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At least 397 records · Page 22

Photoemf in cadmium sulfide

Theoretical and experimental investigations on CdS single crystals and CuxS:CdS photovoltaic cells prepared from CdS single crystals by a chemical-dip procedure are described. The studies are aimed at clarifying cell mechanisms which affect key cell properties (efficiency, reliability, and lifetime) by examining the properties of intrinsic and extrinsic defects in the junction and surface regions and their effects on carrier transport through these regions. The experimental research described includes studies of thermal, infrared, and field quenching of acceptor-doped CdS crystals; investigation of optical and electrical properties of CuxS:CdS photovoltaic cells (current-voltage characteristics, spectral distribution of photocurrent and photovoltage) and the dependence of these properties on temperature and light intensity; measurement of changes, as a result of heat treatment in ultrahigh vacuum, in the spectral distribution of photoconductivity at room temperature and liquid nitrogen temperature, the luminescence spectrum at liquid nitrogen temperature, and the thermally stimulated current curves of CdS crystals; determination of the effect of irradiation with 150 keV (maximum) X-rays on the spectral distribution of photoconductivity and thermally-stimulated current of CdS crystals; and studies of the effect of growth conditions on the photoconductive properties of CdS crystals.

Boeer, K. W.↗

Improved Dynamic Modeling of the Cascade Distillation Subsystem and Analysis of Factors Affecting Its Performance

The Cascade Distillation Subsystem (CDS) is a rotary multistage distiller being developed to serve as the primary processor for wastewater recovery during long-duration space missions. The CDS could be integrated with a system similar to the International Space Station Water Processor Assembly to form a complete water recovery system for future missions. A preliminary chemical process simulation was previously developed using Aspen Custom Modeler® (ACM), but it could not simulate thermal startup and lacked detailed analysis of several key internal processes, including heat transfer between stages. This paper describes modifications to the ACM simulation of the CDS that improve its capabilities and the accuracy of its predictions. Notably, the modified version can be used to model thermal startup and predicts the total energy consumption of the CDS. The simulation has been validated for both NaC1 solution and pretreated urine feeds and no longer requires retuning when operating parameters change. The simulation was also used to predict how internal processes and operating conditions of the CDS affect its performance. In particular, it is shown that the coefficient of performance of the thermoelectric heat pump used to provide heating and cooling for the CDS is the largest factor in determining CDS efficiency. Intrastage heat transfer affects CDS performance indirectly through effects on the coefficient of performance.

Perry, Bruce A.↗

Biomass-derived carbon dots as emerging visual platforms for fluorescent sensing

Biomass-derived carbon dots (CDs) are non-toxic and fluorescently stable, making them suitable for extensive application in fluorescence sensing. The use of cheap and renewable materials not only improves the utilization rate of waste resources, but it is also drawing increasing attention to and interest in the production of biomass-derived CDs. Visual fluorescence detection based on CDs is the focus of current research. This method offers high sensitivity and accuracy and can be used for rapid and accurate determination under complex conditions. Here, this paper describes the biomass precursors of CDs, including plants, animal remains and microorganisms. The factors affecting the use of CDs as fluorescent probes are also discussed, and a brief overview of enhancements made to the preparation process of CDs is provided. In addition, the application prospects and challenges related to biomass-derived CDs are demonstrated.

54 ENVIRONMENTAL SCIENCES↗

Facile preparation of NiS/CdS-t composite photocatalyst for hydrogen evolution from aqueous solution of sulphide/sulphite under visible light

Highlights: ► The nanostructured NiS/CdS photocatalyst was prepared by a facile two-step method. ► After aged for six days, the photocatalyst achieved a maximal rate of H{sub 2} evolution. ► The rate of H{sub 2} evolution on NiS(0.14)/CdS-6 is about 33 times that of CdS-6. - Abstract: The nanostructured NiS/CdS-t (t = aging period in day number) composite photocatalysts were prepared by a facile two-step synthesis method. The photocatalytic activity of H{sub 2} evolution over NiS/CdS could be greatly enhanced by changing the aging period of CdS. The NiS/CdS achieved a maximal rate of H{sub 2} evolution when CdS was aged for 6 days before hydrothermal treatment. It was demonstrated that the composite NiS(0.14)/CdS-6 could achieve a H{sub 2} evolution rate up to 1517 μmol h{sup −1} and show high photocatalytic stability for H{sub 2} evolution under long-term light irradiation. The rate of H{sub 2} evolution on NiS(0.14)/CdS-6 is about 7.5 times that of NiS(0.14)/CdS-3 and 33 times that of CdS-6. The notable improvement can be attributed to the fast electron transfer from CdS to NiS, which is proved by the surface photovoltage spectroscopy and photoluminescent measurements, as well as the increasing percentage of hexagonal-CdS in the mixture of cubic and hexagonal CdS.

