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We use photocatalytic reduction to synthesize mono and bimetallic nanoparticles. This approach reveals a new formation pathway involving continuous nucleation and allows the reaction to be turned on and off without impacting particle outcomes.

The diffusion of poly(ethylene glycol) methyl ether thiol (PEGSH)-functionalized gold nanoparticles (NPs) was measured in polyacrylamide gels with various cross-linking densities. The molecular weight of the PEGSH ligand and particle core size were both varied to yield particles with hydrodynamic diameters ranging from 7 to 21 nm. The gel mesh size was varied from approximately 36 to 60 nm by controlling the cross-linking density of the gel. Because high-molecular-weight ligands are expected to yield more compressible particles, we expected the diffusion constants of the NPs to depend on their hard/soft ratios (where the hard component of the particle consists of the particle core and the soft component of the particle consists of the ligand shell). However, our measurements revealed that NP diffusion coefficients resulted primarily from changes in the overall hydrodynamic diameter and not the ratio of particle core size to ligand size. Across all particles and gels, we found that the diffusion coefficient was well predicted by the confinement ratio calculated from the diameter of the particle and an estimate of the gel mesh size obtained from the elastic blob model and was well described using a hopping model for nanoparticle diffusion. These results suggest that the elastic blob model provides a reasonable estimate of the mesh size that particles "see" as they diffuse through the gel. This work brings new insights into the factors that dictate how NPs move through polymer gels and will inform the development of hydrogel nanocomposites for applications such as drug delivery in heterogeneous, viscoelastic biological materials.

Data-driven optimization of hydrogen production.

Light driven hydrogen production from the water splitting reaction has the ability to reduce dependence on fossil fuels in a green energy future.

Unlike conventional antimicrobials, the study of bacterial resistance to silver nanoparticles (AgNPs) remains in its infancy and the mechanism(s) through which it evolves are limited and inconclusive. The central question remains whether bacterial resistance is driven by the AgNPs, released Ag(I) ions or a combination of these and other factors. Here, we show a specific resistance in an Escherichia coli K-12 MG1655 strain to subinhibitory concentrations of AgNPs, and not Ag(I) ions, as indicated by a statistically significant greater-than-twofold increase in the minimum inhibitory concentration occurring after eight repeated passages that was maintained after the AgNPs were removed and reintroduced. Whole-population genome sequencing identified a cusS mutation associated with the heritable resistance that possibly increased silver ion efflux. Finally, we rule out the effect of particle aggregation on resistance and suggest that the mechanism of resistance may be enhanced or mediated by flagellum-based motility. Bacterial motility may be used as an important predictor of whether a particular bacteria strain can develop AgNP resistance and could inform design of nanoenabled antimicrobials that mechanistically target specific types of bacteria.

Heterogenous nanomaterials containing various inorganic phases have far-reaching impacts both from the physical phenomena they reveal and the technologies they enable. While the variety and impact of these materials has been demonstrated in many reports, there is critical ambiguity in the factors that lead to major bifurcations in developing these heterostructures, for example, the formation of either mixed metal semiconductors or segregated metal-semiconductor phases. Here, we compare outcomes of independently introducing 5 different metal cations (Au3+, Ag+, Hg2+, Pd2+, and Pt2+) to antifluorite copper selenide (Cu2-xSe) nanoparticles (diameter = 52 ± 5 nm). This suite of metal cations allowed us to control for and evaluate a variety of potentially competing intrinsic system parameters including metal cation size, valency, and reduction potential as well as lattice volume change, lattice formation energy, and lattice mismatch. Upon secondary metal addition, we determined that the transformation of a cubic Cu2-xSe lattice will occur via cation exchange reaction when the change in symmetry to the resulting metal selenide phase(s) preserves mutually orthogonal lattice vectors. However, if the new lattice symmetry would be disrupted further, metal deposition is the likely outcome of secondary metal cation addition, forming metal-semiconductor heterostructures. These results suggest a synthesis design rule that relies on an intrinsic property of the material, not the reaction pathway, and indicates that more such factors may be found in other particle and synthetic systems.

