Depletion and Downregulation of Hydrogen Sulfide Using an Activatable Probe for Promoting Photothermal Therapy toward Colorectal Cancers.

Since hydrogen sulfide (H2S) is an important endogenous gaseous mediator, therapeutic manipulation of H2S is promising for anticancer treatment. In this work, we develop a novel theranostic nanoplatform with H2S-specific and photocontrolled synergistic activation for imaging-guided H2S depletion and downregulation along with promoted photothermal therapy. Such a nanoplatform is fabricated by integration of a H2S-responsive molecule probe that can generate a cystathionine-ß-synthase (CBS) inhibitor AOAA and a photothermal transducer into an NIR-light-responsive container. Our nanoplatform can turn on NIR fluorescence specifically in H2S-rich cancers, guiding further laser irradiation. Furthermore, prominent conversion of photoenergy into heat guarantees special container melting with controllable AOAA release for H2S-level downregulation. This smart regulation of the endogenous H2S level amplifies the PTT therapeutic effect, successfully suppressing colorectal tumor in living mice under NIR fluorescence imaging guidance. Thus, we believe that this nanoplatform may provide a powerful tool toward H2S-concerned cancer treatment with an optimized diagnostic and therapeutic effect.

Engineering organelle-specific activatable molecules for ultra-fast and reliable in situ mapping of subcellular nitric oxide.

Nitric oxide (NO), a ubiquitous gaseous transmitter in living systems, is closely associated with physiopathological processes in the endoplasmic reticulum and lysosomes. This free radical gas is very widely but very heterogeneously distributed in the biological microenvironment, which poses a great challenge to specifically detect its localized levels in certain subcellular regions. In this study, we proposed six subcellular targeting probes by rational molecular engineering and selected two probes with optimal performance for the precise spatiotemporal identification of endoplasmic reticulum (ER) and lysosomal NO fluctuations. The probes could rapidly undergo a N-nitrosation reaction with NO at a riveted subcellular location, blocking the initial photoinduced electron transfer (PET) process and generating bright fluorescence for precise mapping of NO in the ER and lysosomes. The screened probes have ultra-sensitive reactivity and ultra-low detection limits for NO, realizing the precise depiction of exogenous and endogenous NO in the corresponding subcellular area. Fluctuations in the subcellular levels of NO during inflammation were also successfully mapped by the probes. Our work will contribute to the accurate study of the physiological and pathological consequences of subcellular NO in various biological events.

Self-Assembled Activatable Probes to Monitor Interactive Dynamics of Intracellular Nitric Oxide and Hydrogen Sulfide.

The increasing understanding of the intricate relationship between two crucial gasotransmitters nitric oxide (NO) and hydrogen sulfide (H2S) in biological actions has generated significant interest. However, comprehensive monitoring of the dynamic fluctuations of endogenous NO and H2S remains a challenge. In this study, we have designed an innovative aggregation-induced reporter SAB-NH-SC with enhanced responsiveness to H2S for visualizing the fluctuations of intracellular NO and H2S. This probe leverages the hydrophilic properties of the pyridinium salt derivative, which can rapidly self-assemble into positively charged nanoparticles under physiological conditions, avoiding the introduction of organic solvents or tedious preparations. Notably, the reporter can repeatedly cycle S-nitrosation and SNO-transnitrosation reactions when successively treated with NO and H2S. Consequently, fluorescence alternation at 751 (H2S) and 639 nm (NO) facilitates the dynamic visualization of the alternating presence of H2S and NO within cells. This dynamic and reversible probe holds immense potential for unraveling the intricate interactions between NO and H2S in a complex network of biological applications.

RSS and ROS Sequentially Activated Carbon Monoxide Release for Boosting NIR Imaging-Guided On-Demand Photodynamic Therapy.

