Freezing process influences cake appearance of a lyophilized amorphous protein formulation with low solid content and high fill configuration.

Low solid content and high fill drug product configuration pose special challenges for achieving elegant cake appearance after lyophilization. In this study, such a configuration for a protein formulation required lyophilization within a narrow primary drying operating space to obtain elegant cakes. Freezing process optimization was explored as a solution. A Design of Experiment (DoE) approach was used to evaluate the effect of shelf cooling rate, annealing temperature, and their interaction on cake appearance. The slope of product resistance (Rp) vs. dried layer thickness (Ldry) was used as the quantitative response because elegant cake appearance correlated with a lower initial Rp and positive slope. As the Rp vs. Ldry slope can be experimentally established within the first 1/6th of the total primary drying duration, partial lyophilization runs were executed, allowing for rapid screening. The DoE model revealed that a slow cooling rate (≤0.3 °C/min) and high annealing temperature (≥-10 °C) resulted in a better cake appearance. Furthermore, X-ray micro-computed tomography showed that elegant cakes exhibited uniform porous structure and larger pores, while inelegant cakes showed dense top layers with smaller pores. With the optimized freezing process, the primary drying operating space was broadened with improved cake appearance and batch homogeneity.

A pH-Activatable Copper-Biomineralized Proenzyme for Synergistic Chemodynamic/Chemo-Immunotherapy against Aggressive Cancers.

Artificial enzymes have demonstrated therapeutic benefits against diverse malignant tumors, yet their antitumor potencies are still severely compromised by non-selective catalysis, low atomic-utilization efficiency, and undesired off-target toxicity. Herein, it is reported that peroxidase-like biomineralized copper (II) carbonate hydroxide nanocrystals inside single albumin nanocages (CuCH-NCs) act as a pH-activatable proenzyme to achieve tumor-selective and synergistic chemodynamic/chemo-immunotherapy against aggressive triple-negative breast cancers (TNBCs). These CuCH-NCs show pH-sensitive Cu2+ release, which spontaneously undergoes glutathione (GSH)-mediated reduction into Cu+ species for catalyzing the evolution of H2 O2 into hydroxyl radicals (·OH) in a single-atom-like manner to cause chemodynamic cell injury, and simultaneously activates non-toxic disulfiram to cytotoxic complex for yielding selective chemotherapeutic damage via blocking cell proliferation and amplifying cell apoptosis. CuCH-NCs exhibit considerable tumor-targeting capacity with deep penetration depth, thus affording preferable efficacy against orthotopic breast tumors through synergistic chemodynamic/chemotherapy, together with good in vivo safety. Moreover, CuCH-NCs arouse distinct immunogenic cell death effect and upregulate PD-L1 expression upon disulfiram combination, and thus synergize with anti-PD-L1 antibody to activate adaptive and innate immunities, together with relieving immunosuppression, finally yielding potent antitumor efficacy against both primary and metastatic TNBCs. These results provide insights into smart and high-performance proenzymes for synergistic therapy against aggressive cancers.

Holographically Activatable Nanoprobe via Glutathione/Albumin-Mediated Exponential Signal Amplification for High-Contrast Tumor Imaging.

Glutathione (GSH)-activatable probes hold great promise for in vivo cancer imaging, but are restricted by their dependence on non-selective intracellular GSH enrichment and uncontrollable background noise. Here, a holographically activatable nanoprobe caging manganese tetraoxide is shown for tumor-selective contrast enhancement in magnetic resonance imaging (MRI) through cooperative GSH/albumin-mediated cascade signal amplification in tumors and rapid elimination in normal tissues. Once targeting tumors, the endocytosed nanoprobe effectively senses the lysosomal microenvironment to undergo instantaneous decomposition into Mn2+ with threshold GSH concentration of ≈ 0.12 mm for brightening MRI signals, thus achieving high contrast tumor imaging and flexible monitoring of GSH-relevant cisplatin resistance during chemotherapy. Upon efficient up-regulation of extracellular GSH in tumor via exogenous injection, the relaxivity-silent interstitial nanoprobe remarkably evolves into Mn2+ that are further captured/retained and re-activated into ultrahigh-relaxivity-capable complex by stromal albumin in the tumor, and simultaneously allows the renal clearance of off-targeted nanoprobe in the form of Mn2+ via lymphatic vessels for suppressing background noise to distinguish tiny liver metastasis. These findings demonstrate the concept of holographic tumor activation via both tumor GSH/albumin-mediated cascade signal amplification and simultaneous background suppression for precise tumor malignancy detection, surveillance, and surgical guidance.