Using a newly designed and developed parallelized photoreactor and colorimetric detection method, a large sampling of bimetallic cocatalysts (Pd/Sn, Pd/Mo, Pd/Ru, Pd/Pb, Pd/Ni, Ni/Sn, Mo/Sn, and Pt...

There is significant interest in earth-abundant plasmonic materials, but whether or not their performance can match or even surpass their noble metal counterparts remains to be established. An impo...

Controlling both the concentration and the distribution of elements in a given material is often crucial to extracting and optimizing synergistic properties of the various constituents. An interesting class of such multielement materials is metal chalcogenide nanoparticles, which exhibit a wide range of composition-dependent optoelectronic properties including both bandgap-mediated processes and localized surface plasmon resonance properties, each of which is useful in applications ranging from energy conversion to sensing. Because metal chalcogenide nanoparticles can support several different metal elements in a variety of chalcogen lattices, this material class has particularly benefited from the ability to control both atom concentration and atom arrangement to tailor final particle properties. The primary method to access complex, multimetallic chalcogenide particles is via a postsynthetic cation exchange strategy. One-pot syntheses have been less explored to access these complex particles, although t...

Rare earth elements (REEs) are strategically important for national security and advanced technologies. Consequently, significant effort has been devoted towards increasing REE domestic production, including the extraction of REEs from coal, coal combustion byproducts, and their associated waste streams such as acid mine drainage. Analytical techniques for rapid quantification of REE content in aqueous phases can facilitate REE recovery through rapid identification of high-value waste streams. In this work, we show that BioMOF-100 can be used as a fluorescent-based sensitizer for emissive REE ion detection in water, providing rapid (10 min) analysis times and sensitive detection (parts-per-billion detection limits) for terbium, dysprosium, samarium, europium, ytterbium, and neodymium, even in the presence of acids or secondary metals.

We introduce the concept of domain building blocks (DBBs) as an effective approach to increasing the diversity and complexity of metal-organic frameworks (MOFs). DBBs are defined as distinct structural or compositional regions within a MOF material. Using the DBB approach, we illustrate how an immense number of multivariate MOF materials can be prepared from a small collection of molecular building blocks comprising the distinct domains. The multivariate nature of the MOFs is determined by the sequence of DBBs within the MOF. We then apply this approach to the construction of a rich library of UiO-67 stratified MOF (sMOF) particles consisting of multiple concentric DBBs. We discuss and highlight the negative consequences of linker exchange reactions on the compositional integrity of DBBs in the UiO-67 sMOFs and propose and demonstrate mitigation strategies. We also demonstrate that individual strata can be specifically postsynthetically addressed and manipulated. Finally, we demonstrate the versatility of these synthetic strategies through the preparation of sMOF-nanoparticle composite materials.

At all length scales, the stability of materials is impacted by their surrounding environment. However, it has now been observed that materials with different dimensions can exhibit markedly different responses to their environment, even for the same material composition. For example, the deterioration of nanomaterials is complicated by the unique chemical and physical properties that arise from changes to their size, shape, and/or surface chemistry. A first step in understanding and predicting nanomaterial stabilities is to leverage the decades of work dedicated to understanding the environment-specific deterioration mechanisms of analogous bulk materials. Then, unique nanoscale properties can be accounted for and used to understand both similarities and differences in deterioration behavior across these length scales. In this review, we specifically consider the stability of group 11 coinage metal surfaces: copper, silver, and gold. We first summarize the chemical mechanisms of environmentally-driven deterioration of these metals in the bulk. We then apply this knowledge to interpret stability studies of nanoparticles made from the same elements. Ultimately, we find that while the reactivity of gold and copper is relatively consistent across length scales, the composition of products formed on silver surfaces differs significantly. These results have important implications for predicting and controlling both desirable and undesirable metal nanoparticle deterioration processes.

