Comparison of MAF-32 and a One-Pot Synthesized Superparamagnetic Iron Oxide/MAF-32 Composite for the Adsorption of Diclofenac.

The global presence of pharmaceutical pollutants in water sources represents a burgeoning public health concern. Recent studies underscore the urgency of addressing this class of emerging contaminants. In this context, our work focuses on synthesizing a composite material, FexOy/MAF-32, through a streamlined one-pot reaction process, as an adsorbent for diclofenac, an emerging environmental contaminant frequently found in freshwater environments and linked to potential toxicity towards several organisms such as fish and mussels. A thorough characterization was performed to elucidate the structural composition of the composite. The material presents magnetic properties attributed to its superparamagnetic behavior, which facilitates the recovery efficiency of the composite post-diclofenac adsorption. Our study further involves a comparative analysis between the FexOy/MAF-32 and a non-magnetic counterpart, comprised solely of 2-ethylimidazolate zinc polymer. This comparison aims to discern the relative advantages and disadvantages of incorporating magnetic iron oxide nanoparticles in the contaminant removal process facilitated by a coordination polymer. Our findings reveal that even a minimal incorporation of iron oxide nanoparticles substantially enhanced the composite's overall performance in pollutant adsorption.

Surface Adsorption and Photoinduced Degradation: A Study of Spinel Ferrite Nanomaterials for Removal of a Model Organic Pollutant from Water.

Spinel oxide nanocrystals are attractive materials for photoinduced advanced oxidation processes that degrade organic pollutants in water due to their chemical stability and tunability, visible light absorption, and magnetic recoverability. However, a systematic understanding of the structural and chemical factors that control the reactivity of specific spinel oxide nanocrystal materials toward photoinduced degradation processes is lacking. This Perspective illustrates these knowledge gaps through an investigation into the impacts of surface chemistry and composition of spinel ferrite nanocrystals of formula MFe2O4 (M = Mg, Fe, Co, Ni, Cu, Zn) on their ability to remove a model organic pollutant (methyl orange (MO)) from water. We identify two mechanisms by which the nanocrystals remove MO from water: (i) surface adsorption and (ii) photoinduced degradation under visible light irradiation in the presence of hydrogen peroxide via the photo-Fenton reaction. Nanocrystals that do not contain any surface ligands are more effective at removing MO from water than nanocrystals that contain surface ligands, despite our observation that the ligand-less nanocrystals do not form stable colloidal dispersions in water, while ligand-coated nanocrystals are colloidally stable. For many of the spinel ferrite compositions studied here, the fraction of methyl orange removal via adsorption to the nanocrystal surface in the absence of photoexcitation is larger than the fraction removed under irradiation. Our data indicate that the composition-dependent surface charge of the nanocrystals controls the degree of surface adsorption of the charged MO molecule. Overall, these results demonstrate that careful consideration of the impacts of surface chemistry on the behavior of spinel ferrite nanocrystals is required to accurately assess and subsequently understand their activity toward the photoinduced degradation of organic molecules.

Acidity of Carboxylic Acid Ligands Influences the Formation of VO2(A) and VO2(B) Nanocrystals under Solvothermal Conditions.

Vanadium dioxide (VO2) can adopt many different crystal structures at ambient temperature and pressure, each with different, and often desirable, electronic, optical, and chemical properties. Understanding how to control which crystal phase forms under various reaction conditions is therefore crucial to developing VO2 for various applications. This paper describes the impact of ligand acidity on the formation of VO2 nanocrystals from the solvothermal reaction of vanadyl acetylacetonate (VO(acac)2) with stoichiometric amounts of water. Carboxylic acids examined herein favor the formation of the monoclinic VO2(B) phase over the tetragonal VO2(A) phase as the concentration of water in the reaction increases. However, the threshold concentration of water required to obtain phase-pure VO2(B) nanocrystals increases as the pKa of the carboxylic acid decreases. We also observe that increasing the concentration of VO(acac)2 or the concentration of acid while keeping the concentration of water constant favors the formation of VO2(A). Single-crystal electron diffraction measurements enable the identification of vanadyl carboxylate species formed in reactions that do not contain enough water to promote the formation of VO2. Increasing the length of the carbon chain on aliphatic carboxylic acids did not impact the phase of VO2 nanocrystals obtained but did result in a change from nanorod to nanoplatelet morphology. These results suggest that inhibiting the rate of hydrolysis of the VO(acac)2 precursor either by decreasing the ratio of water to VO(acac)2 or by increasing the fraction of water molecules that are protonated favors the formation of VO2(A) over VO2(B).

