poses a significant challenge. Herein, a rapid method for screening single-atom catalysts (SACs) possessing different coordination structures toward the CO2RR process to form CO, namely, a metal atom supported on nitrogen-doped carbon nanotubes (M@CNT, M@1N_CNT, M@2N_CNT, and M@3N_CNT), was established using large-scale density functional theory computations. Adopting the free energy of *CO2 and *OH as screening descriptors, Fe@CNT, Cu@1N_CNT, Pd@2N_CNT, and Ni@3N_CNT were found to exhibit high activity for CO in the gas phase with the overpotential values of 0.22, 0.11, 0.13, and 0.05 V, respectively. Water and potassium present on the surface of the active sites can accelerate the activation of CO2 relative to the gas phase. Ni@3N_CNT shows the highest activity and selectivity in the environment having four water and one potassium. Particularly, the least absolute shrinkage and selection operator regression study revealed that the CO2 adsorption is intrinsically governed by the number of electrons lost by the metal atom in the three N-doped systems, which can be correlated to the distance of the metal atom from the plane of the coordination atom in the M@CNT system. Besides, the study proposes equations for the calculation of the free energy of CO2 adsorption. The current work not only advances the exploration of highly active SACs for the heterogeneous electrocatalytic systems for CO2RR but also highlights the significance of water and potassium in the aqueous solution.

Heavy metals pollution characteristics and risk assessment in sediments and waters: The case of Tianjin, China.

Potential health and ecological risks due to heavy metal pollution in surface waters and sediments were evaluated based on a health risk assessment model and a potential ecological risk index method. Combined with the reclamation progress of Tianjin Nangang Industrial Zone, in China, a survey was carried out in the area dealing with heavy metals concentrations in surface waters and sediments, covering from 2008 to 2018. Specifically, concentrations were determined for As, Cd, Hg, Cu, Pb, and Zn. The results show that As、Cd、Hg、Cu 、Pb、Zn average concentrations in surface water were 0.99 µg/L∼1.27 µg/L, 0.13 µg/L∼0.63 µg/L, 0.03 µg/L∼0.13 µg/L, 1.5 µg/L∼4.65 µg/L, 1.25 µg/L∼4.7 µg/L, 13.5 µg/L∼20.99 µg/L and which average concentrations in sediment were 5.12 mg/kg∼12.34 mg/kg, 0.12 mg/kg∼0.18 mg/kg, 0.04 mg/kg ∼0.087 mg/kg, 13.45 mg/kg∼31.92 mg/kg, 13.2 mg/kg ∼21.26 mg/kg, 21.58 mg/kg ∼77.21 mg/kg, respectively. The background values of the Hailuan River basin near the study area were taken as the reference and compared with the national sediment quality standards a tell us the quality of the sediments in Tianjin Nangang coastal area being good. As regards the characteristics of pollution, heavy metals showed a high concentration in 2008 and then decreased significantly, which related to the dredging of large amounts of contaminated surface sediment during port construction. According to the phase equilibrium partition coefficient (Kp) and temporal and spatial distribution characteristics of heavy metals, sediments can be seen as an obvious sink for lead, with this element being mainly affected by exogenous input in coastal seawater. Zn, As, Cd, and Hg contents in surface water were greatly affected by the endogenous release from sediments. The results of the environmental risk assessment showed that the main environmental health risk of Tianjin coastal waters was carcinogenic, and specifically due to As. The potential heavy metals ecological risk assessment results of surface sediments were mild for the affected areas.

Perovskite oxide for emerging photo(electro)catalysis in energy and environment.

Using solar energy to catalyse photo-driven processes to address the energy crisis and environmental pollution plays a role in the path to a sustainable society. Many oxide-based materials, especially perovskite oxides, have been widely investigated as catalysts for photocatalysis in energy and environment because of the low-cost and earth-abundant and good performance. At this stage, there is a need to present a scientific-based evaluation of the technologies developed so far and identify the most sustainable technologies and the existing limitations and opportunities for their commercialisation. This work comprehensively investigated the outcomes using various scientometric indices on perovskite oxide-based photo(electro)catalysts for water splitting, nitrogen fixation, carbon dioxide conversion, organic pollutant degradation, current trends and advances in the field. According to the results achieved, efforts in both energy and environment based on perovskite oxides have been initiated in the 1990s and accelerated since the 2010s. China and the United States were identified as the most contributing countries. Based on the results achieved in this study, the main milestones and current trends in the development of this field have been identified. The aim of this research is to provide useful guidelines for the further investigation of perovskite oxide-based catalysts for photoelectrocatalysis and photocatalysis both in energy and environment on the applications such as water splitting, nitrogen fixation, carbon dioxide conversion, and wastewater treatment.