Unlike conventional antimicrobials, the study of bacterial resistance to silver nanoparticles (AgNPs) remains in its infancy and the mechanism(s) through which it evolves are limited and inconclusive. The central question remains whether bacterial resistance is driven by the AgNPs, released Ag(I) ions or a combination of these and other factors. Here, we show a specific resistance in an Escherichia coli K-12 MG1655 strain to subinhibitory concentrations of AgNPs, and not Ag(I) ions, as indicated by a statistically significant greater-than-twofold increase in the minimum inhibitory concentration occurring after eight repeated passages that was maintained after the AgNPs were removed and reintroduced. Whole-population genome sequencing identified a cusS mutation associated with the heritable resistance that possibly increased silver ion efflux. Finally, we rule out the effect of particle aggregation on resistance and suggest that the mechanism of resistance may be enhanced or mediated by flagellum-based motility.

Polyelemental nanoparticles (PE NPs) containing four or more elements in a single NP have intriguing intrinsic properties compared to their single-element counterparts. The fusion of diverse elements induces synergistic effects including new physical and chemical phenomena. However, conventional methods have not offered effective strategies for the uniform creation of PE NPs with high reproducibility. Recently, with advances in nanoscience, several new methods have been developed using both thermodynamic and kinetic approaches and, often, the interplay between them. In this Perspective, we highlight recent key advances in the design of PE NPs and their underlying formation mechanisms. We discuss the potential applications of PE NPs and the outlook and future directions for this field.

Copper(I) and gold(I) thiolates were synthesized in quantitative or near-quantitative yield by the direct reaction of aqueous Cu(NO3)2 or HAuCl4 with aqueous thiols HSCH2CH2OH and HSCH2CH2OCH2CH2OH. The resulting highly insoluble thiolates had spectroscopic and bulk characteristics consistent with the formation of coordination polymers of general formula [M(SR)]n. The gold(I) thiolates were found to be amorphous solids with significant aurophilic interactions. The copper(I) thiolates, however, formed crystalline solids without discernible cuprophilic interactions. Characterization of the solid state structure of these latter thiolates showed that they consisted of covalently linked ca. two-atom thick Cu–S layers separated by layers of hydrogen bonded thiol side chains.

Silver nanoparticles (AgNPs) and other ionizing engineered nanomaterials (ENMs) are candidates for the development of antimicrobial agents due to their efficacy, multiple modes of bacterial inactivation, and tunability with respect to both the magnitude and mechanisms of antimicrobial activity. Exploiting this versatility requires elucidating the bacterial inactivation pathway(s) of the ENM, and in particular, the link between material properties and the desired biological endpoint. The mechanisms of antimicrobial activity for macrosilver, Ag salts, and AgNPs have been widely studied, and largely attribute this activity to the release of Ag ions via oxidation and dissolution of the surface Ag atoms. However, it has also been established that Ag ion exposure alone does not elicit the same bacterial response as exposure to AgNPs, which suggests that the observed antimicrobial activity is induced not only by solubilized ions but also by the ENM itself. Resolving the role of the AgNP is critical to informing design of nano-enabled antimicrobials a priori. Herein, we present a systematic review of the AgNP antimicrobial activity literature and specifically focus on studies that scale Ag ion controls to the likely quantities of bioavailable Ag released from AgNPs. This literature selection criterion reveals the critical role of scaled ion controls in distinguishing ion and particle contributions to the observed antimicrobial activity. Overall, our analysis of this literature indicates that in most cases of bacteria exposure to AgNPs, particle-specific activity is observed and acts in concert with and/or independently from solubilized Ag ions alone. These results are exciting and suggest that more efficacious Ag- and ENM-enabled antimicrobials can be obtained through ENM design.

