Showing papers in "Journal of the American Chemical Society in 2008"
TL;DR: It is reported that a layered iron-based compound LaOFeAs undergoes superconducting transition under doping with F- ions at the O2- site and exhibits a trapezoid shape dependence on the F- content.
Abstract: We report that a layered iron-based compound LaOFeAs undergoes superconducting transition under doping with F- ions at the O2- site. The transition temperature (Tc) exhibits a trapezoid shape dependence on the F- content, with the highest Tc of ∼26 K at ∼11 atom %.
6,643 citations
TL;DR: The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.
Abstract: Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation Their unique properties are based on the molecular-scale porous character However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications Metal organic frameworks (MOFs) provided a breakthrough in this respect New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability The high stability is based on the combination of strong Zr−O bonds and the ability of the inner Zr6-cluster to rearrange reversibly upon removal or addition of μ3-OH groups, without any changes in the connecting carbox
4,958 citations
TL;DR: The results showed that graphene is a novel class of material promising for biological applications including future in vivo cancer treatment with various aromatic, low-solubility drugs.
Abstract: It is known that many potent, often aromatic drugs are water insoluble, which has hampered their use for disease treatment. In this work, we functionalized nanographene oxide (NGO), a novel graphitic material, with branched polyethylene glycol (PEG) to obtain a biocompatible NGO−PEG conjugate stable in various biological solutions, and used them for attaching hydrophobic aromatic molecules including a camptothecin (CPT) analogue, SN38, noncovalently via π−π stacking. The resulting NGO−PEG−SN38 complex exhibited excellent water solubility while maintaining its high cancer cell killing potency similar to that of the free SN38 molecules in organic solvents. The efficacy of NGO−PEG−SN38 was far higher than that of irinotecan (CPT-11), a FDA-approved water soluble SN38 prodrug used for the treatment of colon cancer. Our results showed that graphene is a novel class of material promising for biological applications including future in vivo cancer treatment with various aromatic, low-solubility drugs.
3,217 citations
TL;DR: The work presented here will not only open a new way for preparing water-soluble graphene dispersions but also provide a general route for fabricating conducting films based on graphene.
Abstract: Flexible graphene films were prepared by the filtration of water-soluble noncovalently functionalized graphene sheets with pyrenebutyrate. The work presented here will not only open a new way for preparing water-soluble graphene dispersions but also provide a general route for fabricating conducting films based on graphene.
3,079 citations
TL;DR: A general approach to EDLC design leading to the maximum energy density is suggested, which has been now proved for both solvated organic salts and solvent-free liquid electrolytes.
Abstract: The research on electrochemical double layer capacitors (EDLC), also known as supercapacitors or ultracapacitors, is quickly expanding because their power delivery performance fills the gap between dielectric capacitors and traditional batteries. However, many fundamental questions, such as the relations between the pore size of carbon electrodes, ion size of the electrolyte, and the capacitance have not yet been fully answered. We show that the pore size leading to the maximum double-layer capacitance of a TiC-derived carbon electrode in a solvent-free ethyl-methylimmidazolium-bis(trifluoro-methane-sulfonyl)imide (EMI-TFSI) ionic liquid is roughly equal to the ion size (∼0.7 nm). The capacitance values of TiC−CDC produced at 500 °C are more than 160 F/g and 85 F/cm3 at 60 °C, while standard activated carbons with larger pores and a broader pore size distribution present capacitance values lower than 100 F/g and 50 F/cm3 in ionic liquids. A significant drop in capacitance has been observed in pores that w...
1,913 citations
TL;DR: An unusual single crystal structure of a 25-gold-atom cluster protected by eighteen phenylethanethiol ligands is reported, which violates the empirical golden rule "cluster of clusters", and is in good correspondence with time-dependent density functional theory calculations for the observed structure.
Abstract: The total structure determination of thiol-protected Au clusters has long been a major issue in cluster research. Herein, we report an unusual single crystal structure of a 25-gold-atom cluster (1.27 nm diameter, surface-to-surface distance) protected by eighteen phenylethanethiol ligands. The Au25 cluster features a centered icosahedral Au13 core capped by twelve gold atoms that are situated in six pairs around the three mutually perpendicular 2-fold axes of the icosahedron. The thiolate ligands bind to the Au25 core in an exclusive bridging mode. This highly symmetric structure is distinctly different from recent predictions of density functional theory, and it also violates the empirical golden rule—“cluster of clusters”, which would predict a biicosahedral structure via vertex sharing of two icosahedral M13 building blocks as previously established in various 25-atom metal clusters protected by phosphine ligands. These results point to the importance of the ligand−gold core interactions. The Au25(SR)1...