Surface functionalized red fluorescent dual-metallic Au/Ag nanoclusters for endoplasmic reticulum imaging.

An efficient method is reported to prepare endoplasmic reticulum-targetable dual-metallic gold-silver nanoclusters, denoted as ER-Au/Ag nanoclusters (NCs), by virtue of a rationally designed molecular ligand. The prepared ER-Au/Ag NCs possesses red-emitting fluorescence with a strong emission at 622 nm and a high fluorescence quantum yield of 5.1%, which could avoid the influence of biological auto-fluorescence. Further investigation results showed that ER-Au/Ag NCs exhibited superior photostability, minimal cytotoxicity, and ER-targeting capability. Enabled by these meritorious features, ER-Au/Ag NCs have been successfully employed for long-term bioimaging of ER in living cells.Graphical abstract A sensitive non-enzymatic fluorescent glucose probe-based ZnO nanorod decorated with Au nanoparticles.

[Risk factors of progressive brain contusion and relationship with outcome].

OBJECTIVE: To investigate the risk factors of progressive brain contusion and to evaluate their impact on patients' outcome. METHODS: One hundred and thirty two patients with traumatic brain contusion were enrolled in the study, including 70 cases with progressive contusion and 62 cases with non-progressive contusion. The risk factors were investigated with univariate and multivariate Logistic regression analysis. RESULTS: The univariate analysis showed that Glasgow Coma Score (GCS) at admission, contusion volume at the first brain CT scans, midline shift, combined with skull fracture, subarachnoid hemorrhage, epidural hematoma, subdural hematoma, location of brain contusion, D-dimer levels, combined with type 2 diabetes were associated with progressive brain contusion. Multivariate Logistic regression analysis showed that GCS at admission, contusion volume at the first CT scans, combined with subarachnoid hemorrhage, combined with type 2 diabetes were the independent risk factors for disease progression. The outcome in the progressive group was more aggravated than that in non-progressive group (P = 0.001). CONCLUSION: Patients with disturbance of consciousness, the larger contusion volume, combined with subarachnoid hemorrhage and diabetes are at risk for progressive brain contusion and unfavorable outcome.

Single and double transition metal atoms doped graphdiyne for highly efficient electrocatalytic reduction of nitric oxide to ammonia.

The electrocatalytic conversion of nitric oxide (NORR) to ammonia (NH3) represents a pivotal approach for sustainable energy transformation and efficient waste utilization. Designing highly effective catalysts to facilitate the conversion of NO into NH3 remains a formidable challenge. In this work, the density functional theory (DFT) is used to design NORR catalysts based on single and double transition metal (TM:Fe, Co, Ni and Cu) atoms supported by graphdiyne (TM@GDY). Among eight catalysts, the Cu2@GDY is selected as a the most stable NORR catalyst with high NH3 activity and selectivity. A pivotal discovery underscores that the NORR mechanism is thermodynamically constrained on single atom catalysts (SACs), while being governed by electrochemical processes on double atom catalysts (DACs), a distinction arising from the different d-band centers of these catalysts. Therefore, this work not only introduces an efficient NORR catalyst but also provides crucial insights into the fundamental parameters influencing NORR performance.

Titanium carbide sealed cadmium sulfide quantum dots on carbon, oxygen-doped boron nitride for enhanced and durable photochemical carbon dioxide reduction.

Despite great efforts that have been made, photocatalytic carbon dioxide (CO2) reduction still faces enormous challenges due to the sluggish kinetics or disadvantageous thermodynamics. Herein, cadmium sulfide quantum dots (CdS QDs) were loaded onto carbon, oxygen-doped boron nitride (BN) and encapsulated by titanium carbide (Ti3C2, MXene) layers to construct a ternary composite. The uniform distribution of CdS QDs and the tight interfacial interaction among the three components could be achieved by adjusting the loading amounts of CdS QDs and MXene. The ternary 100MX/CQ/BN sample gave a productive rate of 2.45 and 0.44 µmol g-1 h-1 for carbon monoxide (CO) and methane (CH4), respectively. This CO yield is 1.93 and 6.13 times higher than that of CdS QDs/BN and BN counterparts. The photocatalytic durability of the ternary composite is significantly improved compared with CdS QDs/BN because MXene can protect CdS from photocorrosion. The characterization results demonstrate that the excellent CO2 adsorption and activation capabilities of BN, the visible light absorption of CdS QDs, the good conductivity of MXene and the well-matched energy band alignment jointly promote the photocatalytic performance of the ternary catalyst.