Here, we determine the impact of bacterial growth media on silver nanoparticle (diameter = 24.0 ± 3.2 nm) surface chemistry, the relationship of this surface chemistry to silver ion release from these nanoparticles, and ultimately the antimicrobial implications of those parameters. Importantly, we investigate the effects of multiple broths, as well as the isolated influence of individual broth components and their bicombinations. Our findings indicate that, in combination, broth components may exhibit additive, synergistic, and/or antagonistic effects on silver ion release. In addition, we find that the silver ion release does not always inversely correlate with ligand density, and interestingly, that the type of correlation (negative or positive) is dependent on the broth media. Finally, the impact of these media-dependent silver ion release profiles on bacterial cytotoxicity is studied using the model organism Escherichia coli. Overall, we establish the specific impacts of silver nanoparticle environment on silver nanoparticle surface chemistry, as well as the influence of those outcomes on bacteria growth in the presence of silver nanoparticles.

Nanoparticle superstructures have received widespread interest due to their unique physical properties that derive from the size, shape, composition, and 3D assembly of their component nanoparticle building blocks. Successful deployment of these materials for target applications requires methods for modifying their surfaces to impart specific properties and functions. To this end, we demonstrate that ligand exchange processes, which are extensively employed for functionalizing discrete nanoparticles, can be used to modify the surfaces of nanoparticle superstructures. We show that peptides coating the external surfaces of hollow, spherical gold nanoparticle superstructures are effectively exchanged with thiolated ligands, while maintaining the integrity of the assembled structure. The resulting superstructures are stable on the bench. These proof-of-principle studies highlight the potential of using ligand exchange to differentiate nanoparticle superstructures, thereby expanding their utility and application scope.

The recent ExecutiveOrder by President Trump attempting to ban temporarily the citizens of seven countries (Iran, Iraq, Libya, Somalia, Sudan, Syria, and Yemen) from entering the United States is having significant consequences within the country and around the world. The Order poses a threat to the health and vitality of science, barring students and scientists from these countries from traveling to the United States to study or to attend conferences. In preventing those members of the international scientific community from traveling beyond U.S. borders without guaranteed safe return, the Executive Order demeans them; in so doing, it demeans us all. Universities and research communities are especially impacted, as major universities have students and often faculty holding passports from one of these seven countries. This temporary ban would affect refugees fleeing war-torn areas, challenging the long-standing notion that the United States is a safe haven for those fleeing persecution and war in addition to being a magnet for talent from every corner of the world. The pages of this journal reflect the geographic, ethnic, and cultural diversity that underpins great science. The ban impacts domestic and global scientific efforts and communities. Science succeeds through the cooperation between collections of individuals and teams around the world discovering and learning from each other. To ensure rapid scientific progress, open communication and exchange between scientists are essential. As scientists, engineers, and clinicians, we have benefited from open interactions and collaborations with visitors and students from all parts of the world as well as through scientific publications and discussions at scientific meetings.

In biological systems, chemical and physical transformations of engineered silver nanomaterials (AgENMs) are mediated, in part, by proteins and other biomolecules. Metalloprotein interactions with AgENMs are also central in understanding toxicity and antimicrobial and resistance mechanisms. Despite their readily available thiolate and amine ligands, zinc finger (ZF) peptides have thus far escaped study in reaction with AgENMs and their Ag(I) oxidative dissolution product. We report spectroscopic studies that characterize AgENM and Ag(I) interactions with two ZF peptides that differ in sequence, but not in metal binding ligands: the ZF consensus peptide CP-CCHC and the C-terminal zinc finger domain of HIV-1 nucleocapsid protein p7 (NCp7_C). Both ZF peptides catalyze AgENM (10 and 40 nm, citrate coated) dissolution and agglomeration, two important AgENM transformations that impact bioreactivity. AgENMs and their oxidative dissolution product, Ag(I)(aq), mediate changes to ZF peptide structure and metalation as well. Spectroscopic titrations of Ag(I) into apo-ZF peptides show an Ag(I)-thiolate charge transfer band, indicative of Ag(I)-ZF binding. Fluorescence studies of the Zn(II)-NCp_7 complex indicate that the Ag(I) also effectively competes with the Zn(II) to drive Zn(II) displacement from the ZFs. Upon interaction with AgENMs, Zn(II) bound ZF peptides show a secondary structural change in circular dichroism spectroscopy toward an apo-like structure. The results suggest that Ag(I) and AgENMs may alter ZF protein function within the cell.

