Managing the Nitrogen Cycle via Plasmonic (Photo)Electrocatalysis: Toward Circular Economy.

As renewable energy sources are either intermittent in nature or remote in location, developing cost-effective, sustainable, modular systems and technologies to store and transport renewables at an industrial scale is imperative. Storing cheap renewable electricity into chemical bonds (i.e., chemical energy storage) could be a transformative opportunity for reliable and resilient grid energy storage. This approach enables renewables to be stored and shipped similarly to fossil fuels. Currently, the chemical industry primarily consumes fossil feedstock as an energy source, which has been the standard for over a century. A paradigm shift is required to move toward a more sustainable route for chemical synthesis by electrifying and decarbonizing the modern chemical industry. As renewable electricity costs decrease, (photo)electrosynthesis is gaining interest for synthesizing high-value and high-energy fuels and molecules in a clean, sustainable, and decentralized manner.The nitrogen cycle is one of the Earth's most critical biogeochemical cycles since nitrogen is a vital element for all living organisms. Artificial nitrogen fixation via a (photo)electrochemical system powered by renewables provides an alternative route to resource- and carbon-intensive thermochemical processes. (Photo)electrochemical nitrogen fixation at a large scale necessitates the discovery of active, selective, and stable heterogeneous (photo)electrocatalysts. In addition, the use of advanced in situ and operando spectroscopic techniques is needed to pinpoint the underlying reaction mechanisms. The selectivity of nitrogen (N2) molecules on the catalyst surface and suppressing thermodynamically favorable side reactions (e.g., hydrogen evolution reaction) are the main bottlenecks in improving the rate of (photo)electrochemical nitrogen fixation in aqueous solutions. The rational design of electrode, electrolyte, and reactors is required to weaken the strong nitrogen-nitrogen triple bond (N≡N) at or near ambient conditions. This Account covers our group's recent advances in synthesizing shape-controlled hybrid plasmonic nanoparticles, including plasmonic-semiconductor and plasmonic-transition metal nanostructures with increased surface areas. The nanocatalysts' selectivity and activity toward nitrogen conversion are benchmarked in liquid- and gas-phase electrochemical systems. We leverage operando vibrational-type spectroscopy (i.e., surface-enhanced Raman spectroscopy (SERS)) to identify intermediate species relevant to nitrogen fixation at the electrode-electrolyte interface to gain mechanistic insights into reaction mechanisms, leading to the discovery of more efficient catalysts. Operando SERS revealed that the nitrogen reduction reaction (NRR) to ammonia on hybrid plasmonic-transition metal nanoparticle surfaces (e.g., Pd-Ag) occurs through an associative mechanism. In the NRR process, hydrazine (N2H4) is consumed as an intermediate species. A femtosecond pulsed laser is used to synthesize hybrid plasmonic photocatalysts with homogeneously distributed Pd atoms on a Au nanorod surface, resulting in enhanced optoelectronic and catalytic properties. The overarching goal is to develop modular photoelectrochemical systems for long-duration renewable energy storage. In the context of nitrogen fixation, we aim to propose strategies to manage the nitrogen cycle through the interconversion of N2 and active nitrogen-containing compounds (e.g., NH3, NOx), enabling a circular nitrogen economy with sustainable and positive social and economic outcomes. The versatile approaches presented in this Account can inform future opportunities in (photo)electrochemical energy conversion systems and solar fuel-based applications.

Collective multipole oscillations direct the plasmonic coupling at the nanojunction interfaces.

We present a systematic study of the effect of higher-multipolar order plasmon modes on the spectral response and plasmonic coupling of silver nanoparticle dimers at nanojunction separation and introduce a coupling mechanism. The most prominent plasmonic band within the extinction spectra of coupled resonators is the dipolar coupling band. A detailed calculation of the plasmonic coupling between equivalent particles suggests that the coupling is not limited to the overlap between the main bands of individual particles but can also be affected by the contribution of the higher-order modes in the multipolar region. This requires an appropriate description of the mechanism that goes beyond the general coupling phenomenon introduced as the plasmonic ruler equation in 2007. In the present work, we found that the plasmonic coupling of nearby Ag nanocubes does not only depend on the plasmonic properties of the main band. The results suggest the decay length of the higher-order plasmon mode is more sensitive to changes in the magnitude of the interparticle axis and is a function of the gap size. For cubic particles, the contribution of the higher-order modes becomes significant due to the high density of oscillating dipoles localized on the corners. This gives rise to changes in the decay length of the plasmonic ruler equation. For spherical particles, as the size of the particle increases (i.e., ≥80 nm), the number of dipoles increases, which results in higher dipole-multipole interactions. This exhibits a strong impact on the plasmonic coupling, even at long separation distances (20 nm).