Neurofilament light oligomers in neurodegenerative diseases: quantification by homogeneous immunoassay in cerebrospinal fluid.

Background: Neurofilament light (NfL) is a widely used biomarker for neurodegeneration. NfL is prone to oligomerisation, but available assays do not reveal the exact molecular nature of the protein variant measured. The objective of this study was to develop a homogeneous ELISA capable of quantifying oligomeric NfL (oNfL) in cerebrospinal fluid (CSF). Methods: A homogeneous ELISA, based on the same capture and detection antibody (NfL21), was developed and used to quantify oNfL in samples from patients with behavioural variant frontotemporal dementia (bvFTD, n=28), non-fluent variant primary progressive aphasia (nfvPPA, n=23), semantic variant PPA (svPPA, n=10), Alzheimer's disease (AD, n=20) and healthy controls (n=20). The nature of NfL in CSF, and the recombinant protein calibrator, was also characterised by size exclusion chromatography (SEC). Results: CSF concentration of oNfL was significantly higher in nfvPPA (p<0.0001) and svPPA patients (p<0.05) compared with controls. CSF oNfL concentration was also significantly higher in nfvPPA compared with bvFTD (p<0.001) and AD (p<0.01) patients. SEC data showed a peak fraction compatible with a full-length dimer (~135 kDa) in the in-house calibrator. For CSF, the peak was found in a fraction of lower molecular weight (~53 kDa), suggesting dimerisation of NfL fragments. Conclusions: The homogeneous ELISA and SEC data suggest that most of the NfL in both the calibrator and human CSF is present as a dimer. In CSF, the dimer appears to be truncated. Further studies are needed to determine its precise molecular composition.

Polaronic optical transitions in hematite (α-Fe2O3) revealed by first-principles electron-phonon coupling.

Polaron formation following optical absorption is a key process that defines the photophysical properties of many semiconducting transition metal oxides, which comprise an important class of materials with potential optoelectronic and photocatalytic applications. In this work, we use hematite (α-Fe2O3) as a model transition metal oxide semiconductor to demonstrate the feasibility of direct optical population of band edge polaronic states. We employ first-principles electron-phonon computations within the framework of the density functional theory+U+J method to reveal the presence of these states within a thermal distribution of phonon displacements and model their evolution with temperature. Our computations reproduce the temperature dependence of the optical dielectric function of hematite with remarkable accuracy and indicate that the band edge optical absorption and second-order resonance Raman spectra arise from polaronic optical transitions involving coupling to longitudinal optical phonons with energies greater than 50 meV. Additionally, we find that the resulting polaron comprises an electron localized to two adjacent Fe atoms with distortions that lie primarily along the coordinates of phonons with energies of 31 and 81 meV.

CSF glial markers are elevated in a subset of patients with genetic frontotemporal dementia.