1,905 citations
TL;DR: This communication presents the recent results that the activity of photocatalytic H2 production can be significantly enhanced when a small amount of MoS2 is loaded on CdS as cocatalyst.
Abstract: This communication presents our recent results that the activity of photocatalytic H2 production can be significantly enhanced when a small amount of MoS2 is loaded on CdS as cocatalyst. The MoS2/CdS catalysts show high rate of H2 evolution from photocatalytic re-forming of lactic acid under visible light irradiation. The rate of H2 evolution on CdS is increased by up to 36 times when loaded with only 0.2 wt % of MoS2, and the activity of MoS2/CdS is even higher than those of the CdS photocatalysts loaded with different noble metals, such as Pt, Ru, Rh, Pd, and Au. The junction formed between MoS2 and CdS and the excellent H2 activation property of MoS2 are supposed to be responsible for the enhanced photocatalytic activity of MoS2/CdS.
1,733 citations
TL;DR: Two major findings are highlighted: ability to tune the photoelectrochemical response and photoconversion efficiency via size control of CdSe quantum dots and improvement in the photoconversions efficiency by facilitating the charge transport through TiO2 nanotube architecture.
Abstract: Different-sized CdSe quantum dots have been assembled on TiO2 films composed of particle and nanotube morphologies using a bifunctional linker molecule. Upon band-gap excitation, CdSe quantum dots inject electrons into TiO2 nanoparticles and nanotubes, thus enabling the generation of photocurrent in a photoelectrochemical solar cell. The results presented in this study highlight two major findings: (i) ability to tune the photoelectrochemical response and photoconversion efficiency via size control of CdSe quantum dots and (ii) improvement in the photoconversion efficiency by facilitating the charge transport through TiO2 nanotube architecture. The maximum IPCE (photon-to-charge carrier generation efficiency) obtained with 3 nm diameter CdSe nanoparticles was 35% for particulate TiO2 and 45% for tubular TiO2 morphology. The maximum IPCE observed at the excitonic band increases with decreasing particle size, whereas the shift in the conduction band to more negative potentials increases the driving force and favors fast electron injection. The maximum power-conversion efficiency
1,608 citations
TL;DR: This study demonstrates that physisorptive materials can achieve affinities and capacities competitive with amine sorbents while greatly reducing the energy cost associated with regeneration.
Abstract: A series of four isostructural microporous coordination polymers (MCPs) differing in metal composition is demonstrated to exhibit exceptional uptake of CO2 at low pressures and ambient temperature. These conditions are particularly relevant for capture of flue gas from coal-fired power plants. A magnesium-based material is presented that is the highest surface area magnesium MCP yet reported and displays ultrahigh affinity based on heat of adsorption for CO2. This study demonstrates that physisorptive materials can achieve affinities and capacities competitive with amine sorbents while greatly reducing the energy cost associated with regeneration.
1,590 citations
TL;DR: Using 1,8-diiodooctane as the processing additive, the efficiency of the BHJ solar cells was improved and the efficiency rating was improved from 3.4% (for the reference device) to 5.1%.
Abstract: Two criteria for processing additives introduced to control the morphology of bulk heterojunction (BHJ) materials for use in solar cells have been identified: (i) selective (differential) solubility of the fullerene component and (ii) higher boiling point than the host solvent. Using these criteria, we have investigated the class of 1,8-di(R)octanes with various functional groups (R) as processing additives for BHJ solar cells. Control of the BHJ morphology by selective solubility of the fullerene component is demonstrated using these high boiling point processing additives. The best results are obtained with R = Iodine (I). Using 1,8-diiodooctane as the processing additive, the efficiency of the BHJ solar cells was improved from 3.4% (for the reference device) to 5.1%.
1,579 citations
TL;DR: Condensation of 1,4-dimethoxybenzene with paraformaldehyde in the presence of BF3.O(C2H5)2 gave novel para-bridged pentacyclic pillar DMB (DMpillar[5]arene), which formed 1:1 host-guest complexes with dialkyl viologen and alkyl pyridinium derivatives.