36 MATERIALS SCIENCE↗

Striking luminescence phenomena of carbon dots and their applications as a double ratiometric fluorescence probes for H2S detection

Here, we report some new observations on the luminescence of carbon dots (CDs) that are passivated with polyethylene glycol, and explored them, for the first time, as highly sensitive H2S detection probe. The as-prepared CDs have an ultraviolet (UV) emission at 350 nm and a green emission at 540 nm when excited at 270 nm, but they have only a green emission at 523 nm when excited at 365 nm. As Na2S is added to the CDs, the UV emission decreases gradually, while the green emission increases slightly, and interestingly a new emission appears at 455 nm is increased linearly in intensity with the increase of Na2S concentration. The blue emission at 455 nm is from the intrinsic core of CDs, and the green emissions at 540 or 523 nm are from their surface states, while the UV emission at 350 nm is from the anchored PEG. Both the emission intensity ratios of F-450/F-350 and F-455/F-523 show an excellent linear relationship with the Na2S concentration in the range of 0-800 mu M, and the detection limit estimated from both of them is approximately 7.0 nM, indicating our method is the most sensitive H2S CDs based detection method reported thus far. Furthermore, the detection was tested successfully for H2S imaging in live cells. We propose that the interactions of H2S with the CDs and the anchored ligands, as well as the energy transfer between the ligands and the CDs, are responsible for the luminescence responses for H2S detection. Our studies enrich the world of carbon dots with plenty of potential applications. (C) 2020 Elsevier Ltd. All rights reserved.

Bioimaging↗

Placental oxidative stress and decreased global DNA methylation are corrected by copper in the Cohen diabetic rat

Fetal Growth Restriction (FGR) is a leading cause for long term morbidity. The Cohen diabetic sensitive rats (CDs), originating from Wistar, develop overt diabetes when fed high sucrose low copper diet (HSD) while the original outbred Sabra strain do not. HSD induced FGR and fetal oxidative stress, more prominent in the CDs, that was alleviated more effectively by copper than by the anti-oxidant vitamins C and E. Our aim was to evaluate the impact of copper or the anti-oxidant Tempol on placental size, protein content, oxidative stress, apoptosis and total DNA methylation. Animals were mated following one month of HSD or regular chow diet and supplemented throughout pregnancy with either 0, 1 or 2 ppm of copper sulfate or Tempol in their drinking water. Placental weight on the 21st day of pregnancy decreased in dams fed HSD and improved upon copper supplementation. Placental/fetal weight ratio increased among the CDs. Protein content decreased in Sabra but increased in CDs fed HSD. Oxidative stress biochemical markers improved upon copper supplementation; immunohistochemistry for oxidative stress markers was similar between strains and diets. Caspase 3 was positive in more placentae of dams fed HSD than those fed RD. Placental global DNA methylation was decreased only among the CDs dams fed HSD. We conclude that FGR in this model is associated with smaller placentae, reduced DNA placental methylation, and increased oxidative stress that normalized with copper supplementation. DNA hypomethylation makes our model a unique method for investigating genes associated with growth, oxidative stress, hypoxia and copper. - Highlights: • Sensitive Cohen diabetic rats (CDs) had small placentae and growth restricted fetuses. • CDs dams fed high sucrose low copper diet had placental global DNA hypomethylation. • Caspase 3 was positive in more placentae of dams fed HSD than those fed RD. • Oxidative stress parameters improved by Tempol and resolved by copper supplementation. • Global DNA hypomethylation was resolved both by Tempol and by copper supplementation. • Placental oxidative stress parameters coincides previous findings in the fetal liver.