BACKGROUND: Neuroinflammation has been shown to be an important pathophysiological disease mechanism in frontotemporal dementia (FTD). This includes activation of microglia, a process that can be measured in life through assaying different glia-derived biomarkers in cerebrospinal fluid. However, only a few studies so far have taken place in FTD, and even fewer focusing on the genetic forms of FTD. METHODS: We investigated the cerebrospinal fluid concentrations of TREM2, YKL-40 and chitotriosidase using immunoassays in 183 participants from the Genetic FTD Initiative (GENFI) study: 49 C9orf72 (36 presymptomatic, 13 symptomatic), 49 GRN (37 presymptomatic, 12 symptomatic) and 23 MAPT (16 presymptomatic, 7 symptomatic) mutation carriers and 62 mutation-negative controls. Concentrations were compared between groups using a linear regression model adjusting for age and sex, with 95% bias-corrected bootstrapped confidence intervals. Concentrations in each group were correlated with the Mini-Mental State Examination (MMSE) score using non-parametric partial correlations adjusting for age. Age-adjusted z-scores were also created for the concentration of markers in each participant, investigating how many had a value above the 95th percentile of controls. RESULTS: Only chitotriosidase in symptomatic GRN mutation carriers had a concentration significantly higher than controls. No group had higher TREM2 or YKL-40 concentrations than controls after adjusting for age and sex. There was a significant negative correlation of chitotriosidase concentration with MMSE in presymptomatic GRN mutation carriers. In the symptomatic groups, for TREM2 31% of C9orf72, 25% of GRN, and 14% of MAPT mutation carriers had a concentration above the 95th percentile of controls. For YKL-40 this was 8% C9orf72, 8% GRN and 0% MAPT mutation carriers, whilst for chitotriosidase it was 23% C9orf72, 50% GRN, and 29% MAPT mutation carriers. CONCLUSIONS: Although chitotriosidase concentrations in GRN mutation carriers were the only significantly raised glia-derived biomarker as a group, a subset of mutation carriers in all three groups, particularly for chitotriosidase and TREM2, had elevated concentrations. Further work is required to understand the variability in concentrations and the extent of neuroinflammation across the genetic forms of FTD. However, the current findings suggest limited utility of these measures in forthcoming trials.

Controlling Cation Distribution and Morphology in Colloidal Zinc Ferrite Nanocrystals.

This paper describes the first synthetic method to achieve independent control over both the cation distribution (quantified by the inversion parameter x) and size of colloidal ZnFe2O4 nanocrystals. Use of a heterobimetallic triangular complex of formula ZnFe2(µ3-O)(µ2-O2CCF3)6(H2O)3 as a single-source precursor, solvothermal reaction conditions, absence of hydroxyl groups from the reaction solvent, and the presence of oleylamine are required to achieve well-defined, crystalline, and monodisperse ZnFe2O4 nanoparticles. The size of the ZnFe2O4 nanocrystals increases as the ratio of oleic acid and oleylamine ligands to precursor increases. The inversion parameter increases with increasing solubility of the precursor in the reaction solvent, with the presence of oleic acid in the reaction mixture, and with decreasing reaction temperature. These results are consistent with a mechanism in which ligand exchange between oleic acid and carboxylate ligands bound to the precursor complex influences the degree to which the reaction produces a kinetically trapped or thermodynamically stable cation distribution. Importantly, these results indicate that preservation of the triangular Zn-O-Fe2 core structure of the precursor in the reactive monomer species is crucial to the production of a phase-pure ZnFe2O4 product and to the ability to tune the cation distribution. Overall, these results demonstrate the advantages of using a single-source precursor and solvothermal reaction conditions to achieve synthetic control over the structure of ternary spinel ferrite nanocrystals.

Development of a sensitive trial-ready poly(GP) CSF biomarker assay for C9orf72-associated frontotemporal dementia and amyotrophic lateral sclerosis.

OBJECTIVE: A GGGGCC repeat expansion in the C9orf72 gene is the most common cause of genetic frontotemporal dementia (FTD) and amyotrophic lateral sclerosis (ALS). As potential therapies targeting the repeat expansion are now entering clinical trials, sensitive biomarker assays of target engagement are urgently required. Our objective was to develop such an assay. METHODS: We used the single molecule array (Simoa) platform to develop an immunoassay for measuring poly(GP) dipeptide repeat proteins (DPRs) generated by the C9orf72 repeat expansion in cerebrospinal fluid (CSF) of people with C9orf72-associated FTD/ALS. RESULTS AND CONCLUSIONS: We show the assay to be highly sensitive and robust, passing extensive qualification criteria including low intraplate and interplate variability, a high precision and accuracy in measuring both calibrators and samples, dilutional parallelism, tolerance to sample and standard freeze-thaw and no haemoglobin interference. We used this assay to measure poly(GP) in CSF samples collected through the Genetic FTD Initiative (N=40 C9orf72 and 15 controls). We found it had 100% specificity and 100% sensitivity and a large window for detecting target engagement, as the C9orf72 CSF sample with the lowest poly(GP) signal had eightfold higher signal than controls and on average values from C9orf72 samples were 38-fold higher than controls, which all fell below the lower limit of quantification of the assay. These data indicate that a Simoa-based poly(GP) DPR assay is suitable for use in clinical trials to determine target engagement of therapeutics aimed at reducing C9orf72 repeat-containing transcripts.

