Domino electroreduction of CO2 to methanol on a molecular catalyst.

Electrochemical carbon dioxide (CO2) reduction can in principle convert carbon emissions to fuels and value-added chemicals, such as hydrocarbons and alcohols, using renewable energy, but the efficiency of the process is limited by its sluggish kinetics1,2. Molecular catalysts have well defined active sites and accurately tailorable structures that allow mechanism-based performance optimization, and transition-metal complexes have been extensively explored in this regard. However, these catalysts generally lack the ability to promote CO2 reduction beyond the two-electron process to generate more valuable products1,3. Here we show that when immobilized on carbon nanotubes, cobalt phthalocyanine-used previously to reduce CO2 to primarily CO-catalyses the six-electron reduction of CO2 to methanol with appreciable activity and selectivity. We find that the conversion, which proceeds via a distinct domino process with CO as an intermediate, generates methanol with a Faradaic efficiency higher than 40 per cent and a partial current density greater than 10 milliamperes per square centimetre at -0.94 volts with respect to the reversible hydrogen electrode in a near-neutral electrolyte. The catalytic activity decreases over time owing to the detrimental reduction of the phthalocyanine ligand, which can be suppressed by appending electron-donating amino substituents to the phthalocyanine ring. The improved molecule-based electrocatalyst converts CO2 to methanol with considerable activity and selectivity and with stable performance over at least 12 hours.

An ultra-small organic dye nanocluster for enhancing NIR-II imaging-guided surgery outcomes.

PURPOSE: The accuracy of surgery for patients with solid tumors can be greatly improved through fluorescence-guided surgery (FGS). However, existing FGS technologies have limitations due to their low penetration depth and sensitivity/selectivity, which are particularly prevalent in the relatively short imaging window (< 900 nm). A solution to these issues is near-infrared-II (NIR-II) FGS, which benefits from low autofluorescence and scattering under the long imaging window (> 900 nm). However, the inherent self-assembly of organic dyes has led to high accumulation in main organs, resulting in significant background signals and potential long-term toxicity. METHODS: We rationalize the donor structure of donor-acceptor-donor-based dyes to control the self-assembly process to form an ultra-small dye nanocluster, thus facilitating renal excretion and minimizing background signals. RESULTS: Our dye nanocluster can not only show clear vessel imaging, tumor and tumor sentinel lymph nodes definition, but also achieve high-performance NIR-II imaging-guided surgery of tumor-positive sentinel lymph nodes. CONCLUSION: In summary, our study demonstrates that the dye nanocluster-based NIR-II FGS has substantially improved outcomes for radical lymphadenectomy.

NIR-II Imaging and Sandwiched Plasmonic Biosensor for Ultrasensitive Intraoperative Definition of Tumor-Invaded Lymph Nodes.

Radical lymphadenectomy remains the cornerstone of preventing tumor metastasis through the lymphatic system. Current surgical resection of lymph nodes (LNs) based on fluorescence-guided surgery (FGS) suffers from low sensitivity/selectivity with only qualitative information, hampering accurate intraoperative decision-making. Herein, we develop a modularized theranostic system including NIR-II FGS and a sandwiched plasmonic chip (SPC). Intraoperative NIR-II FGS and detection of tumor-positive lymph nodes were performed on the gastric tumor to determine the feasibility of the modularized theranostic system in defining LN metastasis. Under the NIR-II imaging window, the orthotopic tumor and sentinel lymph nodes (SLNs) were successfully excised without ambient light interference in the operating room. Importantly, the SPC biosensor achieved 100% sensitivity and 100% specificity for tumor markers and realized rapid and high-throughput intraoperative SLN detection. We propose the synergetic design of combining the NIR-II FGS and suitable biosensor will substantially improve the efficiency of cancer diagnosis and therapy follow-up.

Stabilizing *CO2 Intermediates at the Acidic Interface using Molecularly Dispersed Cobalt Phthalocyanine as Catalysts for CO2 Reduction.