Abstract: Condensation of 1,4-dimethoxybenzene (DMB) with paraformaldehyde in the presence of BF3·O(C2H5)2 gave novel para-bridged pentacyclic pillar DMB (DMpillar[5]arene). Moreover, para-bridged pentacyclic hydroquinone (pillar[5]arene) was prepared. Pillar[5]arene formed 1:1 host–guest complexes with dialkyl viologen and alkyl pyridinium derivatives. However, pillar[5]arene did not form complexes with the diadamantyl viologen derivative since a bulky adamantyl group was unable to thread the cavity of pillar[5]arene.
TL;DR: By using the unique core-shell microspheres with accessible large pores and excellent magnetic property, a fast removal of microcystins with high efficiency can be achieved.
Abstract: Superparamagnetic microspheres with an Fe3O4@SiO2 core and a perpendicularly aligned mesoporous SiO2 shell were synthesized through a surfactant-templating sol−gel approach. The microspheres possess high magnetization (53.3 emu/g), high surface area (365 m2/g), large pore volume (0.29 cm3/g), and uniform mesopore (2.3 nm). By using the unique core−shell microspheres with accessible large pores and excellent magnetic property, a fast removal of microcystins with high efficiency (>95%) can be achieved.
TL;DR: Porous carbon was synthesized by heating the precursor FA within the pores of MOF-5 to display a high specific surface area and important hydrogen uptake and excellent electrochemical properties as an electrode material for electrochemical double-layered capacitor (EDLC).
Abstract: Porous carbon was synthesized by heating the precursor FA within the pores of MOF-5. The resultant carbon displayed a high specific surface area (BET, 2872 m2·g−1) and important hydrogen uptake (2.6 wt % at 760 Torr, −196 °C) as well as excellent electrochemical properties as an electrode material for electrochemical double-layered capacitor (EDLC).
TL;DR: In each case, the very slow and complete delivery of Ibuprofen was achieved under physiological conditions after 3 weeks with a predictable zero-order kinetics, which highlights the unique properties of flexible hybrid solids for adapting their pore opening to optimize the drug-matrix interactions.
Abstract: Flexible nanoporous chromium or iron terephtalates (BDC) MIL-53(Cr, Fe) or M(OH)[BDC] have been used as matrices for the adsorption and in vitro drug delivery of Ibuprofen (or alpha- p-isobutylphenylpropionic acid). Both MIL-53(Cr) and MIL-53(Fe) solids adsorb around 20 wt % of Ibuprofen (Ibuprofen/dehydrated MIL-53 molar ratio = 0.22(1)), indicating that the amount of inserted drug does not depend on the metal (Cr, Fe) constitutive of the hybrid framework. Structural and spectroscopic characterizations are provided for the solid filled with Ibuprofen. In each case, the very slow and complete delivery of Ibuprofen was achieved under physiological conditions after 3 weeks with a predictable zero-order kinetics, which highlights the unique properties of flexible hybrid solids for adapting their pore opening to optimize the drug-matrix interactions.
TL;DR: The plasmonic photocatalysis will be of use as a high performance photocatalyst in nearly all current applications but will beof particular importance for applications in locations of minimal light exposure.
Abstract: Titanium dioxide (TiO2) displays photocatalytic behavior under near-ultraviolet (UV) illumination. In another scientific field, it is well understood that the excitation of localized plasmon polaritons on the surface of silver (Ag) nanoparticles (NPs) causes a tremendous increase of the near-field amplitude at well-defined wavelengths in the near UV. The exact resonance wavelength depends on the shape and the dielectric environment of the NPs. We expected that the photocatalytic behavior of TiO2 would be greatly boosted if it gets assisted by the enhanced near-field amplitudes of localized surface plasmon (LSP). Here we show that this is true indeed. We named this new phenomenon "plasmonic photocatalysis". The key to enable plasmonic photocatalysis is to deposit TiO2 on a NP comprising an Ag core covered with a silica (SiO2) shell to prevent oxidation of Ag by direct contact with TiO2. The most appropriate diameter for Ag NPs and thickness for the SiO2 shell giving rise to LSP in the near UV were estimated from Mie scattering theory. Upon implementing a device that took these design considerations into account, the measured photocatalytic activity under near UV illumination of such a plasmonic photocatalyst, monitored by decomposition of methylene blue, was enhanced by a factor of 7. The enhancement of the photocatalytic activity increases with a decreased thickness of the SiO2 shell. The plasmonic photocatalysis will be of use as a high performance photocatalyst in nearly all current applications but will be of particular importance for applications in locations of minimal light exposure.