Construction adsorption and photocatalytic interfaces between C, O co-doped BN and Pd-Cu alloy nanocrystals for effective conversion of CO2 to CO.

Photocatalytic reduction of carbon dioxide (CO2) into fuels is an auspicious route to alleviate the energy and environmental crisis brought by the continuous depletion of fossil fuels. The CO2 adsorption state on the surface of photocatalytic materials plays a significant role in its efficient conversion. The limited CO2 adsorption capacity of conventional semiconductor materials inhibit their photocatalytic performances. In this work, a bifunctional material for CO2 capture and photocatalytic reduction was fabricated by introducing palladium (Pd)-copper (Cu) alloy nanocrystals onto the surface of carbon, oxygen co-doped boron nitride (BN). The elemental doped BN with abundant ultra-micropores had high CO2 capture ability, and CO2 was adsorbed in the form of bicarbonate on its surface with the presence of water vapor. The Pd/Cu molar ratio had great impact on the grain size of Pd-Cu alloy and their distribution on BN. The CO2 molecules tended to be converted to carbon monoxide (CO) at interfaces of BN and Pd-Cu alloys due to their bidirectional interactions to the adsorbed intermediate species while methane (CH4) evolution might occur on the surface of Pd-Cu alloys. Owing to the uniform distribution of smaller Pd-Cu nanocrystals on BN, more effective interfaces were created in the Pd5Cu1/BN sample and it gave a CO production rate of 7.74 µmolg-1h-1 under simulated solar light irradiation, higher than the other PdCu/BN composites. This work can pave a new way for constructing effective bifunctional photo-catalysts with high selectivity to convert CO2 to CO.

Revealing electrocatalytic CN coupling for urea synthesis with metal-free electrocatalyst.

Urea is ubiquitous in agriculture and industry, but its production consumes a lot of energy. The conversion of nitrogen (N2) and carbon dioxide (CO2) into urea via an electrocatalytic CN coupling reaction under ambient conditions would be a major boon to sustainable development. However, designing a metal - free catalyst with high activity and selectivity for urea remains a major challenge. Herein, by means of density functional theory (DFT) and ab - initio molecular dynamics (AIMD) computations, the B12 cluster doped on nitrogenated graphene (C2N) substrate catalyst (B12@C2N) with superior stability was designed for electrocatalytic urea synthesis starting from the CO2 and N2 through four reaction mechanisms. The nature of the co-adsorption activation of CO2 and N2 on the B12@C2N catalyst was investigated, the electrochemical proton - electron transfer steps and the CN thermochemical coupling led to the synthesis of urea. The study showed that the B12@C2N catalyst exhibited high catalytic activity for urea synthesis with the lowest limiting potential of - 1.01 V following the *HNNH mechanism compared with other mechanisms. The potential - determining step (PDS) is the formation of the *CO+*NH2NH2 species. However, the two - step CN coupling barriers of *NCON species are 0.13 eV and 0.60 eV using AIMD and a "slow - growth" sampling approach in an explicit water molecules model. Calculations also showed that the byproducts of carbon monoxide (CO), methane (CH4), methanol (CH3OH), ammonia (NH3), and hydrogen (H2) can be inhibited on the B12@C2N catalyst. Therefore, the metal - free catalyst not only has a good performance for the hydrogenation of CO2 and N2 promoting the electrochemical reaction, but also facilitates CN thermochemical coupling for urea synthesis. This work provides new insights into the synthesis of urea via the CN coupling reaction on a metal - free electrocatalyst, a process that could contribute to greenhouse gas mitigation to help meet carbon neutrality targets.

In situ rapid synthesis of ionic liquid/ionic covalent organic framework composites for CO2 fixation.

IL/ICOF composites were in situ synthesized via a one-pot route in half an hour under ambient conditions for catalytic cycloaddition of CO2 with epoxides into cyclic carbonates. The prepared composites feature a decent CO2 adsorption capacity of 1.63 mmol g-1 at 273 K and 1 bar and exhibit excellent catalytic performance in terms of yield and durability. This work may pave a new way to design and construct functionalized porous organic frameworks as heterogeneous catalysts for CO2 capture and conversion.