60 APPLIED LIFE SCIENCES↗

Magnetic/NIR-responsive drug carrier, multicolor cell imaging, and enhanced photothermal therapy of gold capped magnetite-fluorescent carbon hybrid nanoparticles

In our paper reports a type of multifunctional hybrid nanoparticle (NP) composed of gold nanocrystals coated on and/or embedded in a magnetite-fluorescent porous carbon core-shell NP template (Fe 3 O 4 @PC-CDs-Au) for biomedical applications, including magnetic/NIR-responsive drug release, multicolor cell imaging, and enhanced photothermal therapy. The synthesis of the Fe 3 O 4 @PC-CDs-Au NPs firstly involves the preparation of core-shell template NPs with magnetite nanocrystals clustered in the cores and fluorescent carbon dots (CDs) embedded in a porous carbon shell, followed by an in situ reduction of silver ions (Ag + ) loaded in the porous carbon shell and a subsequent replacement of Ag NPs with Au NPs through a galvanic replacement reaction using HAuCl 4 as a precursor. Moreover, the Fe 3 O 4 @PC-CDsAu NPs can enter the intracellular region and light up mouse melanoma B16F10 cells in multicolor mode. The porous carbon shell, anchored with hydrophilic hydroxyl/carboxyl groups, endows the Fe 3 O 4 @PC-CDs-Au NPs with excellent stability in the aqueous phase and a high loading capacity (719 mg g -1 ) for the anti-cancer drug doxorubicin (DOX). The superparamagnetic Fe 3 O 4 @PC-CDs-Au NPs with a saturation magnetization of 23.26 emu g -1 produce localized heat under an alternating magnetic field, which triggers the release of the loaded drug. The combined photothermal effects of the Au nanocrystals and the CDs on/in the carbon shell can not only regulate the release rate of the loaded drug, but also efficiently kill tumor cells under NIR irradiation. Finally, in benefitting from their excellent optical properties, their magnetic field and NIR light-responsive drug release capabilities and their enhanced photothermal effect, such nanostructured Fe 3 O 4 @PC-CDs-Au hybrid NPs are very promising for simultaneous imaging diagnostics and high efficacy therapy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Fundamental Piezotronic and Piezo-phototronic Effects in Nanowires

The piezo-phototronic effect is about the use of the piezoelectric potential created inside some materials for enhancing the charge carrier generation or separation at the metal-semiconductor contact or p-n junction. We demonstrate the impact of the piezo-phototronic effect on the photon sensitivity for a ZnO-CdS core-shell micro/nanowire based visible and UVsensor. CdS nanowire arrays were grown on the surface of a ZnO micro/nanowire to form a ZnO-CdS core-shell nanostructure by a facile hydrothermal method. With the two ends of a ZnO-CdS wire bonded on a polymer substrate, a flexible photodetector was fabricated, which is sensitive simultaneously to both green light (548 nm) and UV light (372 nm). The photocurrent and sensitivity of the ZnO_CdS wire photodetector is 103 times higher than that of CdS nanoribbon, and the responsivity (11 A W -1 , 548 nm, at 2 V bias) is nearly 100 times higher than that of ZnSe-nanobelt-based blue/UV-light sensor (0.12 AW -1 , 400 nm, at 30 V bias). Moreover, the performance of the ZnO-CdS wire photodetector upon illumination of visible and UV light can be both further enhanced for more than 10 times with the participation of the piezo-phototronic effect when the device is subjected to a -0.31% compressive strain. This investigation extends the application of the piezo-phototronic effect in a wide spectrum photon detector.

14 SOLAR ENERGY↗

Coronal Magnetography of Solar Active Regions Using Coordinated SOHO/CDS and VLA Observations