Synergistic Phototherapy-Molecular Targeted Therapy Combined with Tumor Exosome Nanoparticles for Oral Squamous Cell Carcinoma Treatment.

Oral squamous cell carcinoma (OSCC) contributes to more than 90% of all oral malignancies, yet the performance of traditional treatments is impeded by limited therapeutic effects and substantial side effects. In this work, we report a combinational treatment strategy based on tumor exosome-based nanoparticles co-formulating a photosensitizer (Indocyanine green) and a tyrosine kinase inhibitor (Gefitinib) (IG@EXOs) for boosting antitumor efficiency against OSCC through synergistic phototherapy-molecular targeted therapy. The IG@EXOs generate distinct photothermal/photodynamic effects through enhanced photothermal conversion efficiency and ROS generation, respectively. In vivo, the IG@EXOs efficiently accumulate in the tumor and penetrate deeply to the center of the tumor due to passive and homologous targeting. The phototherapy effects of IG@EXOs not only directly induce potent cancer cell damage but also promote the release and cytoplasmic translocation of Gefitinib for achieving significant inhibition of cell proliferation and tumor angiogenesis, eventually resulting in efficient tumor ablation and lymphatic metastasis inhibition through the synergistic phototherapy-molecular targeted therapy. We envision that the encouraging performances of IG@EXOs against cancer pave a new avenue for their future application in clinical OSCC treatment.

Organic-Inorganic Hybrid Cuprous Halide Scintillators for Flexible X-ray Imaging.

Recently, organic-inorganic hybrid scintillators have received more and more attention because of their merits of easy preparation, good stability, and nontoxicity. Considering the high cost of traditional inorganic scintillators, here we describe experimental investigations of a low-cost zero-dimensional scintillator comprising organic-inorganic hybrid cuprous halide and its capabilities for sensitive X-ray detection and flexible X-ray imaging. This scintillator is synthesized using a facile antisolvent diffusion method with large scalability (50 g). The crystal structure shows an unreported plane rhombus cuprous halide core, which also demonstrates outstanding photoluminescence with a high quantum yield (99.5%), excellent radioluminescence with an efficient internal light yield (25 000 photon/MeV), and sensitive X-ray response with a low detection limit (40.4 nGy/s). The organic-inorganic hybrid chemical feature allows the fabrication of a flexible film based on this scintillator for fine-resolution X-ray radiography. These advantages endow our organic-inorganic hybrid scintillator with promising potential in wearable and portable medical devices.

Visible Light-Activated Carbon Dots for Inhibiting Biofilm Formation and Inactivating Biofilm-Associated Bacterial Cells.

This study aimed to address the significant problems of bacterial biofilms found in medical fields and many industries. It explores the potential of classic photoactive carbon dots (CDots), with 2,2'-(ethylenedioxy)bis (ethylamine) (EDA) for dot surface functionalization (thus, EDA-CDots) for their inhibitory effect on B. subtilis biofilm formation and the inactivation of B. subtilis cells within established biofilm. The EDA-CDots were synthesized by chemical functionalization of selected small carbon nanoparticles with EDA molecules in amidation reactions. The inhibitory efficacy of CDots with visible light against biofilm formation was dependent significantly on the time point when CDots were added; the earlier the CDots were added, the better the inhibitory effect on the biofilm formation. The evaluation of antibacterial action of light-activated EDA-CDots against planktonic B. subtilis cells versus the cells in biofilm indicate that CDots are highly effective for inactivating planktonic cells but barely inactivate cells in established biofilms. However, when coupling with chelating agents (e.g., EDTA) to target the biofilm architecture by breaking or weakening the EPS protection, much enhanced photoinactivation of biofilm-associated cells by CDots was achieved. The study demonstrates the potential of CDots to prevent the initiation of biofilm formation and to inhibit biofilm growth at an early stage. Strategic combination treatment could enhance the effectiveness of photoinactivation by CDots to biofilm-associated cells.