The syntheses, properties, and broad utility of noble metal plasmonic nanomaterials are now well-established. To capitalize on this exceptional utility, mitigate its cost, and potentially expand it, non-noble metal plasmonic materials have become a topic of widespread interest. As new plasmonic materials come online, it is important to understand and assess their ability to generate comparable or complementary plasmonic properties to their noble metal counterparts, including as both sensing and photoredox materials. Here, we study plasmon-driven chemistry on degenerately doped copper selenide (Cu2–xSe) nanoparticles. In particular, we observe plasmon-driven dimerization of 4-nitrobenzenethiol to 4,4′-dimercaptoazobenzene on Cu2–xSe surfaces with yields comparable to those observed from noble metal nanoparticles. Overall, our results indicate that doped semiconductor nanoparticles are promising for light-driven chemistry technologies.

From size-dependent luminescence to localized surface plasmon resonances, the optical properties that emerge from common materials with nanoscale dimensions have been revolutionary. As nanomaterials get smaller, they approach molecular electronic structures, and this transition from bulk to molecular electronic properties is a subject of far-reaching impact. One class of nanomaterials that exhibit particularly interesting optoelectronic features at this size transition are coinage metal (i.e., group 11 elements copper, silver, and gold) nanoparticles with core diameters between approximately 1 to 3 nm (∼25-200 atoms). Coinage metal nanoparticles can exhibit red or near-infrared photoluminescence features that are not seen in either their molecular or larger nanoscale counterparts. This emission has been exploited both as a probe of electronic behavior at the nanoscale as well as in critical applications such as biological imaging and chemical sensing. Interestingly, it has been demonstrated that their photoluminescence figures of merit such as emission quantum yield, energy, and lifetime are largely independent of particle diameter. Instead, emission from particles at this size range depends heavily on the particle surface chemistry, which includes both its metallic composition and the capping ligand architecture. The strong influence of surface chemistry on these emergent optoelectronic phenomena has powerful implications for both the study and use of these particles, primarily due to the theoretically limitless possible surface ligand architectures and metallic compositions. In this Account, we highlight recent work that studies and uses surface chemistry-mediated photoluminescence from coinage metal nanoparticles. Specifically, we emphasize the distinct, as well as synergistic, roles of the nanoparticle capping ligand and the nanoparticle core for controlling and/or enhancing their near-infrared photoluminescence. We then discuss the implications of surface chemistry-mediated photoluminescence as it relates to downstream applications such as energy transfer, sensing, and biological imaging. We conclude by discussing current challenges that remain in the field, including opportunities to develop new particle synthetic routes, analytical tools, and physical frameworks with which to understand small nanoparticle emission. Taken together, we anticipate that these materials will be foundational both in understanding the unique transition from molecular to bulk electronic structures and in the development of nanomaterials that leverage this transition.