Carbon monoxide shows great therapeutic potential in anti-cancer. In particular, the construction of multifunctional CO delivery systems can promote the precise delivery of CO and achieve ideal therapeutic effects, but there are still great challenges in design. In this work, a RSS and ROS sequentially activated CO delivery system is developed for boosting NIR imaging-guided on-demand photodynamic therapy. This designed system is composed of a CO releaser (BOD-CO) and a photosensitizer (BOD-I). BOD-CO can be specifically activated by hydrogen sulfide with simultaneous release of CO donor and NIR fluorescence that can identify H2 S-rich tumors and guide light therapy, also depleting H2 S in the process. Moreover, BOD-I generates 1 O2 under long-wavelength light irradiation, enabling both PDT and precise local release of CO via a photooxidation mechanism. Such sequential activation of CO release by RSS and ROS ensured the safety and controllability of CO delivery, and effectively avoided leakage during delivery. Importantly, cytotoxicity and in vivo studies reveal that the release of CO combined with the depletion of endogenous H2 S amplified PDT, achieving ideal anticancer results. It is believed that such theranostic nanoplatform can provide a novel strategy for the precise CO delivery and combined therapy involved in gas therapy and PDT.

Molecular Engineering of Luminogens for High-Integrity Imaging of Hydrogen Polysulfides via Activatable Aggregation-Induced Dual-Color Fluorescence.

Understanding biological events associated with H2Sn rather than mediated by H2S is of great significance but remains to be solved due to a lack of high-integrity imaging tools. In this study, we report a chemoselective probe for H2Sn over H2S through the molecular engineering of luminogens. Based on our search for H2Sn-activatable probes with high selectivity, we fabricate water-soluble and biocompatible nanoprobes. Such a designed nanoprobe shows rare aggregation-induced dual-color fluorescence responses to H2Sn, lighting up bright emissions at 588 and 750 nm, respectively. By use of this activatable dual-color fluorescence, high-integrity identification of intracellular H2Sn was successfully realized. Thus, our approach to H2Sn-activated multicolor fluorescent probes could provide valuable insight into interrogating H2Sn-mediated biological events.

Specific imaging of intracellular hydrogen sulfide by a positively charged NIR fluorescent probe.

The poor water solubility of traditional activatable organic molecular probes usually limits their detection ability in physiological environment. In this work, a positively charged H2S probe was designed, which exhibited a significantly enhanced responsiveness to H2S in the aggregated state due to the increased positive charge density on the aggregate surface. Under physiological conditions, the probe could be activated by H2S with specificity and sensitivity to release near-infrared fluorescence signal. Moreover, endogenous H2S levels in living cells were successfully monitored by using this probe. We expect that this probe can provide a new strategy for the design of activatable probes to break the limitation of poor water solubility of conventional organic molecular probes.

Precise Spatiotemporal Identification of Mitochondrial H2S Fluctuations through Exploiting an On-Demand Photoactivated Probe.

Various signal molecules participate in complex biological processes in mitochondria. However, most currently available probes have problems in elucidating the functions of these active species in mitochondria due to the inability to light up these probes exclusively at the desired mitochondrial location, thereby compromising the specificity and accuracy. In this study, we present an on-demand photoactivation approach to the molecular design of optimized probes for precise spatiotemporal identification of mitochondrial H2S fluctuations. The designed probe with native yellow fluorescence can monitor the process into mitochondria but maintains nonfluorescent response to H2S during cellular delivery, providing the accurate timing of accumulation in mitochondria. On-demand photoactivation exclusively at the desired mitochondrial location affords a significant aggregation-enhanced and emissive response to H2S with lighting up red fluorescence at 690 nm, which is the only way to get such an emissive phenomenon and greatly improves the specificity and accuracy of targeting mitochondrial H2S. By using this photocontrolled fluorescence responsiveness to H2S, precise spatiotemporal identification of mitochondrial H2S fluctuations is successfully performed. Our work could facilitate advances toward interrogating the physiological and pathological consequences of mitochondrial H2S in various biological events.

An activatable endoplasmic reticulum-targeted probe for NIR imaging-guided photothermal therapy.