Photoactivated Carbon Dots for Inactivation of Foodborne Pathogens Listeria and Salmonella.

Foodborne pathogens have long been recognized as major challenges for the food industry and repeatedly implicated in food product recalls and outbreaks of foodborne diseases. This study demonstrated the application of a recently discovered class of visible-light-activated carbon-based nanoparticles, namely, carbon dots (CDots), for photodynamic inactivation of foodborne pathogens. The results demonstrated that CDots were highly effective in the photoinactivation of Listeria monocytogenes in suspensions and on stainless steel surfaces. However, it was much less effective for Salmonella cells, but treatments with higher CDot concentrations and longer times were still able to inactivate Salmonella cells. The mechanistic implications of the observed different antibacterial effects on the two types of cells were assessed, and the associated generation of intracellular reactive oxygen species (ROS), the resulting lipid peroxidation, and the leakage of nucleic acid and proteins from the treated cells were analyzed, with the results collectively suggesting CDots as a class of promising photodynamic inactivation agents for foodborne pathogens. IMPORTANCE Foodborne infectious diseases have long been recognized as major challenges in public health. Contaminations of food processing facilities and equipment with foodborne pathogens occur often. There is a critical need for new tools/approaches to control the pathogens and prevent such contaminations in food processing facilities and other settings. This study reports a newly established antimicrobial nanomaterials platform, CDots coupled with visible/natural light, for effective and efficient inactivation of representative foodborne bacterial pathogens. The study will contribute to promoting the practical application of CDots as a new class of promising nanomaterial-based photodynamic inactivation agents for foodborne pathogens.

Enantiospecific Detection of D-Amino Acid through Synergistic Upconversion Energy Transfer.

D-amino acids (DAAs) are indispensable in regulating diverse metabolic pathways. Selective and sensitive detection of DAAs is crucial for understanding the complexity of metabolic processes and managing associated diseases. However, current DAA detection strategies mainly rely on bulky instrumentation or electrochemical probes, limiting their cellular and animal applications. Here we report an enzyme-coupled nanoprobe that can detect enantiospecific DAAs through synergistic energy transfer. This nanoprobe offers near-infrared upconversion capability, a wide dynamic detection range, and a detection limit of 2.2 µM, providing a versatile platform for in vivo noninvasive detection of DAAs with high enantioselectivity. These results potentially allow real-time monitoring of biomolecular handedness in living animals, as well as developing antipsychotic treatment strategies.

Toward understanding the phase-selective growth mechanism of films and geometrically-shaped flakes of 2D MoTe2.

Two-dimensional (2D) molybdenum ditelluride (MoTe2) is an interesting material for fundamental study and applications, due to its ability to exist in different polymorphs of 2H, 1T, and 1T', their phase change behavior, and unique electronic properties. Although much progress has been made in the growth of high-quality flakes and films of 2H and 1T'-MoTe2 phases, phase-selective growth of all three phases remains a huge challenge, due to the lack of enough information on their growth mechanism. Herein, we present a novel approach to growing films and geometrical-shaped few-layer flakes of 2D 2H-, 1T-, and 1T'-MoTe2 by atmospheric-pressure chemical vapor deposition (APCVD) and present a thorough understanding of the phase-selective growth mechanism by employing the concept of thermodynamics and chemical kinetics involved in the growth processes. Our approach involves optimization of growth parameters and understanding using thermodynamical software, HSC Chemistry. A lattice strain-mediated mechanism has been proposed to explain the phase selective growth of 2D MoTe2, and different chemical kinetics-guided strategies have been developed to grow MoTe2 flakes and films.