Catalytic and optical properties can be coupled by combining different metals into nanoscale architectures in which both the shape and the composition provide fine-tuning of functionality. Here, discrete, small Pt nanoparticles (diameter = 3-6 nm) were grown in linear arrays on Au nanoprisms, and the resulting structures are shown to retain strong localized surface plasmon resonances. Multidimensional electron microscopy and spectroscopy techniques (energy-dispersive X-ray spectroscopy, electron tomography, and electron energy-loss spectroscopy) were used to unravel their local composition, three-dimensional morphology, growth patterns, and optical properties. The composition and tomographic analyses disclose otherwise ambiguous details of the Pt-decorated Au nanoprisms, revealing that both pseudospherical protrusions and dendritic Pt nanoparticles grow on all faces of the nanoprisms (the faceted or occasionally twisted morphologies of which are also revealed), and shed light on the alignment of the Pt nanoparticles. The electron energy-loss spectroscopy investigations show that the Au nanoprisms support multiple localized surface plasmon resonances despite the presence of pendant Pt nanoparticles. The plasmonic fields at the surface of the nanoprisms indeed extend into the Pt nanoparticles, opening possibilities for combined optical and catalytic applications. These insights pave the way toward comprehensive nanoengineering of multifunctional bimetallic nanostructures, with potential applications in plasmon-enhanced catalysis and in situ monitoring of chemical processes via surface-enhanced spectroscopy.

Amphiphilic triblock copolymers containing Fe(III) -catecholate complexes formulated as spherical- or cylindrical-shaped micellar nanoparticles (SMN and CMN, respectively) are described as new T1-weighted agents with high relaxivity, low cytotoxicity, and long-term stability in biological fluids. Relaxivities of both SMN and CMN exceed those of established gadolinium chelates across a wide range of magnetic field strengths. Interestingly, shape-dependent behavior is observed in terms of the particles' interactions with HeLa cells, with CMN exhibiting enhanced uptake and contrast via magnetic resonance imaging (MRI) compared with SMN. These results suggest that control over soft nanoparticle shape will provide an avenue for optimization of particle-based contrast agents as biodiagnostics. The polycatechol nanoparticles are proposed as suitable for preclinical investigations into their viability as gadolinium-free, safe, and effective imaging agents for MRI contrast enhancement.

Author(s): Chan, WCW; Chhowalla, M; Farokhzad, O; Glotzer, S; Gogotsi, Y; Hammond, PT; Hersam, MC; Javey, A; Kagan, CR; Kataoka, K; Khademhosseini, A; Kotov, NA; Lee, ST; Lee, YH; Li, Y; Millstone, JE; Mulvaney, P; Nel, AE; Nordlander, PJ; Parak, WJ; Penner, RM; Rogach, AL; Schaak, RE; Sood, AK; Stevens, MM; Wee, ATS; Weil, T; Grant Willson, C; Weiss, PS

Here, we demonstrate efficient energy transfer from near-infrared-emitting ortho-mercaptobenzoic acid-capped gold nanoparticles (AuNPs) to pendant ytterbium(III) cations. These functional materials combine the high molar absorptivity (1.21 × 106 M–1 cm–1) and broad excitation features (throughout the UV and visible regions) of AuNPs with the narrow emissive properties of lanthanides. Interaction between the AuNP ligand shell and ytterbium is determined using both nuclear magnetic resonance and electron microscopy measurements. In order to identify the mechanism of this energy transfer process, the distance of the ytterbium(III) from the surface of the AuNPs is systematically modulated by changing the size of the ligand appended to the AuNP. By studying the energy transfer efficiency from the various AuNP conjugates to pendant ytterbium(III) cations, a Dexter-type energy transfer mechanism is suggested, which is an important consideration for applications ranging from catalysis to energy harvesting. Taken ...