An H2O2-activated, endoplasmic reticulum-targeted theranostic probe was developed. This designed probe could be activated by H2O2, resulting in increased NIR fluorescence and photothermal signals, thus achieving specific recognition of H2O2 and further photothermal therapy in the endoplasmic reticulum of H2O2-overexpressing cancer cells.

Anchoring Pt Particles onto Mesoporousized ZnO Holey Cubes for Triethylamine Detection with Multifaceted Superiorities.

Designing sensing materials with integrating unique spatial structures, functional units, and surface activity is vital to achieve high-performance gas sensor toward triethylamine (TEA) detection. Herein, a simple spontaneous dissolution is used with subsequent thermal decomposition strategy to fabricate mesoporousized ZnO holey cubes. The squaric acid is crucial to coordinate Zn2+ to form a cubic shape (ZnO-0) and then tailor the inner part to open a holey cube with simultaneously mesoporousizing the left cubic body (ZnO-72). To enhance the sensing performance, the mesoporous ZnO holey cubes have been functionalized with catalytic Pt nanoparticles, which deliver superior performances including high response, low detection limit, and fast response and recovery time. Notably, the response of Pt/ZnO-72 towards 200 ppm TEA is up to 535, which is much higher than those of 43 and 224 for pristine ZnO-0 and ZnO-72. A synergistic mechanism combining the intrinsic merits of ZnO, its unique mesoporous holey cubic structure, the oxygen vacancies, and the catalytic sensitization effect of Pt has been proposed for the significant enhancement in TEA sensing. Our work provides an effective facile approach to fabricate an advanced micro-nano architecture with manipulating its spatial structure, functional units, and active mesoporous surface for promising TEA gas sensors.

Polypyrrole/Schiff Base Composite as Electromagnetic Absorbing Material with High and Tunable Absorption Performance.

In recent years, Schiff base-related conjugated systems have received extensive attention, but little research has been done in the field of electromagnetic materials. In this work, an organic conjugated system based on polypyrrole/hydrazone Schiff base (PPy/HSB) composites was constructed via a Schiff base synthetic route and their electromagnetic behavior was investigated. The electromagnetic response of PPy/HSB complexes demonstrates fine electromagnetic absorption performance. When the filler loading is 30 wt% in a paraffin matrix, an absorption peak of -43.1 dB was achieved and its effective absorption bandwidth (EAB) was located in the range of 10.88-18.0 GHz. The electromagnetic response behavior of PPy/HSB complexes is explained by models involving electronic structure, multi-polarization and conductive network. The mechanisms of PPy/HSB complexes formation and HSB crystallization are also discussed through the compatibility of PPy/HSB and the structure of HSB. Moreover, the morphology transformation of HSB in the PPy/HSB systems has been studied. This study opens the exploration of organic-dielectric conjugated systems in the field of electromagnetic materials, and significantly broadens the application range of organic-dielectric-dielectric composites.

Activatable photothermal agents with target-initiated large spectral separation for highly effective reduction of side effects.

Photothermal agents (PTAs) with minimized side effects are critical for transforming cancer photothermal therapy (PTT) into clinical applications. However, most currently available PTAs lack true selective activation to reduce side effects because of heavy spectral overlap between photothermal agents and their corresponding products. This study reports the construction of activatable PTAs with target-initiated large spectral separation for highly effective reduction of side effects. Such designed probes involve two H2O2-activatable PTAs, aza-BOD-B1 (single activatable site) and aza-BOD-B2 (multiple activatable site). After interacting with H2O2, aza-BOD-B1 only displays a mild absorption redshift (60 nm) from 750 nm to 810 nm with serious spectral overlap, resulting in a mild photothermal effect on normal tissues upon 808 nm light irradiation. In contrast, aza-BOD-B2 displays a large absorption spectral separation (150 nm) from 660 nm to 810 nm, achieving true selective activation to minimize side effects during PTT of cancer. Besides, in vitro and in vivo investigations demonstrated that aza-BOD-B2 can specifically induce photothermal ablation of cancer cells and tumors while leaving normal sites undamaged, whereas aza-BOD-B1 exhibits undesirable side effects on normal cells. Our study provides a practical solution to the problem of undesired side effects of phototherapy, an advance in precision medicine.