Ultrathin Bi2O2S nanosheet near-infrared photodetectors.

Recently, a zipper two-dimensional (2D) material Bi2O2Se belonging to the layered bismuth oxychalcogenide (Bi2O2X: X = S, Se, Te) family, has emerged as an alternate candidate to van der Waals 2D materials for high-performance electronic and optoelectronic applications. This hints towards exploring the other members of the Bi2O2X family for their true potential and bismuth oxysulfide (Bi2O2S) could be the next member for such applications. Here, we demonstrate for the first time, the scalable room-temperature chemical synthesis and near-infrared (NIR) photodetection of ultrathin Bi2O2S nanosheets. The thickness of the freestanding nanosheets was around 2-3 nm with a lateral dimension of ∼80-100 nm. A solution-processed NIR photodetector was fabricated from ultrathin Bi2O2S nanosheets. The photodetector showed high performance, under 785 nm laser illumination, with a photoresponsivity of 4 A W-1, an external quantum efficiency of 630%, and a normalized photocurrent-to-dark-current ratio of 1.3 × 1010 per watt with a fast response time of 100 ms. Taken together, the findings suggest that Bi2O2S nanosheets could be a promising alternative 2D material for next-generation large-area flexible electronic and optoelectronic devices.

Carbon dots for effective photodynamic inactivation of virus.

The antiviral function of carbon dots (CDots) with visible light exposure was evaluated, for which the model bacteriophages MS2 as a surrogate of small RNA viruses were used. The results show clearly that the visible light-activated CDots are highly effective in diminishing the infectivity of MS2 in both low and high titer samples to the host E. coli cells, and the antiviral effects are dot concentration- and treatment time-dependent. The action of CDots apparently causes no significant damage to the structural integrity and morphology of the MS2 phage or the breakdown of the capsid proteins, but does result in the protein carbonylation (a commonly used indicator for protein oxidation) and the degradation of viral genomic RNA. Mechanistically the results may be understood in the framework of photodynamic effects that are associated with the unique excited state properties and processes of CDots. Opportunities for potentially broad applications of CDots coupled with visible/natural light in the prevention and control of viral transmission and spread are highlighted and discussed.

NaCeF4:Gd,Tb Scintillator as an X-ray Responsive Photosensitizer for Multimodal Imaging-Guided Synchronous Radio/Radiodynamic Therapy.

Photosensitizers (PSs) that are directly responsive to X-ray for radiodynamic therapy (RDT) with desirable imaging abilities have great potential applications in cancer therapy. Herein, the cerium (Ce)-doped NaCeF4:Gd,Tb scintillating nanoparticle (ScNP or scintillator) is first reported. Due to the sensitization effect of the Ce ions, Tb ions can emit fluorescence under X-ray irradiation to trigger X-ray excited fluorescence (XEF). Moreover, Ce and Tb ions can absorb the energy of secondary electrons generated by X-ray to produce reactive oxide species (ROS) for RDT. With the intrinsic absorption of X-ray by lanthanide elements, the NaCeF4:Gd,Tb ScNPs also act as a computed tomography (CT) imaging contrast agent and radiosensitizers for radiotherapy (RT) sensitization synchronously. Most importantly, the transverse relaxation time of Gd3+ ions is shortened due to the doping of Ce and Tb ions, leading to the excellent performance of our ScNPs in T2-weighted MR imaging for the first time. Both in vitro and in vivo studies verify that our synthesized ScNPs have good performance in XEF, CT, and T2-weighted MR imaging, and a synchronous RT/RDT is achieved with significant suppression on tumor progression under X-ray irradiation. Importantly, no systemic toxicity is observed after intravenous injection of ScNPs. Our work highlights that ScNPs have potential in multimodal imaging-guided RT/RDT of deep tumors.

Activating Antitumor Immunity and Antimetastatic Effect Through Polydopamine-Encapsulated Core-Shell Upconversion Nanoparticles.

