Influence of Surface Chemistry on Metal Deposition Outcomes in Copper Selenide-Based Nanoheterostructure Synthesis.

The use of nanoparticle surface chemistry to direct metal deposition has been well-studied in the modification of metal nanoparticle substrates but is not yet well-established for metal chalcogenide particle substrates, although integration of these particles into nanoheterostructures is of high interest. In this report, we investigate the effect of Cu2-xSe surface chemistry on the morphology of metal deposition on these plasmonic semiconductor nanoparticles. Specifically, we functionalize Cu2-xSe nanoparticles with a suite of 12 different ligands and investigate how different aspects of the ligand structure do or do not impact the morphology and extent of subsequent metal deposition on the Cu2-xSe surface. Surprisingly, our results indicate that the morphology of the resulting metal deposits and the extent of metal deposition onto the existing Cu2-xSe particle substrate are indistinguishable for the majority of ligands tested. An exception to these findings is observed for particles functionalized by quaternary alkylammonium bromides, which exhibit statistically distinct metal deposition patterns compared to all other ligands tested. We hypothesize that this unique behavior is due to a cooperative binding mechanism of the quaternary alkylammonium bromides to the surface of copper selenide. Taken together, these results yield both new strategies for controlling postsynthetic modification of copper selenide nanoparticles and also reveal limitations of surface chemistry-based approaches for this system.

Multimetallic post-synthetic modifications of copper selenide nanoparticles.

In this report, we investigate the addition of two metal cations, simultaneously and sequentially to Cu2-xSe nanoparticles. The metal combinations (Ag-Au, Ag-Pt, Hg-Au and Hg-Pt) are chosen such that one metal adds to the structure via cation exchange and the other adds to the structure via metal deposition when added individually to Cu2-xSe nanoparticles. Surprisingly, we find that for each metal combination, across all three synthesis routes, cation exchange and metal deposition products are obtained without deviation from the outcomes seen in the binary metal systems. However, within those outcomes the data show several types of heterogeneities in the morphologies formed including extent and composition of cation exchange products as well as the extent and composition of the metal deposited products. Taken together, these results suggest a hierarchical control for nanoheterostructure morphologies where the pathways of cation exchange or metal deposition in post-synthetic modification of Cu2-xSe exhibit relatively general outcomes as a function of metal, regardless of synthetic approach or metal combination. However, the detailed composition and interface populations of the resulting materials are more sensitive to both metal identities and synthetic procedure (e.g. order of reagent addition), suggesting that certain principles of metal chalcogenide post-synthetic modification are excitingly robust, while also revealing new avenues for both mechanistic discovery and structural control.

Continuous nucleation of metallic nanoparticles via photocatalytic reduction.

Whether in organic synthesis or solar energy conversion, light can be a powerful reagent in chemical reactions and introduce new opportunities for synthetic control including duration, intensity, interval, and energy of irradiation. Here, we report the use of a molecular photosensitizer as a reducing agent in metallic nanoparticle syntheses. Using this approach, we report three key findings. (1) Nanoparticles produced by photocatalytic reduction form via a continuous nucleation mechanism, as opposed to burst and burst-like nucleation processes typically observed in metal nanoparticle syntheses. (2) Because nucleation is continuous, as long as the solution is irradiated (and there remains excess reagents in solution), nanoparticle nucleation can be turned on and off by controlling the timing and duration of irradiation, with no observable particle growth. (3) This synthetic method extends to the formation of bimetallic nanoparticles, which we show also form via a continuous nucleation pathway, and follow predicted patterns of metal incorporation as a function of the magnitude of the difference between the reduction potentials of the two metals. Taken together, these results establish a versatile synthetic method for the formation of multimetallic nanoparticles using visible light.

Connecting Cation Exchange and Metal Deposition Outcomes via Hume-Rothery-Like Design Rules Using Copper Selenide Nanoparticles.

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.

Staphylococcal catalase regulates its virulence and induces arthritis in catalase deficient mice.

To figure out whether in vivo expression of Staphylococcal catalase could correlate with the virulence and pathogenicity of the bacteria in the catalase deficient Swiss albino mice. 3 Amino 1, 2, 4 triazole (ATZ) (2 mg/g body wt) treated catalase deficient mice were infected with virulent S. aureus and bacterial burden, antioxidant enzyme levels were estimated after 3, 5 and 10 days of infection. Arthritic scores and levels of serum uric acid in mice were also determined. ATZ treatment was found to have slowed down the clearance of bacteria from blood and their rapid elimination from spleen. Increased tissue catalase activities in the spleen and liver of ATZ pre-treated mice even after 5 days of infection suggested its bacterial origin. It was further verified by zymographic analysis. Increased swelling of joints was observed after 5 days of infection. Uric acid level was found lesser in ATZ treated mice. ATZ treatment slowed the bacterial passage from blood with a lower tissue anti-oxidant enzymes leading to induction of joint inflammation.