CO2 electroreduction (CO2 R) operating in acidic media circumvents the problems of carbonate formation and CO2 crossover in neutral/alkaline electrolyzers. Alkali cations have been universally recognized as indispensable components for acidic CO2 R, while they cause the inevitable issue of salt precipitation. It is therefore desirable to realize alkali-cation-free CO2 R in pure acid. However, without alkali cations, stabilizing *CO2 intermediates by catalyst itself at the acidic interface poses as a challenge. Herein, we first demonstrate that a carbon nanotube-supported molecularly dispersed cobalt phthalocyanine (CoPc@CNT) catalyst provides the Co single-atom active site with energetically localized d states to strengthen the adsorbate-surface interactions, which stabilizes *CO2 intermediates at the acidic interface (pH=1). As a result, we realize CO2 conversion to CO in pure acid with a faradaic efficiency of 60 % at pH=2 in flow cell. Furthermore, CO2 is successfully converted in cation exchanged membrane-based electrode assembly with a faradaic efficiency of 73 %. For CoPc@CNT, acidic conditions also promote the intrinsic activity of CO2 R compared to alkaline conditions, since the potential-limiting step, *CO2 to *COOH, is pH-dependent. This work provides a new understanding for the stabilization of reaction intermediates and facilitates the designs of catalysts and devices for acidic CO2 R.

Unlocking the NIR-II AIEgen for High Brightness through Intramolecular Electrostatic Locking.

Fluorescent imaging and biosensing in the near-infrared-II (NIR-II) window holds great promise for non-invasive, radiation-free, and rapid-response clinical diagnosis. However, it's still challenging to develop bright NIR-II fluorophores. In this study, we report a new strategy to enhance the brightness of NIR-II aggregation-induced emission (AIE) fluorophores through intramolecular electrostatic locking. By introducing sulfur atoms into the side chains of the thiophene bridge in TSEH molecule, the molecular motion of the conjugated backbone can be locked through intramolecular interactions between the sulfur and nitrogen atoms. This leads to enhanced NIR-II fluorescent emission of TSEH in both solution and aggregation states. Notably, the encapsulated nanoparticles (NPs) of TSEH show enhanced brightness, which is 2.6-fold higher than TEH NPs with alkyl side chains. The in vivo experiments reveal the feasibility of TSEH NPs in vascular and tumor imaging with a high signal-to-background ratio and precise resection for tiny tumors. In addition, polystyrene nanospheres encapsulated with TSEH are utilized for antigen detection in lateral flow assays, showing a signal-to-noise ratio 1.9-fold higher than the TEH counterpart in detecting low-concentration antigens. This work highlights the potential for developing bright NIR-II fluorophores through intramolecular electrostatic locking and their potential applications in clinical diagnosis and biomedical research.

Low-Dose NIR-II Preclinical Bioimaging Using Liposome-Encapsulated Cyanine Dyes.

Fluorescence imaging in the second near-infrared window (NIR-II, 1000-1700 nm) provides a powerful tool for in vivo structural and functional imaging in deep tissue. However, the lack of biocompatible contrast agents with bright NIR-II emission has hindered its application in fundamental research and clinical trials. Herein, a liposome encapsulation strategy for generating ultrabright liposome-cyanine dyes by restricting dyes in the hydrophobic pockets of lipids and inhibiting the aggregation, as corroborated by computational modeling, is reported. Compared with free indocyanine green (ICG, an US Food and Drug Administration-approved cyanine dye), liposome-encapsulated ICG (S-Lipo-ICG) shows a 38.7-fold increase in NIR-II brightness and enables cerebrovascular imaging at only one-tenth dose over a long period (30 min). By adjusting the excitation wavelength, two liposome-encapsulated cyanine dyes (S-Lipo-ICG and S-Lipo-FD1080) enable NIR-II dual-color imaging. Moreover, small tumor nodules (2-5 mm) can be successfully distinguished and removed with S-Lipo-ICG image-guided tumor surgery in rabbit models. This liposome encapsulation maintains the metabolic pathway of ICG, promising for clinical implementation.