The purpose of this project is to apply the coronal magnetographic technique to SOHO (Solar Heliospheric Observatory) /CDS (Coronal Diagnostic Spectrometer) EUV (Extreme Ultraviolet Radiation) and coordinated VLA microwave observations of solar active regions to derive the strength and structure of the coronal magnetic field. A CDS observing plan was developed for obtaining spectra needed to derive active region differential emission measures (DEMs) required for coronal magnetography. VLA observations were proposed and obtained. SOHO JOP 100 was developed, tested, approved, and implemented to obtain coordinated CDS (Coronal Diagnostic Spectrometer)/EIT (Ultraviolet Imaging Telescope)/ VLA (Very Large Array)/ TRACE (Transition Region and Coronal Explorer)/ SXT (Solar X Ray Telescope) observations of active regions on April 12, May 9, May 13, and May 23. Analysis of all four data sets began, with heaviest concentration on COS data. It is found that 200-pixel (14 A in NIS1) wavelength windows are appropriate for extracting broadened Gaussian line profile fit parameters for lines including Fe XIV at 334.2, Fe XVI at 335.4, Fe XVI at 360.8, and Mg IX at 368.1 over the 4 arcmin by 4 arcmin CDS field of view. Extensive efforts were focused on learning and applying were focused on learning and applying CDS software, and including it in new IDL procedures to carry out calculations relating to coronal magnetography. An important step is to extract Gaussian profile fits to all the lines needed to derive the DEM in each spatial pixel of any given active region. The standard CDS absolute intensity calibration software was applied to derived intensity images, revealing that ratios between density-insensitive lines like Fe XVI 360.8/335.4 yield good agreement with theory. However, the resulting absolute intensities of those lines are very high, indicating that revisions to the CDS absolute intensity calibrations remain to be included in the CDS software, an essential step to deriving reliable coronal magnetograms. With lessons learned and high quality data obtained during the past year, coronal magnetography will be successfully pursued under my new SOHO GI program.

Brosius, Jeffrey W.↗

SSBRP User Operations Facility (UOF) Overview and Development Strategy

This paper will present the Space Station Biological Research Project (SSBRP) User Operations Facility (UOF) architecture and development strategy. A major element of the UOF at NASA Ames Research Center, the Communication and Data System (CDS) will be the primary focus of the discussions. CDS operational, telescience, security, and development objectives will be discussed along with CDS implementation strategy. The implementation strategy discussions will include: Object Oriented Analysis & Design, System & Software Prototyping, and Technology Utilization. A CDS design overview that includes: CDS Context Diagram, CDS Architecture, Object Models, Use Cases, and User Interfaces will also be presented. CDS development brings together "cutting edge" technologies and techniques such as: object oriented development, network security, multimedia networking, web-based data distribution, JAVA, and graphical user interfaces. Use of these "cutting edge" technologies and techniques translates directly to lower development and operations costs.

Picinich, Lou↗

Improved Dynamic Modeling of the Cascade Distillation Subsystem and Integration with Models of Other Water Recovery Subsystems

The Cascade Distillation Subsystem (CDS) is a rotary multistage distiller being developed to serve as the primary processor for wastewater recovery during long-duration space missions. The CDS could be integrated with a system similar to the International Space Station (ISS) Water Processor Assembly (WPA) to form a complete Water Recovery System (WRS) for future missions. Independent chemical process simulations with varying levels of detail have previously been developed using Aspen Custom Modeler (ACM) to aid in the analysis of the CDS and several WPA components. The existing CDS simulation could not model behavior during thermal startup and lacked detailed analysis of several key internal processes, including heat transfer between stages. The first part of this paper describes modifications to the ACM model of the CDS that improve its capabilities and the accuracy of its predictions. Notably, the modified version of the model can accurately predict behavior during thermal startup for both NaCl solution and pretreated urine feeds. The model is used to predict how changing operating parameters and design features of the CDS affects its performance, and conclusions from these predictions are discussed. The second part of this paper describes the integration of the modified CDS model and the existing WPA component models into a single WRS model. The integrated model is used to demonstrate the effects that changes to one component can have on the dynamic behavior of the system as a whole.