Small gold nanoparticles (∼1.4-2.2 nm core diameters) exist at an exciting interface between molecular and metallic electronic structures. These particles have the potential to elucidate fundamental physical principles driving nanoscale phenomena and to be useful in a wide range of applications. Here, we study the optoelectronic properties of aqueous, phosphine-terminated gold nanoparticles (core diameter = 1.7 ± 0.4 nm) after ligand exchange with a variety of sulfur-containing molecules. No emission is observed from these particles prior to ligand exchange, however the introduction of sulfur-containing ligands initiates photoluminescence. Further, small changes in sulfur substituents produce significant changes in nanoparticle photoluminescence features including quantum yield, which ranges from 0.13 to 3.65% depending on substituent. Interestingly, smaller ligands produce the most intense, highest energy, narrowest, and longest-lived emissions. Radiative lifetime measurements for these gold nanoparticle conjugates range from 59 to 2590 μs, indicating that even minor changes to the ligand substituent fundamentally alter the electronic properties of the luminophore itself. These results isolate the critical role of surface chemistry in the photoluminescence of small metal nanoparticles and largely rule out other mechanisms such as discrete (Au(I)-S-R)n impurities, differences in ligand densities, and/or core diameters. Taken together, these experiments provide important mechanistic insight into the relationship between gold nanoparticle near-infrared emission and pendant ligand architectures, as well as demonstrate the pivotal role of metal nanoparticle surface chemistry in tuning and optimizing emergent optoelectronic features from these nanostructures.

Copper-containing nanomaterials are attractive due to the natural abundance, low cost, and unique catalytic properties of copper metal. Copper may also be used as a representative system to study the formation of mixed metal nanoparticles containing 3d transition metals. These elements pose challenges to traditional metal nanoparticle synthesis strategies due to competing formation of both oxides and hydroxides, depending on metal identity. Here, we analyze copper deposition pathways on gold nanoprism substrates using a combination of electron microscopy and X-ray photoelectron spectroscopy techniques, demonstrating conditions for both core@shell and island growth modes. Elemental analysis by X-ray photoelectron spectroscopy and Auger electron spectroscopy indicate that the final nanoparticle products contain metallic copper. Together, these results elucidate important trends for incorporating 3d transition metals into traditional colloidal syntheses of multimetallic nanostructures.

Solution phase noble metal nanoparticle growth reactions are comprised of deceptively simple steps. Analytical methods with high chemical, spatial, and temporal resolution are crucial to understanding these reactions and subsequent nanoparticle properties. However, approaches for the characterization of solid inorganic materials and solution phase molecular species are often disparate. One powerful technique to address this gap is nuclear magnetic resonance (NMR) spectroscopy, which can facilitate routine, direct, molecular-scale analysis of nanoparticle formation and morphology in situ, in both the solution and the solid phase. A growing body of work indicates that NMR analyses should yield an exciting complement to the existing canon of routine nanoparticle characterization methods such as electron microscopy and optical absorption spectroscopy. Here, we discuss recent developments in the application of NMR techniques to the study of noble metal nanoparticle growth, surface chemistry, and physical prope...

We use nuclear magnetic resonance spectroscopy methods to quantify the extent of ligand exchange between different types of thiolated molecules on the surface of gold nanoparticles. Specifically, we determine ligand density values for single-moiety ligand shells and then use these data to describe ligand exchange behavior with a second, thiolated molecule. Using these techniques, we identify trends in gold nanoparticle functionalization efficiency with respect to ligand type, concentration, and reaction time as well as distinguish between functionalization pathways where the new ligand may either replace the existing ligand shell (exchange) or add to it ("backfilling"). Specifically, we find that gold nanoparticles functionalized with thiolated macromolecules, such as poly(ethylene glycol) (1 kDa), exhibit ligand exchange efficiencies ranging from 70% to 95% depending on the structure of the incoming ligand. Conversely, gold nanoparticles functionalized with small-molecule thiolated ligands exhibit exchange efficiencies as low as 2% when exposed to thiolated molecules under identical exchange conditions. Taken together, the reported results provide advances in the fundamental understanding of mixed ligand shell formation and will be important for the preparation of gold nanoparticles in a variety of biomedical, optoelectronic, and catalytic applications.