How do we engage people in testing for COVID-19? A rapid qualitative evaluation of a testing programme in schools, GP surgeries and a university.

BACKGROUND: The UK Scientific Advisory Group for Emergencies (SAGE) emphasises the need for high levels of engagement with communities and individuals to ensure the effectiveness of any COVID-19 testing programme. A novel pilot health surveillance programme to assess the feasibility of weekly community RT-LAMP (Reverse transcription loop-mediated isothermal amplification) testing for the SARS-CoV-2 virus using saliva samples collected at home was developed and piloted by the University of Southampton and Southampton City Council. METHODS: Rapid qualitative evaluation was conducted to explore experiences of those who took part in the programme, of those who declined and of those in the educational and healthcare organisations involved in the pilot testing who were responsible for roll-out. This included 77 interviews and 20 focus groups with 223 staff, students, pupils and household members from four schools, one university, and one community healthcare NHS trust. The insights generated and informed the design and modification of the Southampton COVID-19 Saliva Testing Programme and the next phase of community-testing. RESULTS: Discussions revealed that high levels of communication, trust and convenience were necessary to ensure people's engagement with the programme. Participants felt reassured by and pride in taking part in this novel programme. They suggested modifications to reduce the programme's environmental impact and overcome cultural barriers to participation. CONCLUSIONS: Participants' and stakeholders' motivations, challenges and concerns need to be understood and these insights used to modify the programme in a continuous, real-time process to ensure and sustain engagement with testing over the extended period necessary. Community leaders and stakeholder organisations should be involved throughout programme development and implementation to optimise engagement.

Modelling local structural and electronic consequences of proton and hydrogen-atom uptake in VO2 with polyoxovanadate clusters.

We report the synthesis and characterisation of a series of siloxide-functionalised polyoxovanadate-alkoxide (POV-alkoxide) clusters, [V6O6(OSiMe3)(OMe)12] n (n = 1-, 2-), that serve as molecular models for proton and hydrogen-atom uptake in vanadium dioxide, respectively. Installation of a siloxide moiety on the surface of the Lindqvist core was accomplished via addition of trimethylsilyl trifluoromethylsulfonate to the fully-oxygenated cluster [V6O7(OMe)12]2-. Characterisation of [V6O6(OSiMe3)(OMe)12]1- by X-ray photoelectron spectroscopy reveals that the incorporation of the siloxide group does not result in charge separation within the hexavanadate assembly, an observation that contrasts directly with the behavior of clusters bearing substitutional dopants. The reduced assembly, [V6O6(OSiMe3)(OMe)12]2-, provides an isoelectronic model for H-doped VO2, with a vanadium(iii) ion embedded within the cluster core. Notably, structural analysis of [V6O6(OSiMe3)(OMe)12]2- reveals bond perturbations at the siloxide-functionalised vanadium centre that resemble those invoked upon H-atom uptake in VO2 through ab initio calculations. Our results offer atomically precise insight into the local structural and electronic consequences of the installation of hydrogen-atom-like dopants in VO2, and challenge current perspectives of the operative mechanism of electron-proton co-doping in these materials.

Evaluation of electrochemical properties of nanostructured metal oxide electrodes immersed in redox-inactive organic media.