Dynamic Hybrid Metasurfaces.

Efficient hybrid plasmonic-photonic metasurfaces that simultaneously take advantage of the potential of both pure metallic and all-dielectric nanoantennas are identified as an emerging technology in flat optics. Nevertheless, postfabrication tunable hybrid metasurfaces are still elusive. Here, we present a reconfigurable hybrid metasurface platform by incorporating the phase-change material Ge2Sb2Te5 (GST) into metal-dielectric meta-atoms for active and nonvolatile tuning of properties of light. We systematically design a reduced-dimension meta-atom, which selectively controls the hybrid plasmonic-photonic resonances of the metasurface via the dynamic change of optical constants of GST without compromising the scattering efficiency. As a proof-of-concept, we experimentally demonstrate two tunable metasurfaces that control the amplitude (with relative modulation depth as high as ≈80%) or phase (with tunability >230°) of incident light promising for high-contrast optical switching and efficient anomalous to specular beam deflection, respectively. Our findings further substantiate dynamic hybrid metasurfaces as compelling candidates for next-generation reprogrammable meta-optics.

Targeting cancer cell integrins using gold nanorods in photothermal therapy inhibits migration through affecting cytoskeletal proteins.

Metastasis is responsible for most cancer-related deaths, but the current clinical treatments are not effective. Recently, gold nanoparticles (AuNPs) were discovered to inhibit cancer cell migration and prevent metastasis. Rationally designed AuNPs could greatly benefit their antimigration property, but the molecular mechanisms need to be explored. Cytoskeletons are cell structural proteins that closely relate to migration, and surface receptor integrins play critical roles in controlling the organization of cytoskeletons. Herein, we developed a strategy to inhibit cancer cell migration by targeting integrins, using Arg-Gly-Asp (RGD) peptide-functionalized gold nanorods. To enhance the effect, AuNRs were further activated with 808-nm near-infrared (NIR) light to generate heat for photothermal therapy (PPTT), where the temperature was adjusted not to affect the cell viability/proliferation. Our results demonstrate changes in cell morphology, observed as cytoskeleton protrusions-i.e., lamellipodia and filopodia-were reduced after treatment. The Western blot analysis indicates the downstream effectors of integrin were attracted toward the antimigration direction. Proteomics results indicated broad perturbations in four signaling pathways, Rho GTPases, actin, microtubule, and kinases-related pathways, which are the downstream regulators of integrins. Due to the dominant role of integrins in controlling cytoskeleton, focal adhesion, actomyosin contraction, and actin and microtubule assembly have been disrupted by targeting integrins. PPTT further enhanced the remodeling of cytoskeletal proteins and decreased migration. In summary, the ability of targeting AuNRs to cancer cell integrins and the introduction of PPTT stimulated broad regulation on the cytoskeleton, which provides the evidence for a potential medical application for controlling cancer metastasis.

Efficacy, long-term toxicity, and mechanistic studies of gold nanorods photothermal therapy of cancer in xenograft mice.

Gold nanorods (AuNRs)-assisted plasmonic photothermal therapy (AuNRs-PPTT) is a promising strategy for combating cancer in which AuNRs absorb near-infrared light and convert it into heat, causing cell death mainly by apoptosis and/or necrosis. Developing a valid PPTT that induces cancer cell apoptosis and avoids necrosis in vivo and exploring its molecular mechanism of action is of great importance. Furthermore, assessment of the long-term fate of the AuNRs after treatment is critical for clinical use. We first optimized the size, surface modification [rifampicin (RF) conjugation], and concentration (2.5 nM) of AuNRs and the PPTT laser power (2 W/cm2) to achieve maximal induction of apoptosis. Second, we studied the potential mechanism of action of AuNRs-PPTT using quantitative proteomic analysis in mouse tumor tissues. Several death pathways were identified, mainly involving apoptosis and cell death by releasing neutrophil extracellular traps (NETs) (NETosis), which were more obvious upon PPTT using RF-conjugated AuNRs (AuNRs@RF) than with polyethylene glycol thiol-conjugated AuNRs. Cytochrome c and p53-related apoptosis mechanisms were identified as contributing to the enhanced effect of PPTT with AuNRs@RF. Furthermore, Pin1 and IL18-related signaling contributed to the observed perturbation of the NETosis pathway by PPTT with AuNRs@RF. Third, we report a 15-month toxicity study that showed no long-term toxicity of AuNRs in vivo. Together, these data demonstrate that our AuNRs-PPTT platform is effective and safe for cancer therapy in mouse models. These findings provide a strong framework for the translation of PPTT to the clinic.