Synergistic phototherapy has the potential to conquer the extreme heterogeneity and complexity of difficult tumors and result in better cancer treatment outcomes than monomodal photodynamic therapy (PDT) or photothermal therapy (PTT). However, the previous approaches to combining PDT and PTT are mainly focused on primary tumor obliteration while neglecting tumor metastasis, which is responsible for about 90% of cancer deaths. It is shown that a combined PDT/PTT approach, based on upconversion-polymer hybrid nanoparticles with surface-loaded chlorin e6 photosensitizer, can enhance primary tumor elimination and elicit antitumor immunity against disseminated tumors. The specifical arrangement of an external upconversion coating over the polymer core ensures adequate photoabsorption by the upconversion nanoparticles for the generation of reactive oxygen species upon single near-infrared light irradiation. Furthermore, it is found that synergistic phototherapy can elicit robust systemic and humoral antitumor immune responses. When combined with immune checkpoint blockades, it can inhibit tumor relapse and metastasis as well as prolong the survival of tumor-bearing mice in two types of tumor metastasis models. This study may establish a new modality for enhancing immunogenic cell death through a synergistic phototherapeutic nanoplatform and extend this strategy to overcome tumor metastasis with an augmented antitumor immune response.

Adsorption and Electrochemistry of Carbon Monoxide at the Ionic Liquid-Pt Interface.

In this work, CO adsorption and oxidation processes were studied with cyclic voltammetry and anodic adsorptive stripping chronoamperometry in two structural different ionic liquids (ILs) (i.e., 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Bmpy][NTf2] and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][NTf2]). Multiple redox processes were observed in the ILs. During the anodic oxidation processes, the NTf2- anion is oxidized to form NTf2• radical and CO is oxidized to CO2 and produces a proton in these ILs when a trace amount of water is present. The products of oxidation processes (NTf2• radical and proton) can be reduced at cathodic processes. Results show that the cation in these ILs can facilitate the formation of an electrolyte-electrode interface structure that influences the amount of CO adsorbed as well as the subsequent CO oxidation current and charge. By selecting the anodic and cathodic potentials, we developed an innovative electroanalytical method for CO sensing based on a simple double-potential adsorptive stripping chronoamperometry. The method allows calibration of the concurrent NTf2- anion and CO redox processes as well as the double-layer charging and discharging processes in the IL with the presence of a trace amount of water providing quantitative analysis of CO concentration with high accuracy and sensitivity. The reported method is the first work to show that quantitative CO detection can be achieved in the presence of complex dynamic interfacial processes in the ILs. The trace water present in the ILs is beneficial for CO oxidation, but a large amount of water is detrimental for the CO oxidation in ambient condition.

The dominant role of surface functionalization in carbon dots' photo-activated antibacterial activity.

Background: Carbon dots (CDots) have recently been demonstrated their effective visible light-activated antimicrobial activities toward bacteria. This study was to evaluate and understand the roles of the surface functionalities in governing the antimicrobial activity of CDots. Methods: Using the laboratory model bacteria Bacillus subtilis, the photo-activated antimicrobial activities of three groups of CDots with specifically selected different surface functionalization moieties were evaluated and compared. The first group consisting of CDots with surface functionalization by 2,2-(ethylenedioxy)bis(ethylamine) (EDA) vs. 3-ethoxypropylamine (EPA), was evaluated to determine the effect of different terminal groups/charges on their photo-activated antibacterial activities. The second group consisting of CDots functionalized with oligomeric polyethylenimine (PEI) and those prepared by the carbonization of PEI - citric acid mixture, was to evaluate the effects of dot surface charges vs. fluorescent quantum yields on their antimicrobial activities. The third group consisting of CDots functionalized with PEI of 1,200 vs. 600 in average molecular weight was evaluated for the effect of molecular weight of surface passivation molecular on their antimicrobial activities. Results: The results indicated the EDA-CDots in the first group was more effective and was attributed to the positive charges from the protonation of the amino groups (-NH2) being more favorable to interactions with bacterial cells. The evaluation of the second group CDots suggested the same surface charge effect dominating the antibacterial performance over the fluorescent quantum yields. The evaluation of the third group CDots functionalized with PEI of 1,200 vs. 600 in average molecular weight, indicated the latter was significantly more effective. Conclusions: The results from this study highlighted the dominant role of surface functionalities in governing CDots' light activated antimicrobial activity and should have significant implications to the further design and development of CDots as a new class of visible light-activated antibacterial agents.