This paper describes analysis of dropcast nanocrystalline and electrochemically deposited films of NiO and α-Fe2O3 as model metal oxide semiconductors immersed in redox-inactive organic electrolyte solutions using electrochemical impedance spectroscopy (EIS). Although the data reported here fit a circuit commonly used to model EIS data of metal oxide electrodes, which comprises an RC circuit nested inside a second RC circuit that is in series with a resistor, our interpretation of the physical meaning of these circuit elements differs from that applied to EIS measurements of metal oxide electrodes immersed in redox-active media. The data presented here are most consistent with an interpretation in which the nested RC circuit represents charge transfer between the metal oxide film and the underlying metal electrode, and the non-nested RC circuit represents the resistance and capacitance associated with formation of a charge-compensating double-layer at the exposed interface between the metal electrode and electrolyte solution. Applying this interpretation to analysis of EIS data collected for metal oxide films in organic media enables the impact of film morphology on electrochemical behavior to be distinguished from the effects of the intrinsic electronic structure of the metal oxide. This distinction is crucial to the evaluation of nanostructured metal oxide electrodes for electrochemical energy storage and electrocatalysis applications.

Thermally Activated Optical Absorption into Polaronic States in Hematite.

Polaron formation, whereby an electron or hole strongly couples to a lattice distortion, inhibits the carrier mobility of many first-row transition metal oxide semiconductors. Recently reported XUV transient absorption measurements of hematite (α-Fe2O3) demonstrate formation of electron small polarons upon photoexcitation into an undistorted charge-transfer state followed by subpicosecond lattice reorganization. Here, we show that polaronic states of hematite can be accessed directly via optical transitions from the ground state in a thermally activated lattice. Thermal difference spectra collected from 30 to 573 K combined with Stokes resonance Raman spectra indicate strong coupling between optical transitions near the band-edge (2.1-2.3 eV) and zone-center a1g and longitudinal (LO) optical phonons. Density functional theory calculations of the electronic and vibrational structures of pristine and polaron-distorted hematite lattices confirm that the geometric distortion corresponding to electron small polaron formation lies along the 28-meV a1g and 81-meV LO phonon coordinates and reproduce the features observed in the experimental thermal difference and resonance Raman spectra.

Cation Distribution in Spinel Ferrite Nanocrystals: Characterization, Impact on their Physical Properties, and Opportunities for Synthetic Control.

Metal oxide materials that adopt the spinel crystal structure, such as metal ferrites (MFe2O4), present tetrahedral (A) and octahedral [B] sublattice sites surrounded by oxygen anions that provide a relatively weak crystal-field splitting. The formula of a metal ferrite material is most precisely described as (M1-xFex)[MxFe2-x]O4, where the parentheses and square brackets denote the tetrahedral and octahedral sites, respectively, and x is the inversion parameter quantifying the distribution of M2+ and Fe3+ cations among these sites. The electronic, magnetic, and optical properties of spinel ferrites all depend on the magnitude of x, which, in turn, depends on the relative sizes of the cations, their charge, and the relative crystal-field stabilization afforded by tetrahedral or octahedral coordination. Compared to bulk spinel ferrites, the large surface-area-to-volume ratio of spinel ferrite nanocrystals provides additional structural degrees of freedom that enable access to a broader range of x values. Achieving synthetic control over the degree of inversion in addition to the size and shape is critical to tuning the properties of spinel ferrite nanocrystals. In this Forum Article, we review physical inorganic methods used to quantify x in spinel ferrite nanocrystals, describe how the electronic, magnetic, and optical properties of these nanocrystals depend on x, and discuss emerging strategies for achieving synthetic control over this parameter.

Heterometallic trinuclear oxo-centered clusters as single-source precursors for synthesis of stoichiometric monodisperse transition metal ferrite nanocrystals.

The use of heterobimetallic metal complexes as molecular single-source precursors is a promising strategy for the targeted synthesis of phase-pure stoichiometric ternary metal oxide nanocrystals. However, the design and synthesis of these precursors is not trivial and can require considerable effort. Using spinel metal ferrite nanocrystals of formula MFe2O4 (M = Fe2+, Co2+, Ni2+, Cu2+, and Zn2+) as a model system, this paper evaluates the efficacy of the single-source precursor approach by comparing directly nanocrystals synthesized from the solvothermal reaction of heterobimetallic trinuclear oxo-bridged clusters of formula MIIFeIII2(µ3-O)(µ2-O2CR)6(H2O)3, R = CF3 to nanocrystals synthesized from the solvothermal reaction of stoichiometric mixtures of multi-source precursors, such as metal acetate or nitrate salts. For each M explored here, the clusters form phase-pure MFe2O4 nanocrystals with significantly narrower size distributions than nanocrystals synthesized from multi-source-precursors. In the case of M = Cu, the multi-source metal salt precursors produce a mixture of CuO and CuFe2O4. Additionally, changing the electronic nature of the R-group on the bridging carboxylate ligand from electron withdrawing (CF3) to electron donating (CH3 or C(CH3)3) decreases the average diameter of the resulting nanocrystals by a factor of two. The cluster molecules therefore offer superior control over both morphology and composition for transition metal ferrite nanocrystals. We hypothesize that this remarkable performance arises from the presence of pre-formed M2+-O-Fe3+ moieties in the cluster molecules that enable direct nucleation of MFe2O4 and preclude nucleation of binary oxide impurities.