Dispersed Nickel Phthalocyanine Molecules on Carbon Nanotubes as Cathode Catalysts for Li-CO2 Batteries.

The Li-CO2 battery has great potential for both CO2 utilization and energy storage, but its practical application is limited by low energy efficiency and short cycle life. Efficient cathode catalysts are needed to address this issue. Herein, this work reports on molecularly dispersed electrocatalysts (MDEs) of nickel phthalocyanine (NiPc) anchored on carbon nanotubes (CNTs) as the cathode catalyst for Li-CO2 batteries. The dispersed NiPc molecules efficiently catalyze CO2 reduction, while the conductive and porous CNTs networks facilitate CO2 evolution reaction, leading to enhanced discharging and charging performance compared to the NiPc and CNTs mixture. Octa-cyano substitution on NiPc (NiPc-CN) further enhances the interaction between the molecule and CNTs, resulting in better cycling stability. The Li-CO2 battery with the NiPc-CN MDE cathode shows a high discharge voltage of 2.72 V and a small discharging-charging potential gap of 1.4 V, and can work stably for over 120 cycles. The reversibility of the cathode is confirmed by experimental characterizations. This work lays a foundation for the development of molecular catalysts for Li-CO2 battery cathodes.

Light-sheet microscopy in the near-infrared II window.

Non-invasive deep-tissue three-dimensional optical imaging of live mammals with high spatiotemporal resolution is challenging owing to light scattering. We developed near-infrared II (1,000-1,700 nm) light-sheet microscopy with excitation and emission of up to approximately 1,320 nm and 1,700 nm, respectively, for optical sectioning at a penetration depth of approximately 750 µm through live tissues without invasive surgery and at a depth of approximately 2 mm in glycerol-cleared brain tissues. Near-infrared II light-sheet microscopy in normal and oblique configurations enabled in vivo imaging of live mice through intact tissue, revealing abnormal blood flow and T-cell motion in tumor microcirculation and mapping out programmed-death ligand 1 and programmed cell death protein 1 in tumors with cellular resolution. Three-dimensional imaging through the intact mouse head resolved vascular channels between the skull and brain cortex, and allowed monitoring of recruitment of macrophages and microglia to the traumatic brain injury site.

Heterogeneous Molecular Catalysts of Metal Phthalocyanines for Electrochemical CO2 Reduction Reactions.

ConspectusMolecular catalysts, often deployed in homogeneous conditions, are favorable systems for structure-reactivity correlation studies of electrochemical reactions because of their well-defined active site structures and ease of mechanistic investigation. In pursuit of selective and active electrocatalysts for the CO2 reduction reactions which are promising for converting carbon emissions to useful fuels and chemical products, it is desirable to support molecular catalysts on substrates because heterogeneous catalysts can afford the high current density and operational convenience that practical electrolyzers require. Herein, we share our understanding in the development of heterogenized metal phthalocyanine catalysts for the electrochemical reduction of CO2. From the optimization of preparation methods and material structures for the electrocatalytic activity toward CO2 reduction to CO, we find that molecular-level dispersion of the active material and high electrical conductivity of the support are among the most important factors controlling the activity. The molecular nature of the active site enables mechanism-based optimization. We demonstrate how electron-withdrawing and -donating ligand substituents can be utilized to modify the redox property of the molecule and improve its catalytic activity and stability. Adjusting these factors further allows us to achieve electrochemical reduction of CO2 to methanol with appreciable activity, which has not been attainable by conventional molecular catalysts. The six-electron reduction process goes through CO as the key intermediate. Rapid and continuous electron delivery to the active site favors further reduction of CO to methanol. We also point out that, in homogeneous electrocatalysis where the catalyst molecules are dissolved in the electrolyte solution, even if the molecular structure remains intact, the actual catalysis may be dominated by molecules permanently adsorbed on the electrode surface and is thus heterogeneous in nature. This account uses our research on CO2 electroreduction reactions catalyzed by metal phthalocyanine molecules to illustrate our understanding about heterogeneous molecular electrocatalysis, which is also applicable to other electrochemical systems.