TL;DR: The crystal structure of the thiolate gold nanoparticle [TOA+][Au25(SCH2CH2Ph)18-], where TOA+ = N(C8H17)4+.
Abstract: We report the crystal structure of the thiolate gold nanoparticle [TOA+][Au25(SCH2CH2Ph)18-], where TOA+ = N(C8H17)4+. The crystal structure reveals three types of gold atoms: (a) one central gold atom whose coordination number is 12 (12 bonds to gold atoms); (b) 12 gold atoms that form the vertices of an icosahedron around the central atom, whose coordination number is 6 (five bonds to gold atoms and one to a sulfur atom), and (c) 12 gold atoms that are stellated on 12 of the 20 faces of the Au13 icosahedron. The arrangement of the latter gold atoms may be influenced by aurophilic bonding. Together they form six orthogonal semirings, or staples, of −Au2(SCH2CH2Ph)3− in an octahedral arrangement around the Au13 core.
TL;DR: This study reveals that the alternating copolymer HOMO energy level is mainly fixed by the carbazole moiety, whereas the LUMO energylevel is mainly related to the nature of the electron-withdrawing comonomer.
Abstract: On the basis of theoretical models and calculations, several alternating polymeric structures have been investigated to develop optimized poly(2,7-carbazole) derivatives for solar cell applications. Selected low band gap alternating copolymers have been obtained via a Suzuki coupling reaction. A good correlation between DFT theoretical calculations performed on model compounds and the experimental HOMO, LUMO, and band gap energies of the corresponding polymers has been obtained. This study reveals that the alternating copolymer HOMO energy level is mainly fixed by the carbazole moiety, whereas the LUMO energy level is mainly related to the nature of the electron-withdrawing comonomer. However, solar cell performances are not solely driven by the energy levels of the materials. Clearly, the molecular weight and the overall organization of the polymers are other important key parameters to consider when developing new polymers for solar cells. Preliminary measurements have revealed hole mobilities of about ...
TL;DR: A general approach to fine-tuning the upconversion emission colors, based upon a single host source of NaYF4 nanoparticles doped with Yb3+, Tm3+, and Er3+, is presented.
Abstract: A general approach to fine-tuning the upconversion emission colors, based upon a single host source of NaYF4 nanoparticles doped with Yb3+, Tm3+, and Er3+, is presented. The emission intensity balance can be precisely controlled using different host-activator systems and dopant concentrations. The approach allows access to a wide range of luminescence emission from visible to near-infrared by single-wavelength excitation.
TL;DR: Two new heteroleptic polypyridyl ruthenium complexes are reported with high molar extinction coefficients by extending the pi-conjugation of spectator ligands, with a motivation to enhance the optical absorptivity of mesoporous titania film and charge collection yield in a dye-sensitized solar cell.
Abstract: We report two new heteroleptic polypyridyl ruthenium complexes, coded C101 and C102, with high molar extinction coefficients by extending the π-conjugation of spectator ligands, with a motivation t...
TL;DR: A bioorthogonal reaction that proceeds with unusually fast reaction rates without need for catalysis: the cycloaddition of s-tetrazine and trans-cyclooctene derivatives, which enables protein modification at low concentration.
Abstract: Described is a bioorthogonal reaction that proceeds with unusually fast reaction rates without need for catalysis: the cycloaddition of s-tetrazine and trans-cyclooctene derivatives. The reactions tolerate a broad range of functionality and proceed in high yield in organic solvents, water, cell media, or cell lysate. The rate of the ligation between trans-cyclooctene and 3,6-di-(2-pyridyl)-s-tetrazine is very rapid (k2 2000 M−1 s−1). This fast reactivity enables protein modification at low concentration.
TL;DR: Results indicate that PSBTBT is a promising polymer material for applications in polymer solar cells.