Perry, Bruce↗

Clinical Decision Support Project

As NASA plans for exploration missions into deep space, significant challenges are realized due to the distance from Earth. Beside the effects of microgravity and radiation exposure, the astronauts face the additional constraints of isolation, lack of resupply, increasingly difficult evacuation, and delayed and disrupted communication with ground-based medical care providers. These constraints require a paradigm shift from current medical care where crews rely on the real-time communications with ground-based medical care providers toward Earth-independent medical operations for astronaut medical care. Medical expertise and decision-making are ground-based for current International Space Station and planned Lunar missions. However, a deep space exploration crew will need to autonomously perform the detection, diagnosis, treatment, and prevention of medical conditions. One approach to provide Earth-independent medical operations is to augment the requisite knowledge, skills, and abilities (KSAs) of a time-constrained crew—operating under stressful conditions, combatting fatigue, and facing a potential medical crisis—with a robust clinical decision support system (CDSS). The CDSS is envisioned as an integrated, software-based tool deployed on a laptop computer or handheld device. The CDSS will assist the crew and ground support when interacting with knowledge/data bases (e.g. records, pharmacy, schedule), instrumentation (e.g. imaging, physiological monitoring devices), and habitat (e.g. wellness system, task performance system) and vehicle systems (e.g. environmental system, communication system). In addition, the human interface will employ a context-based approach that accounts for the crew’s situation. Thus, extraneous and clinically/operationally non-relevant information are reduced to avoid an increase in cognitive load. The framework of an ideal spaceflight CDSS is to include core and advanced analytical features that maintain a flexible platform for integrating new technology in the future. The Exploration Medical Capability (ExMC) Element of the Human Research Program (HRP) is expanding the boundaries of space medical systems to advance the care of astronauts on future exploration missions beyond low Earth orbit by actively identifying and testing next-generation medical care and crew health maintenance technologies. The Clinical Decision Support (CDS) project addressed ap Medical-701 within the Inflight Medical Conditions risk: “We need to increase inflight medical capabilities and identify new capabilities that (a) maximize benefit and/or (b) reduce “costs” on human system/mission/vehicle resources.” Though mass, volume, and power will face increasing constraints, the projected computational capabilities of spacecraft systems will increase exponentially as information technology advances in this decade and beyond. Hence, data, software, and computational resources will play an essential and synergistic role in maintaining crew health, wellness, and performance in deep space missions. The focus of the CDS project was to develop recommended requirements for an in-vehicle CDSS that acts as a ‘virtual assistant’ for delivering optimal health, performance, and medical care during exploration missions. In fiscal year 2022 (FY22), the CDS project was chartered to baseline and/or revise all CDS project related documentation and update the CDS project model to include the revised CDSS Concept of Operations, revised systems-based modeling language (SysML) activity diagrams, and baseline requirements. The focus of this presentation will be an overview of the CDS products and CDS model content.

Decision Support↗

Charge transfer and optical properties of wurtzite-type ZnS/(CdS/ZnS){sub n} (n = 2, 4, 8) superlattices

Graphical abstract: (a) Normalized temperature-dependent PL spectra of ZnS/(CdS/ZnS){sub 4} superlattices from 5 to 300 K and (b) schematic of charge transfer at CdS/ZnS interface. - Highlights: • Wurtzite ZnS/(CdS/ZnS){sub n} superlattices were prepared at 100 °C by pulsed laser deposition. • Surface phonon of ZnS and multiple phonons modes of ZnS and CdS were observed. • The charge transfer of electrons from CdS electron to ZnS holes by excitation energy was found. - Abstract: ZnS/(CdS/ZnS){sub n} (n = 2, 4, 8) superlattices were deposited on sapphire substrate by pulsed laser deposition (PLD) with alternate cadmium sulfide (CdS) and zinc sulfide (ZnS) crystals at 100 °C. The prepared samples with an average thickness of ∼30 nm for ZnS layer and ∼60 nm for CdS layer have a wurtzite-type structure. Surface phonon of ZnS and multiple phonons modes for ZnS and CdS were observed from Raman spectra. PL spectra show a strong green emission at ∼496 nm, two weak emission bands at ∼400 and ∼577 nm, where the emission band at 400 nm was attributed to the recombination of surface defects states to valence, the emission band at 577 nm as the recombination of Cd{sub i}–V{sub Cd} centers, and the strong emission at ∼496 nm is from the charge transfer of electrons from CdS electron to ZnS holes by excitation energy.