Strong Dependence of Quantum-Dot Delayed Luminescence on Excitation Pulse Width.

Delayed luminescence involving charge-carrier trapping and detrapping has recently been identified as a widespread and possibly universal phenomenon in colloidal quantum dots. Its near-power-law decay suggests a relationship with blinking. Here, using colloidal CuInS2 and CdSe quantum dots as model systems, we show that short (nanosecond) excitation pulses yield less delayed luminescence intensity and faster delayed luminescence decay than observed with long (millisecond) square-wave excitation pulses. Increasing the excitation power also affects the delayed luminescence intensity, but the delayed luminescence decay kinetics appear much less sensitive to excitation power than to excitation pulse width. An idealized four-state kinetic model reproduces the major experimental trends and highlights the very slow approach to steady state during photoexcitation, stemming from extremely slow detrapping of the metastable charge-separated state responsible for delayed luminescence. The impacts of these findings on proposed relationships between delayed luminescence and blinking are discussed.

Luminescent Colloidal Semiconductor Nanocrystals Containing Copper: Synthesis, Photophysics, and Applications.

Copper-doped semiconductors are classic phosphor materials that have been used in a variety of applications for many decades. Colloidal copper-doped semiconductor nanocrystals have recently attracted a great deal of interest because they combine the solution processability and spectral tunability of colloidal nanocrystals with the unique photoluminescence properties of copper-doped semiconductor phosphors. Although ternary and quaternary semiconductors containing copper, such as CuInS2 and Cu2ZnSnS4, have been studied primarily in the context of their photovoltaic applications, when synthesized as colloidal nanocrystals, these materials have photoluminescence properties that are remarkably similar to those of copper-doped semiconductor nanocrystals. This review focuses on the luminescent properties of colloidal copper-doped, copper-based, and related copper-containing semiconductor nanocrystals. Fundamental investigations into the luminescence of copper-containing colloidal nanocrystals are reviewed in the context of the well-established luminescence mechanisms of bulk copper-doped semiconductors and copper(I) molecular coordination complexes. The use of colloidal copper-containing nanocrystals in applications that take advantage of their luminescent properties, such as bioimaging, solid-state lighting, and luminescent solar concentrators, is also discussed.

Singlet-Triplet Splittings in the Luminescent Excited States of Colloidal Cu(+):CdSe, Cu(+):InP, and CuInS2 Nanocrystals: Charge-Transfer Configurations and Self-Trapped Excitons.

The electronic and magnetic properties of the luminescent excited states of colloidal Cu(+):CdSe, Cu(+):InP, and CuInS2 nanocrystals were investigated using variable-temperature photoluminescence (PL) and magnetic circularly polarized luminescence (MCPL) spectroscopies. The nanocrystal electronic structures were also investigated by absorption and magnetic circular dichroism (MCD) spectroscopies. By every spectroscopic measure, the luminescent excited states of all three materials are essentially indistinguishable. All three materials show very similar broad PL line widths and large Stokes shifts. All three materials also show similar temperature dependence of their PL lifetimes and MCPL polarization ratios. Analysis shows that this temperature dependence reflects Boltzmann population distributions between luminescent singlet and triplet excited states with average singlet-triplet splittings of ∼1 meV in each material. These similarities lead to the conclusion that the PL mechanism in CuInS2 NCs is fundamentally different from that of bulk CuInS2 and instead is the same as that in Cu(+)-doped NCs, which are known to luminesce via charge-transfer recombination of conduction-band electrons with copper-localized holes. The luminescence of CuInS2 nanocrystals is explained well by invoking exciton self-trapping, in which delocalized photogenerated holes contract in response to strong vibronic coupling at lattice copper sites to form a luminescent excited state that is essentially identical to that of the Cu(+)-doped semiconductor nanocrystals.