Multiplexed evaluation of immunity against SARS-CoV-2 variants using surface enhanced fluorescence from a nanostructured plasmonic chip.

Generated by the immune system post-infection or through vaccination, the effectiveness of antibodies against emerging SARS-CoV-2 variants is crucial for protecting individuals from the COVID-19 pandemic. Herein, a platform for the multiplexed evaluation of SARS-CoV-2 neutralizing antibodies against various variants was designed on the basis of near-infrared (NIR) surface enhanced fluorescence by nano-plasmonic gold chip (pGOLD). Antibody level across variants (Wild-type, Alpha, Beta, Delta, Omicron) was confirmed by the sera from recovered-individuals who were unvaccinated and had infected with Wild-type, Delta, Omicron variants. However, the neutralizing activity against Omicron variant was markedly decreased for individuals infected by Wild-type (~ 5.6-fold) and Delta variant (~ 19.1-fold). To the opposite, neutralizing antibody from individuals recovered from Omicron variant infection showed weak binding strength against non-Omicron variants. Antibody evolution over time was studied with individuals 196-530 days post Wild-type infection. Decreasing IgG antibody titer accompanied by increasing IgG binding avidity with elongated post-infection period were observed for the sera from Wild-type recovered-individuals with different post-infection times, suggesting that after the primary infection, a great number of antibodies were generated and then gradually decreased, while the antibody matured over time. By comparing the IgG level of individuals vaccinated for 27-51 days with individual post-infection, we found that ca. 1 month after two doses of vaccination, the antibody level was comparable to that of 500 days post-infection, and vaccination could enhance IgG avidity more efficiently. This work demonstrated a platform for the multiplexed, high-throughput and rapid screening of acquired immunity against SARS-CoV-2 variants, providing a new approach for the analysis of vaccine effectiveness, immunity against emerging variants, and related serological study.

Highly active oxygen evolution integrated with efficient CO2 to CO electroreduction.

Electrochemical reduction of CO2 to useful chemicals has been actively pursued for closing the carbon cycle and preventing further deterioration of the environment/climate. Since CO2 reduction reaction (CO2RR) at a cathode is always paired with the oxygen evolution reaction (OER) at an anode, the overall efficiency of electrical energy to chemical fuel conversion must consider the large energy barrier and sluggish kinetics of OER, especially in widely used electrolytes, such as the pH-neutral CO2-saturated 0.5 M KHCO3 OER in such electrolytes mostly relies on noble metal (Ir- and Ru-based) electrocatalysts in the anode. Here, we discover that by anodizing a metallic Ni-Fe composite foam under a harsh condition (in a low-concentration 0.1 M KHCO3 solution at 85 °C under a high-current ∼250 mA/cm2), OER on the NiFe foam is accompanied by anodic etching, and the surface layer evolves into a nickel-iron hydroxide carbonate (NiFe-HC) material composed of porous, poorly crystalline flakes of flower-like NiFe layer-double hydroxide (LDH) intercalated with carbonate anions. The resulting NiFe-HC electrode in CO2-saturated 0.5 M KHCO3 exhibited OER activity superior to IrO2, with an overpotential of 450 and 590 mV to reach 10 and 250 mA/cm2, respectively, and high stability for >120 h without decay. We paired NiFe-HC with a CO2RR catalyst of cobalt phthalocyanine/carbon nanotube (CoPc/CNT) in a CO2 electrolyzer, achieving selective cathodic conversion of CO2 to CO with >97% Faradaic efficiency and simultaneous anodic water oxidation to O2 The device showed a low cell voltage of 2.13 V and high electricity-to-chemical fuel efficiency of 59% at a current density of 10 mA/cm2.