Systematic Toxicity Evaluations of High-Performance Carbon "Quantum" Dots.

Carbon dots (CDots) in a general structure of small carbon nanoparticles with various surface passivation schemes have emerged to represent a new class of carbon nanomaterials in now a rapidly advancing and expanding research field. Among various synthesis methods, the use of pre-processed and selected small carbon nanoparticles for deliberate chemical functionalization of the particle surface with organic molecules have produced high-performance and structurally better defined CDots. Specifically, small organic molecules 2,2'-(ethylenedioxy)bis(ethylamine) and 3-ethoxypropylamine were used for the effective surface passivation of the carbon nanoparticles via chemical functionalization to yield CDots that are brightly fluorescent and also structurally ultra-compact, amenable to various desired cell imaging applications. Thus, a systematic evaluation of these CDots on their cytotoxicity profiles is necessary, and performed in this study by using a diverse selection of cell lines. Also for fluorescence imaging, CDots were modified with their encapsulating selected organic dyes for much enhanced red/near-IR fluorescence emissions. These modified CDots with the dyes as guest were also evaluated for their cytotoxicity profiles. The results suggest that the CDots without and with the guest dyes are generally nontoxic to the selected cell lines, further supporting the notion that CDots can be used as high-performance yet nontoxic bioimaging agents.

Synergistic photoactivated antimicrobial effects of carbon dots combined with dye photosensitizers.

BACKGROUND: Carbon quantum dots (CDots) have recently been reported as a new class of visible light activated antimicrobial nanomaterials. This study reports the synergistic photoactivated antimicrobial interactions of CDots with photosensitizers on bacterial cells. METHODS: The antimicrobial effects of the CDots with surface passivation molecules 2,2'-(ethylenedioxy)bis(ethylamine) in combination with photosensitizer methylene blue (MB) or toluidine blue (TB) at various concentrations were evaluated against Escherichia coli cells with and without 1-hour visible light illumination. The broth microdilution checkerboard method and isobologram analysis were used for determining if synergistic effect existed between CDots and MB or TB. RESULTS: The results showed that CDots alone at a concentration of 5 µg/mL did not display antimicrobial effects, 1 µg/mL MB alone only decreased 1.86 log of viable cell numbers, but the combination treatment with 5 µg/mL CDots combined with 1 µg/mL MB completely inhibited bacteria growth, resulted in 6.2 log viable cell number reduction, suggesting synergistic interaction between the two. The antimicrobial effects of CDots/TB combination exhibited similarly synergistic effects on E. coli cells. These synergistic effects between CDots and MB or TB were further confirmed using the checkerboard microdilution methods, where the fractional inhibitory concentration index value (0.5) and the isobologram analyses. The synergistic interactions were also correlated to the increased generation of intracellular reactive oxygen species in E. coli cells upon the combination treatments of CDots/MB or CDots/TB. CONCLUSION: The study demonstrated the synergistic photoactivated antimicrobial effects of CDots in combination with other photosensitizers. Such synergistic effect may open new strategies for developing highly effective antimicrobial methods.

Rationally Designed Monodisperse Gd2 O3 /Bi2 S3 Hybrid Nanodots for Efficient Cancer Theranostics.