Electronic doping and redox-potential tuning in colloidal semiconductor nanocrystals.

Electronic doping is one of the most important experimental capabilities in all of semiconductor research and technology. Through electronic doping, insulating materials can be made conductive, opening doors to the formation of p-n junctions and other workhorses of modern semiconductor electronics. Recent interest in exploiting the unique physical and photophysical properties of colloidal semiconductor nanocrystals for revolutionary new device technologies has stimulated efforts to prepare electronically doped colloidal semiconductor nanocrystals with the same control as available in the corresponding bulk materials. Despite the impact that success in this endeavor would have, the development of general and reliable methods for electronic doping of colloidal semiconductor nanocrystals remains a long-standing challenge. In this Account, we review recent progress in the development and characterization of electronically doped colloidal semiconductor nanocrystals. Several successful methods for introducing excess band-like charge carriers are illustrated and discussed, including photodoping, outer-sphere electron transfer, defect doping, and electrochemical oxidation or reduction. A distinction is made between methods that yield excess band-like carriers at thermal equilibrium and those that inject excess charge carriers under thermal nonequilibrium conditions (steady state). Spectroscopic signatures of such excess carriers, accessible by both equilibrium and nonequilibrium methods, are reviewed and illustrated. A distinction is also proposed between the phenomena of electronic doping and redox-potential shifting. Electronically doped semiconductor nanocrystals possess excess band-like charge carriers at thermal equilibrium, whereas redox-potential shifting affects the potentials at which charge carriers are injected under nonequilibrium conditions, without necessarily introducing band-like charge carriers at equilibrium. Detection of the key spectroscopic signatures of band-like carriers allows distinction between these two regimes. Both electronic doping and redox-potential shifting can be powerful tools for tuning the performance of nanocrystals in electronic devices. Finally, key chemical challenges associated with nanocrystal electronic doping are briefly discussed. These challenges are centered largely on the availability of charge-carrier reservoirs with suitable redox potentials and on the relatively poor control over nanocrystal surface traps. In most cases, the Fermi levels of colloidal nanocrystals are defined by the redox properties of their surface traps. Control over nanocrystal surface chemistries is therefore essential to the development of general and reliable strategies for electronically doping colloidal semiconductor nanocrystals. Overall, recent progress in this area portends exciting future advances in controlling nanocrystal compositions, surface chemistries, redox potentials, and charge states to yield new classes of electronic nanomaterials with attractive physical properties and the potential to stimulate unprecedented new semiconductor technologies.

Photoluminescence Blinking and Reversible Electron Trapping in Copper-Doped CdSe Nanocrystals.

Single-particle photoluminescence blinking is observed in the copper-centered deep-trap luminescence of copper-doped CdSe (Cu(+):CdSe) nanocrystals. Blinking dynamics for Cu(+):CdSe and undoped CdSe nanocrystals are analyzed to identify the effect of Cu(+), which selectively traps photogenerated holes. Analysis of the blinking data reveals that the Cu(+):CdSe and CdSe nanocrystal "off"-state dynamics are statistically identical, but the Cu(+):CdSe nanocrystal "on" state is shorter lived. Additionally, a new and pronounced temperature-dependent delayed luminescence is observed in the Cu(+):CdSe nanocrystals that persists long beyond the radiative lifetime of the luminescent excited state. This delayed luminescence is analogous to the well-known donor-acceptor pair luminescence of bulk copper-doped phosphors and is interpreted as revealing metastable charge-separated excited states formed by reversible electron trapping at the nanocrystal surfaces. A mechanistic link between this delayed luminescence and the luminescence blinking is proposed. Collectively, these data suggest that electron (rather than hole) trapping/detrapping is responsible for photoluminescence intermittency in these nanocrystals.