36 MATERIALS SCIENCE↗

Synthesis and characterization of CdS/BiPO{sub 4} heterojunction photocatalyst

Highlights: • A CdS/BiPO{sub 4} heterojunction was prepared by the solvothermal method. • The CdS/BiPO{sub 4} composite has the higher photocatalytic activity than the individual ones. • The optimal mass ratio of CdS to BiPO{sub 4} was 0.5. • The heterojunction structure of CdS/BiPO{sub 4} induces an effective electron–hole separation. - Abstract: A series of CdS/BiPO{sub 4} heterojunction photocatalysts with the visible-light response were synthesized by the solvothermal method. The resulting products were characterized by X-ray diffraction, Transmission electron microscopy, X-ray photoelectron spectroscopy, and UV–vis diffuse reflection spectroscopy. CdS nanoparticles with the size at range of 5–7 nm were immobilized on the surface of BiPO{sub 4} nanorods. The CdS/BiPO{sub 4} composite exhibited much higher photodegradation rate of methylene blue under visible light irradation compared to the pure CdS and BiPO{sub 4}. The optimal mass ratio of CdS to BiPO{sub 4} was 0.5, the photodegradation rate of which is 2.1 times higher than that of CdS. The enhancement of photocatalytic activity is attributed to the heterojunction structure of CdS/BiPO{sub 4} composite which induced the effective electron–hole separation between CdS and BiPO{sub 4}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effective shuttling of photoexcitons on CdS/NiO core/shell photocatalysts for enhanced photocatalytic hydrogen production

Highlights: • CdS/NiO leaf-like morphology was prepared by hydrothermal, citrate mediated growth. • CdS/NiO hierarchical catalyst showed improved rate of photocatalytic H{sub 2} generation. • CdS/NiO showed 2 folds higher rate of H{sub 2} production than CdS under visible light irradiation. • Optimized catalyst showed good stability for 30 h of continuous irradiation. - Abstract: Hierarchical structure of NiO immobilized on CdS photocatalyst (CdS/NiO) was synthesized for stable and efficient H{sub 2} production. The catalyst is designed to suppress the photo-corrosion behaviour without affecting catalytic activity of CdS structures having tamarind leaf-like morphology is protected by fabricating thin-layer of NiO. The exterior thin-layer transmits the light into CdS in-turn exciton moved to surface for reaction with adsorbed reactant species. Structural, morphological and optical properties were studied using X-ray diffraction (XRD), ultraviolet-visible light (UV–vis) diffuse reflectance spectra (DRS), high resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS). The results illustrates that synthesized catalyst composed of crystalline CdS/NiO hierarchical structure that absorbs light in the visible spectrum and improved charge carrier separation than CdS or NiO alone. The photocatalytic activity was examined for H{sub 2} generation under visible light irradiation using Xe-lamp as light source. In order to achieve enhanced H{sub 2} production rate amount of NiO loading was optimized and results were found in the following order CdS/NiO > CdS. Under optimal conditions the catalyst showed stable H{sub 2} evolution for 30 h of continuous irradiation. Under optimal conditions catalyst showed visible light to H{sub 2} conversion efficiency of 6.63%.

36 MATERIALS SCIENCE↗

Band alignment of front contact layers for high-efficiency CdTe solar cells

Resistive oxide materials play an important role in the front contact of CdTe solar cells. The high-resistance transparent (HRT) or “buffer” layer has been used extensively in CdTe thin-film photovoltaics to enable a reduction in CdS thickness while maintaining near-maximum device voltage and fill factor. SnO 2 - and ZnO-based alloys were tested as HRT layers on a fluorine-doped tin oxide transparent conducting oxide. SnO 2 -based alloy HRT layers were deposited via atmospheric pressure chemical vapor deposition (APCVD). Alloying ZnO with MgO to create MgxZn 1–x O (MZO) via radio-frequency sputter deposition was explored as a way to reduce the electron affinity of ZnO HRT layers. Additionally, to fully understand the behavior of these materials, many devices were fabricated with either no CdS layer, a sublimated CdS layer, or a sputtered, oxygenated CdS layer. MZO layers resulted in high open-circuit voltage and device efficiency even with the complete elimination of the CdS layer. In both HRT systems, controlling electron affinity to optimize front contact band alignment is an important consideration. Band measurements using photoelectron spectroscopy and synchrotron techniques correlate band alignment measurements with efficiency parameters in the design of HRT and CdS layers.