We report the use of gold nanoparticle surface chemistry as a tool for site-selective noble metal deposition onto colloidal gold nanoparticle substrates. Specifically, we demonstrate that partial passivation of the gold nanoparticle surface using thiolated ligands can induce a transition from linear palladium island deposition to growth of palladium selectively at plasmonic hotspots on the edges or vertices of the underlying particle substrate. Further, we demonstrate the broader applicability of this approach with respect to substrate morphology (e.g., prismatic and rod-shaped nanoparticles), secondary metal (e.g., palladium, gold, and platinum), and surface ligand (e.g., surfactant molecules and n-alkanethiols). Taken together, these results demonstrate the important role of metal–ligand surface chemistry and ligand packing density on the resulting modes of multimetallic nanoparticle growth, and in particular, the ability to direct that growth to particle regions of impact such as plasmonic hotspots.

Recently, a wide variety of new nanoparticle compositions have been identified as potential plasmonic materials including earth-abundant metals such as aluminum, highly doped semiconductors, as well as metal pnictides. For semiconductor compositions, plasmonic properties may be tuned not only by nanoparticle size and shape, but also by charge carrier density which can be controlled via a variety of intrinsic and extrinsic doping strategies. Current methods to quantitatively determine charge carrier density primarily rely on interpretation of the nanoparticle extinction spectrum. However, interpretation of nanoparticle extinction spectra can be convoluted by factors such as particle ligands, size distribution and/or aggregation state which may impact the charge carrier information extracted. Therefore, alternative methods to quantify charge carrier density may be transformational in the development of these new materials and would facilitate previously inaccessible correlations between particle synthetic routes, crystallographic features, and emergent optoelectronic properties. Here, we report the use of

The use of nanoparticles in biomedicine critically depends on their surface chemistry. For metal nanoparticles, a common way to tune this surface chemistry is through mass action ligand exchange, where ligand exchange can be used to expand the functionality of the resulting nanoparticle conjugates. Specifically, the quantity, identity, and arrangement of the molecules in the resulting ligand shell each can be tuned significantly. Here, we describe methods to exchange and quantify thiolated and non-thiolated ligands on gold nanoparticle surfaces. Importantly, these strategies allow the quantification of multiple ligand types within a single ligand shell, simultaneously providing ligand composition and ligand density information. These results are crucial for both designing and assigning structure-function relationships in bio-functionalized nanoparticles, and these methods can be applied to a broad range of nanoparticle cores and ligand types including peptides, small molecule drugs, and oligonucleotides.

The use of nanoparticles in biomedicine critically depends on their surface chemistry. For metal nanoparticles, a common way to tune this surface chemistry is through mass action ligand exchange, where ligand exchange can be used to expand the functionality of the resulting nanoparticle conjugates. Specifically, the quantity, identity, and arrangement of the molecules in the resulting ligand shell each can be tuned significantly. Here, we describe methods to exchange and quantify thiolated and non-thiolated ligands on gold nanoparticle surfaces. Importantly, these strategies allow the quantification of multiple ligand types within a single ligand shell, simultaneously providing ligand composition and ligand density information. These results are crucial for both designing and assigning structure-function relationships in bio-functionalized nanoparticles, and these methods can be applied to a broad range of nanoparticle cores and ligand types including peptides, small molecule drugs, and oligonucleotides.

We demonstrate the synthesis of discrete, composition-tunable gold-cobalt nanoparticle alloys (% Co = 0–100%; diameter = 2–3 nm), in contrast with bulk behavior, which shows immiscibility of Au and Co at room temperature across all composition space. These particles are characterized by transmission electron microscopy and 1H NMR techniques, as well as inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy. In particular, 1H NMR methods allow the simultaneous evaluation of composition-tunable magnetic properties as well as molecular characterization of the colloid, including ligand environment and hydrodynamic diameter. These experiments also demonstrate a route to optimize bimodal imaging modalities, where we identify AuxCoyNP compositions that exhibit both bright NIR emission (2884 m −1cm−1) as well as some of the highest per-particle T 2 relaxivities (12200 mm NP −1s−1) reported to date for this particle size range.