Accessing Organonitrogen Compounds via C-N Coupling in Electrocatalytic CO2 Reduction.

Given the limited product variety of electrocatalytic CO2 reduction reactions solely from CO2 and H2O as the reactants, it is desirable to expand the product scope by introducing additional reactants that provide elemental diversity. The integration of inorganic heteroatom-containing reactants into electrocatalytic CO2 reduction could, in principle, enable the sustainable synthesis of valuable products, such as organonitrogen compounds, which have widespread applications but typically rely on NH3 derived from the energy-intensive and fossil-fuel-dependent Haber-Bosch process for their industrial-scale production. In this Perspective, research progress toward building C-N bonds in N-integrated electrocatalytic CO2 reduction is highlighted, and the electrosyntheses of urea, acetamides, and amines are examined from the standpoints of reactivity, catalyst structure, and, most fundamentally, mechanism. Mechanistic discussions of C-N coupling in these advances are emphasized and critically evaluated, with the aim of directing future investigations on improving the product yield and broadening the product scope of N-integrated electrocatalytic CO2 reduction.

Selective and High Current CO2 Electro-Reduction to Multicarbon Products in Near-Neutral KCl Electrolytes.

Reducing CO2 to value-added multicarbon (C2+) fuels and chemicals using renewable energy is a viable way to circumvent CO2 buildup in the atmosphere and facilitate closing the carbon cycle. To date it remains a challenge to achieve high product selectivity and long-term stability of electrocatalytic carbon dioxide reduction reaction (CO2RR) especially at practically relevant high current levels >100 mA cm-2. Here, we report a simple electrodeposited Cu electrocatalyst on a hydrophobic porous gas-diffusion layer (GDL) electrode affording stable and selective CO2RR to C2+ products in near-neutral KCl electrolytes. By directing the CO2 stream to fully submerged hydrophobic GDLs in a H-cell, high C2+ partial current densities near 100 mA cm-2 were achieved. In a flow-cell setup, the Cu/GDL cathode in 2 M KCl afforded stable CO2RR superior to that in widely used KOH electrolytes. We found that Cu etching/corrosion associated with trace oxygen played a role in the catalyst instability in alkaline media under cathodic CO2RR conditions, a problem largely suppressed in near-neutral electrolyte. A two-electrode CO2 electrolyzer was constructed with a Cu/GDL cathode in KCl catholyte and an anode comprised of nickel-iron hydroxide on nickel foam (NiFe/NF) in a KOH anolyte separated by Nafion membrane. By periodically adding HCl to the KCl catholyte to compensate the increasing pH and remove accumulated (bi)carbonates, we observed little decay over ∼30 h in flow-cell CO2RR activity and selectivity at 150 mA cm-2 with a high Faradaic efficiency (FE) of ∼75% and energy efficiency of 40% for C2+ products.

Establishing Multifunctional Interface Layer of Perovskite Ligand Modified Lead Sulfide Quantum Dots for Improving the Performance and Stability of Perovskite Solar Cells.

While organic-inorganic halide perovskite solar cells (PSCs) show great potential for realizing low-cost and easily fabricated photovoltaics, the unexpected defects and long-term stability against moisture are the main issues hindering their practical applications. Herein, a strategy is demonstrated to address the main issues by introducing lead sulfide quantum dots (QDs) on the perovskite surface as the multifunctional interface layer on perovskite film through establishing perovskite as the ligand on PbS QDs. Meanwhile, the multifunctions are featured in three aspects including the strong interactions of PbS QDs with perovskites particularly at the grain boundaries favoring good QDs coverage on perovskites for ultimate smooth morphology; an inhibition of iodide ions mobilization by the strong interaction between iodide and the incorporated QDs; and the reduction of the dangling bonds of Pb2+ by the sulfur atoms of PbS QDs. Finally, the device performances are highly improved due to the reduced defects and non-radiative recombination. The results show that both open-circuit voltage and fill factor are significantly improved to the high values of 1.13 V and 80%, respectively in CH3 NH3 PbI3 -based PSCs, offering a high efficiency of 20.64%. The QDs incorporation also enhances PSCs' stability benefitting from the induced hydrophobic surface and suppressed iodide mobilization.