14 SOLAR ENERGY↗

Mechanistic Insights into Dinitrogen Reduction to Ammonia in Light-Controlled Nanocrystal:Nitrogenase Complexes

Developing systems that can efficiently capture photon energy and convert this energy into fuels and chemicals requires understanding how to assemble molecular components with diverse functions into complete systems possessing selectivity and efficiency in directing charge carriers to catalytic reactions. There are many challenges to achieving this goal. One promising approach is the development of hybrid systems that combine semiconductor nanocrystals (NCs) for light capture and enzymes as efficient catalysts. Such biohybrid systems capitalize on the tunable electronic and optical properties of NCs while leveraging the unmatched specificity and efficiency of enzymes in catalyzing chemical reactions, thereby offering opportunities to surpass the limitations of each component alone. Here, we focus on recent progress in developing a biohybrid system that combines CdS NCs for photon capture with the enzyme nitrogenase to accomplish light-driven dinitrogen (N 2 ) reduction to ammonia (NH 3 ). Integrating light-harvesting materials with biological catalysts requires a deep understanding of NC properties, protein stability, and electron transfer (ET), making it an inherently multidisciplinary problem. The reduction of N 2 to NH 3 is a challenging reaction, with a high demand in both agriculture and industrial chemical production. This reaction is intrinsically energy intensive, due to the need to activate the N≡N triple bond. The current standard industrial approach to N 2 reduction, the Haber−Bosch reaction, obtains the necessary energy input from fossil fuels, whereas biological systems capable of N 2 reduction utilize the hydrolysis of ATP as their energy source. Replacing these costly, energy-intensive inputs with renewable light energy represents a critical step toward sustainable NH 3 production. Recent progress has demonstrated that semiconductor CdS NCs can be coupled to the catalytic component of nitrogenase, the MoFe protein, to form a biohybrid CdS NC:MoFe protein complex, enabling light-driven N 2 reduction rather than energy input from fossil fuels or ATP. This illustrates how inorganic NCs can functionally replace the natural Fe protein partner, yielding a biohybrid catalyst that enables controlled electron delivery and provides not only light-driven NH 3 production but also new approaches for probing enzyme catalytic function. The CdS NC:MoFe protein biohybrid system enables light-initiated electron delivery at ambient temperature, as well as temperatures below freezing, allowing for stabilization and spectroscopic characterization of key reaction intermediates. These findings highlight how photochemical biohybrids can serve as both functional catalysts and mechanistic probes. Beyond studies of the nitrogenase mechanism, studies of the CdS NC:MoFe system reveal how variables such as NC size, electrostatic binding interactions, and sacrificial electron donors (SEDs) govern complex stability, charge transfer efficiency, and catalytic performance. In addition, studies of nitrogenase and the high activation barrier for N 2 reduction are enabling investigations of new and interesting questions regarding the properties and limitations of NC biocatalysis. In this Account, we describe the key features of CdS NC:MoFe protein biohybrids and the parameters for optimal light-driven N 2 reduction, and how controlling ET with light illuminates the path to new insights into the nitrogenase mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cyanine-Incorporated Amorphous Polymeric Carbon Dots for Optical Reactive Oxygen Species Sensing

Reactive oxygen species (ROS) are common cellular oxidants that when overproduced by cellular stressors cause harm to cells. Detection of ROS is of utmost importance to understanding a wide variety of cellular function and toxicity mechanisms. Conventional ROS fluorescence assays involve using a single dye to visualize the ROS quantity. Herein, we describe ROS-sensitive, fluorescent-dye-incorporated carbon dots with dual fluorescence capabilities and good biocompatibility. Carbon dots (CDs) made of citric acid and urea were synthesized with incorporated cyanine-3-amine (Cy3), a bright red fluorescent dye, to create Cy3-CDs. Additionally, to get Cy3 into the ROS-sensitive form, this work demonstrated that Cy3 alone and Cy3 within carbon dots can be electrochemically reduced to their colorless ROS-sensitive form. Cy3, CDs, and Cy3-CDs are all responsive to additions of superoxide, leading to an increase in the fluorescence. Overall, this work examines how O 2 •– and additional oxidizers interact with CDs, Cy3, and Cy3-CDs, and molecular-level hypotheses are explored that will inform the design of future carbon dot-based ROS sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