Multifunctional nanotheranostic agents are of particular importance in the field of precise nanomedicine. However, a critical challenge remains in the rational fabrication of monodisperse multicomponent nanoparticles with enhanced multifunctional characteristics for efficient cancer theranostics. Here, a rational and facile synthesis of monodisperse Gd2 O3 /Bi2 S3 hybrid nanodots (Gd/Bi-NDs) is demonstrated as a multifunctional nanotheranostic agent using a albumin nanoreactor for computed tomography (CT)/photoacoustics (PA)/magnetic resonance (MR) imaging and simultaneous photothermal tumor ablation. Two nanoprecipitation reactions in one albumin nanoreactor are simultaneously conducted to generate ultrasmall Gd/Bi-NDs with both orthorhombic Bi2 S3 and cubic Gd2 O3 nanostructures. Their hybrid nanostructure generates distinctly enhanced longitudinal relaxivity in the spatially confined albumin nanocage as compared to monocomponent Gd2 O3 nanodots. Moreover, such hybrid nanodots possess multiple desirable characteristics including superior photobleaching resistance, efficient cellular uptake, preferable tumor accumulation, good in vivo clearance, and negligible acute toxicity, thereby leading to complementary PA/CT/MR imaging with spatial and anatomic characteristics, as well as effective photothermal tumor ablation without regrowth. These results represent a promising approach to fabricate monodisperse multicomponent nanotheranostic agents for efficient cancer theranostics.

Continuous amperometric hydrogen gas sensing in ionic liquids.

We report an innovative amperometric hydrogen sensor that addresses current primary issues (i.e. signal drift, low selectivity and speed) in continuous and real-time gas sensing. Utilizing the unique properties and redox reactions of hydrogen in the ionic liquids (ILs), 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Bmpy][NTf2] and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][NTf2], we demonstrate the real-time and continuous sensing of hydrogen with high sensitivity, selectivity and repeatability in both anaerobic and aerobic conditions using simple constant potential amperometry. The varying adsorption of hydrogen at the IL-electrode interface in different ILs is shown to allow tuning of the sensitivity of the sensor. Taking advantage of oxygen in ambient conditions, we demonstrate that the unique chemical reaction of the analyte with the oxygen enables selective quantification of hydrogen in an ambient environment. A sensor calibration based on a kinetics analysis (i.e. the change of the rate of current signal (ΔI/Δt1/2)) rather than an equilibrium analysis was demonstrated to allow fast and quantitative analysis of hydrogen concentration. The ionic liquid hydrogen sensor exhibits high sensitivity, selectivity, speed, accuracy, repeatability and stability. Together with the miniaturization and affordability of amperometric sensor readout electronics, the IL-based electrochemical gas sensor is expected to enable area-wide sensing instead of point measurements for environmental, health and occupational safety applications.

Albumin-coordinated assembly of clearable platinum nanodots for photo-induced cancer theranostics.

Photoactive noble metal nanoparticles are of increasing importance toward personalized cancer therapy in the field of precision nanomedicine. A critical challenge remains in the exploration of clinically potential noble metal nanoparticles for highly efficient cancer theranostics. Here, we introduce albumin-coordinated assembly of clearable Pt nanodots (Pt-NDs) with monodisperse nanostructure as high-performance theranostic agents for imaging-guided photothermal tumor ablation. We precisely manipulate the reduction and growth of tetravalent Pt ions into ultrasmall nanodots through albumin-directed growth kinetics, thereby leading to the synthesis of monodisperse 6.7 nm Pt-NDs with albumin molecules as the corona. Pt-NDs exhibit the surface plasmon resonance at 225 nm with enhanced near-infrared (NIR) absorbance, ideal resistance to photo-bleaching, distinct photoacoustic and X-ray signals, as well as remarkable photothermal effect through non-radiative relaxation under NIR light irradiation. In particular, Pt-NDs possess preferable tumor accumulation, and effective in vivo excretory capability. Thus, these nanodots promote preferable in vivo microscopic photoacoustics and spatially anatomic CT imaging with enhanced contrast, as well as potent hyperthermia-mediated tumor ablation. These findings represent a facile and general approach to fabricate high-performance noble metal nanostructures with clinical potential for cancer theranostics.