Proteoliposome-based full-length ZnT8 self-antigen for type 1 diabetes diagnosis on a plasmonic platform.

Identified as a major biomarker for type 1 diabetes (T1D) diagnosis, zinc transporter 8 autoantibody (ZnT8A) has shown promise for staging disease risk and disease diagnosis. However, existing assays for ZnT8 autoantibody (ZnT8A) are limited to detection by soluble domains of ZnT8, owing to difficulties in maintaining proper folding of a full-length ZnT8 protein outside its native membrane environment. Through a combined bioengineering and nanotechnology approach, we have developed a proteoliposome-based full-length ZnT8 self-antigen (full-length ZnT8 proteoliposomes; PLR-ZnT8) for efficient detection of ZnT8A on a plasmonic gold chip (pGOLD). The protective lipid matrix of proteoliposomes improved the proper folding and structural stability of full-length ZnT8, helping PLR-ZnT8 immobilized on pGOLD (PLR-ZnT8/pGOLD) achieve high-affinity capture of ZnT8A from T1D sera. Our PLR-ZnT8/pGOLD exhibited efficient ZnT8A detection for T1D diagnosis with ∼76% sensitivity and ∼97% specificity (n = 307), superior to assays based on detergent-solubilized full-length ZnT8 and the C-terminal domain of ZnT8. Multiplexed assays using pGOLD were also developed for simultaneous detection of ZnT8A, islet antigen 2 autoantibody, and glutamic acid decarboxylase autoantibody for diagnosing T1D.

Molecular imaging of biological systems with a clickable dye in the broad 800- to 1,700-nm near-infrared window.

Fluorescence imaging multiplicity of biological systems is an area of intense focus, currently limited to fluorescence channels in the visible and first near-infrared (NIR-I; ∼700-900 nm) spectral regions. The development of conjugatable fluorophores with longer wavelength emission is highly desired to afford more targeting channels, reduce background autofluorescence, and achieve deeper tissue imaging depths. We have developed NIR-II (1,000-1,700 nm) molecular imaging agents with a bright NIR-II fluorophore through high-efficiency click chemistry to specific molecular antibodies. Relying on buoyant density differences during density gradient ultracentrifugation separations, highly pure NIR-II fluorophore-antibody conjugates emitting ∼1,100 nm were obtained for use as molecular-specific NIR-II probes. This facilitated 3D staining of ∼170-µm histological brain tissues sections on a home-built confocal microscope, demonstrating multicolor molecular imaging across both the NIR-I and NIR-II windows (800-1,700 nm).

Organic Spherical Nucleic Acids for the Transport of a NIR-II-Emitting Dye Across the Blood-Brain Barrier.

DNA nanotechnology plays an increasingly important role in the biomedical field; however, its application in the design of organic nanomaterials is underexplored. Herein, we report the use of DNA nanotechnology to transport a NIR-II-emitting nanofluorophore across the blood-brain barrier (BBB), facilitating non-invasive imaging of brain tumors. Specifically, the DNA block copolymer, PS-b-DNA, is synthesized through a solid-phase click reaction. We demonstrate that its self-assembled structure shows exceptional cluster effects, among which BBB-crossing is the most notable. Therefore, PS-b-DNA is utilized as an amphiphilic matrix to fabricate a NIR-II nanofluorephore, which is applied in in vivo bioimaging. Accordingly, the NIR-II fluorescence signal of the DNA-based nanofluorophore localized at a glioblastoma is 3.8-fold higher than the NIR-II fluorescence signal of the PEG-based counterpart. The notably increased imaging resolution will significantly benefit the further diagnosis and therapy of brain tumors.