Polystyrene-Modulated Polypyrrole to Achieve Controllable Electromagnetic-Wave Absorption with Enhanced Environmental Stability.

The moderation of the dielectric properties of polymer composites and their environmental stability need to be considered comprehensively in the design of microwave-absorbing materials. In this work, polypyrrole/polystyrene (PPy/PS) composited particles were synthesized through a facile in situ bulk polymerization procedure. The PS component can be modulated conveniently by controlling the polymerization time. FTIR and Raman analyses disclosed that the PS component was immobilized in PPy via covalent bonds. The electromagnetic characterization results indicated that the dielectric properties and, thus, the microwave absorption could be controlled when the styrene polymerization was prolonged from 6 h (PPy-6) to 19 h (PPy-19). The composite PPy-19 displayed an optimal reflection loss of -51.7 dB with a matching thickness of 3.16 mm, and the effective absorption bandwidth (EAB) even reached 5.8 GHz at 2.4 mm. The PS component endowed PPy/PS composites with more robust environmental stability than homogeneous PPy. After being exposed to air for 365 days and hydrothermally treated at 100 °C for 12 h, PPy-19 still exhibited a reflection loss superior to -20 dB. The present work provides a new insight into the adjustment of the electromagnetic properties of PPy composites to fabricate high-performance microwave absorbers with superior environmental stability.

Gas sensing materials roadmap.

Gas sensor technology is widely utilized in various areas ranging from home security, environment and air pollution, to industrial production. It also hold great promise in non-invasive exhaled breath detection and an essential device in future internet of things. The past decade has witnessed giant advance in both fundamental research and industrial development of gas sensors, yet current efforts are being explored to achieve better selectivity, higher sensitivity and lower power consumption. The sensing layer in gas sensors have attracted dominant attention in the past research. In addition to the conventional metal oxide semiconductors, emerging nanocomposites and graphene-like two-dimensional materials also have drawn considerable research interest. This inspires us to organize this comprehensive 2020 gas sensing materials roadmap to discuss the current status, state-of-the-art progress, and present and future challenges in various materials that is potentially useful for gas sensors.

Longitudinal changes in COVID-19 clinical measures and correlation with the extent of CT lung abnormalities.

Rationale: To assess the longitudinal changes and relationships of clinical measures and extent of CT lung abnormalities in COVID-19. Methods: 81 patients with COVID-19 were prospectively enrolled and followed until discharge. CT scores were quantified on a basis of a CT scoring system where each lung was divided into 3 zones: upper (above the carina), middle, and lower (below the inferior pulmonary vein) zones; each zone was evaluated for percentage of lung involvement on a scale of 0-4 (0, 0%; 1, 0-24%; 2, 25% - 49%; 3, 50% -74%; 4, >74%).Temporal trends of CT scores and the laboratory parameters characteristic of COVID-19 were analyzed. Correlations between the two were determined at three milestones (initial presentation, worst CT manifestation, and recovery finding before discharge). Their correlations with duration to worst CT manifestation and discharge from symptom onset were evaluated. Results: CT scores peaked during illness days 6-11 (median: 5), and stayed steady. C-reactive protein and lactate dehydrogenase increased, peaked on illness days 6-8 and 8-11 (mean: 23.5 mg/L, 259.9 U/L), and gradually declined. Continual decrease and increase were observed in hemoglobin and lymphocyte count, respectively. Albumin reduced and remained at low levels with a nadir on illness days 12-15 (36.6 g/L). Both initial (r = 0.58, 0.64, p < 0.05) and worst CT scores (r = 0.47, 0.65, p < 0.05) were correlated with C-reactive protein and lactate dehydrogenase; and CT scores before discharge, only with albumin (r = -0.41, p < 0.05). Duration to worst CT manifestation was associated with initial and worst CT scores (r = 0.33, 0.29, p < 0.05). No parameters were related to timespan to discharge. Conclusion: Our results illustrated the temporal changes of characteristic clinical measures and extent of CT lung abnormalities in COVID-19. CT scores correlated with some important laboratory parameters, and might serve as prognostic factors.