Perovskite oxides for oxygen transport: Chemistry and material horizons.

Oxygen permeable membrane, which has the advantages of high separation selectivity, low energy consumption and simple process in oxygen separation, can be used in the fields of environment and energy, such as pure oxygen preparation, fuel cell, oxygen-enriched combustion and chemical reactor for methane catalytic conversion (e.g. partial oxidation of methane, carbon dioxide reforming with methane). New materials and technological development are needed to achieve this target for GHG reformation. In this direction, mixed ionic-electronic conducting (MIEC) oxides based on perovskite oxides are one of the prominent materials for oxygen transport at high temperatures. These compounds were created into solid ceramic membranes with considerable electronic and oxygen ionic conductivity. As a result of the differential partial pressure of oxygen across the membrane, this process enables the ionic transfer of oxygen from the air, providing the driving force for oxygen ion transport. Notably, over the last 40 years, the defect theory has been applied to a wide range of MIEC materials, providing insight into electronic and ionic transport, widely applied to designing catalysts for wastewater treatment and gas purification. However, a critical review by in-depth analysis from the material side on perovskite oxides for oxygen transport is needed. This work evaluates the research community's significant and relevant contributions in the perovskite oxides for gas separation domain over the previous four decades in conjunction with theoretical concepts, which would give rise to the fundamental understanding of the impact of various transitional metal elements on oxygen transport performance and stability in a different atmosphere.

Effect of nickel-based electrocatalyst size on electrochemical carbon dioxide reduction: A density functional theory study.

The electrochemical carbon dioxide (CO2) reduction reaction (CO2RR) used for converting higher-value chemicals is a promising solution to mitigate CO2 emissions. Nickel (Ni)-based catalysts have been identified as a potential candidate for CO2 activation and conversion. However, in the CO2RR, the size effect of the Ni-based electrocatalysts has not been well explored. Herein, the single Ni atom and the Ni4 cluster doped nitrogen-doped carbon nanotube (Ni@CNT and Ni4@CNT), and the Ni (110) facet were designed to explore the size effect in the CO2RR by using density functional theory (DFT) calculations. The results show that carbon monoxide (CO) is produced on the Ni@CNT with a free energy barrier of 0.51 eV. The reduction product of CO2 on the Ni4@CNT and Ni(110) facet is methane (CH4) in both cases, via different reaction pathways, and the Ni(110) facet is a more efficient electrocatalyst with a low overpotential of 0.27 V when compared to Ni4@CNT (0.50 V). The rate-determining step (RDS) is the formation of *CHO on the Ni4@CNT (The "*" represents the catalytic surface), while the *COH formation is the RDS on the Ni(110) facet. Meanwhile, the Ni(110) facet also has the highest selectivity of CH4 among the three catalysts. The CO2 reduction product changes from CO to CH4 with the increasing size of the Ni-based catalysts. These results demonstrate that the catalytic activity and selectivity of CO2RR highly depend on the size of the Ni-based catalysts.

A two-photon fluorescence probe with endoplasmic reticulum targeting ability for turn-on sensing photosensitized singlet oxygen in living cells and brain tissues.

Endoplasmic reticulum (ER) is an indispensable organelle responsible for protein synthesis, transportation, and maintenance of Ca2+ homeostasis in eukaryotic cells. Recent studies highlighted that ER-targeted photosensitizers with high yield of singlet oxygen (1O2) are effective in selectively disrupting ER function and are promising candidates for anticancer therapy. Unfortunately, no ER targetable fluorescent probes for determining 1O2 photosensitized in this photodynamic therapy process is available. In this work, we synthesized an ER-targetable, two-photon fluorescence probe, ER-1O2, for fluorescence turn-on sensing of 1O2. ER-1O2 demonstrated high sensitivity to 1O2 sensing with a wide detection range (0-2.75 µM) and a low detection limit (0.11 µM). ER-1O2 also displayed excellent selectivity toward 1O2 out of other ROS and metal ions. Notably, ER-1O2 exhibited low cytotoxicity but with specific ER targetable capability. On account of these advantageous features, fluctuations of 1O2 in living cells and brain tissues were effectively visualized by ER-1O2.

Constructing highly porous carbon materials from porous organic polymers for superior CO2 adsorption and separation.