Donor Engineering for NIR-II Molecular Fluorophores with Enhanced Fluorescent Performance.

Organic fluorophores have been widely used for biological imaging in the visible and the first near-infrared windows. However, their application in the second near-infrared window (NIR-II, 1000-1700 nm) is still limited mainly due to low fluorescence quantum yields (QYs). Here, we explore molecular engineering on the donor unit to develop high performance NIR-II fluorophores. The fluorophores are constructed by a shielding unit-donor(s)-acceptor-donor(s)-shielding unit structure. Thiophene is introduced as the second donor connected to the shielding unit, which can increase the conjugation length and red-shift the fluorescence emission. Alkyl thiophene is employed as the first donor connected to the acceptor unit. The bulky and hydrophobic alkyl thiophene donor affords larger distortion of the conjugated backbone and fewer interactions with water molecules compared to other donor units studied before. The molecular fluorophore IR-FTAP with octyl thiophene as the first donor and thiophene as the second donor exhibits fluorescence emission peaked at 1048 nm with a QY of 5.3% in aqueous solutions, one of the highest for molecular NIR-II fluorophore reported so far. Superior temporal and spatial resolutions have been demonstrated with IR-FTAP fluorophore for NIR-II imaging of the blood vessels of a mouse hindlimb.

Developing a Bright NIR-II Fluorophore with Fast Renal Excretion and Its Application in Molecular Imaging of Immune Checkpoint PD-L1.

Fluorescence imaging in the second near-infrared (NIR-II) window holds impressive advantages of enhanced penetration depth and improved signal-to-noise ratio. Bright NIR-II fluorophores with renal excretion ability and low tissue accumulation are favorable for in vivo molecular imaging applications as they can render the target-mediated molecular imaging process easily distinguishable. Here, a probe (anti-PD-L1-BGP6) comprising a fluorophore (IR-BGP6) covalently bonded to the programmed cell death ligand-1 monoclonal antibody (PD-L1 mAb) for molecular imaging of immune checkpoint PD-L1 (a targeting site upregulated in various tumors for cancer imaging) in the NIR-II window is reported. Through molecular optimization, the bright NIR-II fluorophore IR-BGP6 with fast renal excretion (≈91% excretion in general through urine within the first 10 h postinjection) is developed. The conjugate anti-PD-L1-BGP6 succeeds in profiling PD-L1 expression and realizes efficient noninvasive molecular imaging in vivo, achieving a tumor to normal tissue (T/NT) signal ratio as high as ≈9.5. Compared with the NIR-II fluorophore with high nonspecific tissue accumulation, IR-BGP6 derived PD-L1 imaging significantly enhances the molecular imaging performance, serving as a strong tool for potentially studying underlying mechanism of immunotherapy. The work provides rationales to design renal-excreted NIR-II fluorophores and illustrate their advantages for in vivo molecular imaging.

Self-Cleaning Catalyst Electrodes for Stabilized CO2 Reduction to Hydrocarbons.

A surface-restructuring strategy is presented that involves self-cleaning Cu catalyst electrodes with unprecedented catalytic stability toward CO2 reduction. Under the working conditions, the Pd atoms pre-deposited on Cu surface induce continuous morphological and compositional restructuring of the Cu surface, which constantly refreshes the catalyst surface and thus maintains the catalytic properties for CO2 reduction to hydrocarbons. The Pd-decorated Cu electrode can catalyze CO2 reduction with relatively stable selectivity and current density for up to 16 h, which is one of the best catalytic durability performances among all Cu electrocatalysts for effective CO2 conversion to hydrocarbons. The generality of this approach of utilizing foreign metal atoms to induce surface restructuring toward stabilizing Cu catalyst electrodes against deactivation by carbonaceous species accumulation in CO2 reduction is further demonstrated by replacing Pd with Rh.