ZnO-Decorated In/Ga Oxide Nanotubes Derived from Bimetallic In/Ga MOFs for Fast Acetone Detection with High Sensitivity and Selectivity.

The development of acetone gas sensors is desirable but challenging for both air quality monitoring and medical diagnosis. Herein, starting from bimetallic In/Ga metal-organic frameworks (MOFs) (MIL-68 (In/Ga)), a facile strategy is proposed to couple with zinc ions to design In/Ga oxide (IGO)@ZnO core-shell nanotubes for efficient acetone detection. In such a heterostructure, tiny ZnO nanoparticles are closely decorated on IGO nanotubes, which is beneficial to enlarge the specific surface area and create rich oxygen vacancies and heterojunction interfaces. Benefiting from the structural merits and synergetic effects, the IGO@ZnO-based gas sensor exhibits a low detection limitation (200 ppb), a high response, good linearity relationship between the sensing responses and wide testing acetone concentrations, and fast response and recovery time (6.8/6.1 s) with good selectivity and stability. These sensing performances strongly indicate the practical application to quantitatively detect acetone.

Temporal Changes of CT Findings in 90 Patients with COVID-19 Pneumonia: A Longitudinal Study.

Background CT may play a central role in the diagnosis and management of coronavirus disease 2019 (COVID-19) pneumonia. Purpose To perform a longitudinal study to analyze the serial CT findings over time in patients with COVID-19 pneumonia. Materials and Methods During January 16 to February 17, 2020, 90 patients (33 men, 57 women; mean age, 45 years) with COVID-19 pneumonia were prospectively enrolled and followed up until being discharged, death, or the end of the study. A total of 366 CT scans were acquired and reviewed by two groups of radiologists for the patterns and distribution of lung abnormalities, total CT scores, and number of zones involved. Those features were analyzed for temporal change. Results CT scores and number of zones involved progressed rapidly, peaked during illness days 6-11 (median CT score, 5; median number of zones involved, five), and were followed by persistence of high levels. The predominant pattern of abnormalities after symptom onset was ground-glass opacity (35 of 78 scans [45%] to 49 of 79 scans [62%] in different periods). The percentage of mixed pattern peaked on illness days 12-17 (30 of 78 scans [38%]) and became the second most predominant pattern thereafter. Pure ground-glass opacity was the most prevalent subtype of ground-glass opacity after symptom onset (20 of 50 scans [40%] to 20 of 28 scans [71%]). The percentage of ground-glass opacity with irregular linear opacity peaked on illness days 6-11 (14 of 50 scans [28%]) and became the second most prevalent subtype thereafter. The distribution of lesions was predominantly bilateral and subpleural. Sixty-six of the 70 patients discharged (94%) had residual disease on final CT scans (median CT score, 4; median number of zones involved, four), with ground-glass opacity (42 of 70 patients [60%]) and pure ground-glass opacity (31 of 42 patients [74%]) the most common pattern and subtype. Conclusion The extent of lung abnormalities at CT peaked during illness days 6-11. The temporal changes of the diverse CT manifestations followed a specific pattern, which might indicate the progression and recovery of the illness. © RSNA, 2020 Online supplemental material is available for this article.

Nanoparticles Assembled CdIn2O4 Spheres with High Sensing Properties towards n-Butanol.

Cd/In-glycerate spheres are synthesized through a simple solvothermal method. After thermal treatment, these Cd/In-glycerates can be converted into CdIn2O4 spheres. Many characterization methods were performed to reveal the microstructure and morphology of the CdIn2O4. It was found that pure CdIn2O4 phase was obtained for the Cd/In starting materials at ratios of 1:1.6. The CdIn2O4 spheres are composed by a large number of nanoparticles subunits. The CdIn2O4 sphere-based sensor exhibited a low detection limit (1 ppm), high response (81.20 to 500 ppm n-butanol), fast response (4 s) and recovery (10 s) time, good selectivity, excellent repeatability, and stability at 280 °C. Our findings highlight the possibility to develop a novel gas sensor based on CdIn2O4 for application in n-butanol detection with high performance.