The increase in atmospheric carbon dioxide (CO2) concentration has led to numerous problems related to our living environment, seeking an efficient carbon capture and storage (CCS) strategy associated with low energy consumption and expenditures is highly desirable. Here, we demonstrate a facile approach to synthesize a series of highly porous carbon materials derived from porous organic polymers synthesized from three low-cost isomers of triphenyl using chemical activation with KOH at different temperatures. Compared with the precursor porous organic polymers, the porosity of the prepared porous carbon materials is significantly enhanced with surface areas as high as 3367 m2 g-1 and pore volumes up to 1.224 cm3 g-1. Notably, such porous carbon materials deliver an exceptionally high CO2 adsorption capacity of 7.78 mmol g-1 at 273 K and 1 bar, a value that is superior to most of the previously reported adsorbents. In addition, these porous organic polymers and derived porous carbon materials exhibit high CO2/N2 selectivity at ambient conditions. Therefore, the facile construction of highly porous carbon materials from porous organic polymers may offer an efficient strategy for CO2 adsorption and separation and further mitigates greenhouse effect.

Metal-polyphenol cross-linked titanium carbide membranes with stable interlayer spacing for efficient wastewater treatment.

Membranes based on transition metal carbides/nitrides (MXenes) have significant water treatment potential because of their unique molecular sieving properties and excellent permeation performance. However, hydrophilic MXenes swell upon water immersion, and improving their stability remains challenging. In this study, a Fe3+-tannic acid (TA) complex was used as a cross-linker and surface modifier to prepare high-performance titanium carbide (Ti3C2Tx) MXene laminar membranes. Fe3+-TA formation on the nanosheets increased the interlayer spacing and stabilized the laminar structure. The membrane with the highest performance among the as-prepared membranes exhibited a high water permeance of 90.5 L/m-2(-|-)h-1 bar-1 (which is twice that of the pristine Ti3C2Tx membrane) and good separation efficiency (methyl blue rejection rate: ∼99.8 %; Na2SO4 rejection rate: ∼5.0 %). Furthermore, the Fe3+-TA complex enhanced the membrane hydrophilicity, resulting in excellent antifouling properties. This study provides an environmentally friendly and facile method for fabricating two-dimensional loose nanofiltration membranes for textile wastewater treatment.

Transition metal oxide-based membranes for oxygen separation.

Tonnage oxygen production is still mostly based on the traditional technology of cryogenic distillation, a century-old, capital- and energy-intensive method. It is critical to create a novel low-cost, energy-efficient approach that can meet the growing demand for oxygen in industry from the clean environmental or energy standpoint. Ruddlesden-Popper (RP) perovskite like oxides -based ionic transport membranes for the oxygen transport have recently been developed as a possible replacement for the traditional cryogenic approach. In this work, we detailly reviewed the progress of RP perovskite oxides based membranes for oxygen transport from separation mechanism, material types, synthesis methods to the final separation performance. This work advances the development of RP perovskite membranes for oxygen transport.

Endoplasmic reticulum-targeted polymer dots encapsulated with ultrasonic synthesized near-infrared carbon nanodots and their application for in vivo monitoring of Cu2.

Endoplasmic reticulum (ER) is the largest organelle in eukaryotic cells and plays a variety of functions in living cells include protein folding, calcium homeostasis, and lipid biosynthesis. Normal function of ER is crucial for cell survival, while disequilibrium of ER can cause misfolding of proteins and ER stress, leading to many serious diseases. It has been documented that ER stress is closely related to the metabolism of Cu2+, as ER is the main intracellular accumulation space of Cu2+ and toxic reactive oxygen species can be generated by Cu2+ via Fenton and Haber-Weiss reactions. In this context, developing a powerful tool capable of selective and sensitive monitoring of Cu2+ in ER and investigating its role in physiological and pathological processes is of great importance. Herein, we report the first ER targeted near infrared (NIR) nanosensor, polymer dots encapsulated with NIR hydrophobic carbon nanodots, for detecting Cu2+ in biosystems. This nanosensor with stable fluorescence showed a fast response toward Cu2+ (120 s) and can be used for the quantification of Cu2+ in a linear range covering from 0.25 to 9.0 µM with a detection limit of 13 nM. In addition, the fluorescence variations of the nanosensor are remarkably specific to Cu2+ in comparison with the other metal ions and amino acids. Moreover, the developed nanosensor exhibited low cytotoxicity, good biocompatibility, and ER targeting ability. Because of these excellent spectroscopic features, the nanosensor was successfully utilized for visualizing Cu2+ fluctuations at the living cell, zebrafish and mouse levels, which further proved its potential application in biological systems.