Abstract: A new low band gap silole-containing conjugated polymer, PSBTBT, was designed and synthesized. Photovoltaic properties of PSBTBT were initially investigated, and an average power conversion efficiency (PCE) of 4.7% with a best PCE of 5.1% was recorded under illumination (AM 1.5G, 100 mW/cm(2)). The response range of the device covers the whole visible range from 380 to 800 nm. These results indicate that PSBTBT is a promising polymer material for applications in polymer solar cells.
TL;DR: The synthesized C, N, and S-doped titania nanomaterials show an increased electron density of states above the valence band of TiO2, which explains the red-shifted light absorption of these potential photocatalysts and simultaneously suggests a lowered potential as photooxidants compared to Degussa P25 TiO 2.
Abstract: The origin of the visible-light absorption of main-group element (C, N, S) doped TiO2 nanostructures is investigated via diffuse reflectance and valence band X-ray photoelectron spectroscopy. The synthesized C-, N-, and S-doped titania nanomaterials show an increased electron density of states above the valence band of TiO2, which explains the red-shifted light absorption of these potential photocatalysts and simultaneously suggests a lowered potential as photooxidants compared to Degussa P25 TiO2.
TL;DR: Results clearly demonstrate that the unique nanotubes structure can facilitate the propagation and kinetic separation of photogenerated charges, suggesting potentially important applications of the inorganic QDs sensitized TiO2 nanotube-array films in solar cell applications.
Abstract: Novel CdS quantum dots (QDs) sensitized TiO2 nanotube-array photoelectrodes were investigated for their photoelectrochemical (PEC) performance. The highly ordered TiO2 nanotube arrays were synthesized by anodic oxidation and CdS QDs were deposited into the pores of the nanotube arrays by a sequential chemical bath deposition method. It is found that the CdS QDs deposited in the pores of the TiO2 nanotube arrays may significantly increase the liquid junction PEC short circuit photocurrent (from 0.22 to 7.82 mA/cm2) and cell efficiency (up to 4.15%). These results clearly demonstrate that the unique nanotube structure can facilitate the propagation and kinetic separation of photogenerated charges, suggesting potentially important applications of the inorganic QDs sensitized TiO2 nanotube-array films in solar cell applications.
TL;DR: Graphite oxide samples were prepared by a simplified Brodie method and AB stacking of the layers in the GO was inferred from an electron diffraction study, which suggests that carboxyl and alkyl groups are at the edges of the flakes of graphite oxide.
Abstract: Graphite oxide (GO) samples were prepared by a simplified Brodie method. Hydroxyl, epoxide, carboxyl, and some alkyl functional groups are present in the GO, as identified by solid-state 13C NMR, Fourier-transform infrared spectroscopy, and X-ray photoemission spectroscopy. Starting with pyrolytic graphite (interlayer separation 3.36 A), the average interlayer distance after 1 h of reaction, as determined by X-ray diffraction, increased to 5.62 A and then increased with further oxidation to 7.37 A after 24 h. A smaller signal in 13C CPMAS NMR compared to that in 13C NMR suggests that carboxyl and alkyl groups are at the edges of the flakes of graphite oxide. Other aspects of the chemical bonding were assessed from the NMR and XPS data and are discussed. AB stacking of the layers in the GO was inferred from an electron diffraction study. The elemental composition of GO prepared using this simplified Brodie method is further discussed.
TL;DR: A luminescent microporous metal-organic framework Tb(BTC)G has been developed for the recognition and sensing of anions, exhibiting a high-sensitivity sensing function with respect to fluoride.
Abstract: A luminescent microporous metal−organic framework Tb(BTC)G has been developed for the recognition and sensing of anions, exhibiting a high-sensitivity sensing function with respect to fluoride.
TL;DR: Surfactant-wrapped chemically converted graphene sheets obtained from reduction of graphene oxide with hydrazine were functionalized by treatment with aryl diazonium salts, allowing alternative avenues for simple incorporation into different polymer matrices.
Abstract: Surfactant-wrapped chemically converted graphene sheets obtained from reduction of graphene oxide with hydrazine were functionalized by treatment with aryl diazonium salts. The nanosheets are characterized by X-ray photoelectron spectroscopy, attenuated total reflectance infrared spectroscopy, Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. The resulting functionalized nanosheets disperse readily in polar aprotic solvents, allowing alternative avenues for simple incorporation into different polymer matrices.