A nickel foam modified with electrodeposited cobalt and phosphor for amperometric determination of dopamine.

Considering the importance of dopamine (DA) detection for neuroscience and disease diagnosis, herein, an electrochemical sensor for dopamine is described. It is based on the use of a Ni-Co-P nanostructure fabricated on nickel foam via electrode position from cobalt chloride and ammonium phosphate for 10 min. Time-dependent experiments show the transformation of Ni-Co-P nanoparticles to spheres. The resulting electrode display excellent electrochemical response to DA. Figures of merit include (a) a working potential of 0.55 V (vs. Ag/AgCl); (b) an electrochemical sensitivity of 5262 µA mM-1 cm-2; (c) a wide linear range (from 0.5 to 2350 µM), and (d) a 1 µM detection limit. The outstanding electrochemical performance is explained by the synergistic effects of large surface area, improved electron transfer, presence of free binders, and the presence of three active components (nickel, cobalt and phosphonium ion). Graphical abstract A Ni-Co-P nanostructure was electrodeposited on nickel foam to obtain an electrochemical sensor for amperometric determination of dopamine with outstanding performance.

MOFs-Derived Porous NiFe2O4 Nano-Octahedrons with Hollow Interiors for an Excellent Toluene Gas Sensor.

Toluene is extensively used in many industrial products, which needs to be effectively detected by sensitive gas sensors even at low-ppm-level concentrations. Here, NiFe2O4 nano-octahedrons were calcinated from NiFe-bimetallic metal-organic framework (MOFs) octahedrons synthesized by a facile refluxing method. The co-existence of p-Phthalic acid (PTA) and 3,3-diaminobenzidine (DAB) promotes the formation of smooth NiFe-bimetallic MOFs octahedrons. After subsequent thermal treatment, a big weight loss (about 85%) transformed NiFe2O4 nanoparticles (30 nm) into NiFe2O4 porous nano-octahedrons with hollow interiors. The NiFe2O4 nano-octahedron based sensor exhibited excellent gas sensing properties for toluene with a nice stability, fast response, and recovery time (25 s/40 s to 100 ppm toluene), and a lower detection limitation (1 ppm) at 260 °C. The excellent toluene-sensing properties can not only be derived from the hollow interiors combined with porous nano-octahedrons to favor the diffusion of gas molecules, but also from the efficient catalytic activity of NiFe2O4 nanoparticles.

Biomass carbon derived from pine nut shells decorated with NiO nanoflakes for enhanced microwave absorption properties.

Electromagnetic absorption materials have gained increasing attention. In this study, we report NiO decorated biomass porous carbon derived from pine nut shells as a promising microwave absorbing material by a facile strategy. The NiO/biomass porous carbon (BPC) is thermally converted from Ni(OH)2/BPC with BPC as the base for precipitation. All products were characterized by XRD, Raman, and SEM techniques, which reveals that the NiO nanoflakes were uniformly self-assembled on the surface of the activated carbon. Compared with counterparts of pure Ni(OH)2 and Ni(OH)2/BPC, a large reflection loss peak of -33.8 dB at 16.4 GHz is achieved for the NiO/BPC composites, and the absorption bandwidth less than -10 dB can reach up to about 6.7 GHz (from 11.3 to 18.0 GHz) with a thickness of 8 mm. The enhanced microwave absorption properties originate from the electric/dielectric polarization and the unique NiO decorated BPC structures. The expanded interfaces, such as NiO-NiO, Ni-BPC and NiO-paraffin interfaces in the complicated porous composites, could boost the interfacial polarization as well as related relaxation which results in enhanced dielectric loss and electromagnetic absorbing properties. In addition, NiO/BPC nanocomposites exhibit comparatively better matching of permittivity and permeability. It is expected that our present investigation could provide a new possibility for biomass based fabrication of potential microwave absorbing materials.