TL;DR: The carbon catalyst can be readily separated from the saccharide solution after reaction for reuse in the reaction without loss of activity, and the catalytic performance of the carbon catalyst is attributed to the ability of the material to adsorb beta-1,4 glucan, which does not adsorb to other solid acids.
Abstract: The hydrolysis of cellulose into saccharides using a range of solid catalysts is investigated for potential application in the environmentally benign saccharification of cellulose. Crystalline pure cellulose is not hydrolyzed by conventional strong solid Bronsted acid catalysts such as niobic acid, H-mordenite, Nafion and Amberlyst-15, whereas amorphous carbon bearing SO 3H, COOH, and OH function as an efficient catalyst for the reaction. The apparent activation energy for the hydrolysis of cellulose into glucose using the carbon catalyst is estimated to be 110 kJ mol (-1), smaller than that for sulfuric acid under optimal conditions (170 kJ mol (-1)). The carbon catalyst can be readily separated from the saccharide solution after reaction for reuse in the reaction without loss of activity. The catalytic performance of the carbon catalyst is attributed to the ability of the material to adsorb beta-1,4 glucan, which does not adsorb to other solid acids.
TL;DR: Using methods developed to produce uniform, crack-free micrometer-thick films, CulnSe2 nanocrystals were tested in prototype photovoltaic devices and exhibited a reproducible photvoltaic response.
Abstract: Chalcopyrite copper indium sulfide (CuInS2) and copper indium gallium selenide (Cu(InxGa1-x)Se2; CIGS) nanocrystals ranging from ∼5 to ∼25 nm in diameter were synthesized by arrested precipitation in solution. The In/Ga ratio in the CIGS nanocrystals could be controlled by varying the In/Ga reactant ratio in the reaction, and the optical properties of the CuInS2 and CIGS nanocrystals correspond to those of the respective bulk materials. Using methods developed to produce uniform, crack-free micrometer-thick films, CuInSe2 nanocrystals were tested in prototype photovoltaic devices. As a proof-of-concept, the nanocrystal-based devices exhibited a reproducible photovoltaic response.
TL;DR: A low-temperature wafer-scale etching and thin film deposition method for fabricating silicon n-p core-shell nanowire solar cells and showed efficiencies up to nearly 0.5%, limited primarily by interfacial recombination and high series resistance.
Abstract: We have demonstrated a low-temperature wafer-scale etching and thin film deposition method for fabricating silicon n−p core−shell nanowire solar cells. Our devices showed efficiencies up to nearly 0.5%, limited primarily by interfacial recombination and high series resistance. Surface passivation and contact optimization will be critical to improve device performance in the future.
TL;DR: This work shows that the "giant" NQDs (g-NQDs) are functionally distinct from standard core-only, core/shell and even core/multishell NQds, and are substantially less sensitive to changes in surface chemistry.
Abstract: Semiconductor nanocrystal quantum dots (NQDs) comprise an important class of inorganic fluorophores for applications from optoelectronics to biology. Unfortunately, to date, NQD optical properties (e.g., their efficient and particle-size-tunable photoluminescence) have been susceptible to instabilities at the bulk and single-particle levels. Specifically, ensemble quantum yields (QYs) in emission are dependent upon NQD surface chemistry and chemical environment, while at the single-particle level, NQDs are characterized by significant fluorescence intermittency (blinking) that hinders applications as single-photon light sources for quantum informatics and biolabels for real-time monitoring of single biomolecules. Furthermore, while NQDs are significantly more photostable than their organic dye counterparts, traditional NQDs photobleach over periods of seconds to many minutes. Here, we demonstrate for the first time that by encapsulating the NQD core in a sufficiently thick inorganic shell, we are able to divorce NQD function from NQD surface chemistry and chemical environment. We show that our "giant" NQDs (g-NQDs) are functionally distinct from standard core-only, core/shell and even core/multishell NQDs. g-NQDs are substantially less sensitive to changes in surface chemistry. They do not photobleach under continuous laser excitation over periods of several hours repeated over several days, and they exhibit markedly different blinking behavior; >20% of the g-NQDs do not blink, while >40% have on-time fractions of >80%. All of these observations are in stark contrast with control samples comprising core-only and standard, thinner core/multishell NQDs.