Operando Investigation into Dynamic Evolution of Cathode-Electrolyte Interfaces in a Li-Ion Battery.

While Li-ion battery cathode-electrolyte interfaces (CEIs) have been extensively investigated in recent decades, accurately identifying the chemical nature and tracking the dynamics of the CEIs during electrochemical cycling still remain a grand challenge. Here we report our findings in the investigation into the dynamic evolution of the interface between a LiNi0.33Co0.33Mn0.33O2 (LNMC) cathode and an ethylene carbonate/dimethyl carbonate (EC/DMC)-based electrolyte using surface-enhanced Raman spectroscopy (SERS) performed on a model cell under typical battery operating conditions. In particular, the strong SERS activity provided by a monolayer of Au nanocubes deposited on a model LNMC electrode (additive-free) enables quasi-quantitative assessment of the CEI evolution during cycling, proving information vital to revealing the dynamics of the species adsorbed on the LNMC surface as a function of cell potential. Furthermore, our theoretical calculation, which is based on the interaction between a model interface-bound molecule and a model LNMC surface, agrees with our experimental observation. The carefully designed operando SERS platform has demonstrated high sensitivity, good surface specificity, and excellent compatibility with extensive electrochemical measurements; it is also applicable to fundamental studies of dynamic interfaces in other electrochemical energy storage and conversion systems.

Improving the Flow Cytometry-based Detection of the Cellular Uptake of Gold Nanoparticles.

Due to the considerable amount of applications of gold nanoparticles (AuNPs) in biological systems, there is a great need for an improved methodology to quantitatively measure the uptake of AuNPs in cells. Flow cytometry has the ability to measure intracellular AuNPs by collecting the light scattering from a large population of live cells through efficient single cell analysis. Traditionally, the side scattering setting of the flow cytometer, which is associated with a 488 nm excitation laser (SSC channel), is used to detect nanoparticle uptake. This method is limited as AuNPs do not have the optimized response when excited with this laser. Here, we reported that the use of more red-shifted excitation lasers will greatly enhance the optical signal needed for the flow cytometry-based detection of AuNSs (26 nm in diameter) and AuNRs (67 nm × 33 nm, length × width) uptake in triple negative breast cancer cells (MDA-MB-231).

Carrier dynamics and the role of surface defects: Designing a photocatalyst for gas-phase CO2 reduction.

In2O3-x(OH)y nanoparticles have been shown to function as an effective gas-phase photocatalyst for the reduction of CO2 to CO via the reverse water-gas shift reaction. Their photocatalytic activity is strongly correlated to the number of oxygen vacancy and hydroxide defects present in the system. To better understand how such defects interact with photogenerated electrons and holes in these materials, we have studied the relaxation dynamics of In2O3-x(OH)y nanoparticles with varying concentration of defects using two different excitation energies corresponding to above-band-gap (318-nm) and near-band-gap (405-nm) excitations. Our results demonstrate that defects play a significant role in the excited-state, charge relaxation pathways. Higher defect concentrations result in longer excited-state lifetimes, which are attributed to improved charge separation. This correlates well with the observed trends in the photocatalytic activity. These results are further supported by density-functional theory calculations, which confirm the positions of oxygen vacancy and hydroxide defect states within the optical band gap of indium oxide. This enhanced understanding of the role these defects play in determining the optoelectronic properties and charge carrier dynamics can provide valuable insight toward the rational development of more efficient photocatalytic materials for CO2 reduction.

UV Resonance Raman Study of Apoptosis, Platinum-Based Drugs, and Human Cell Lines.

As a noninvasive molecular analysis technique, ultraviolet resonance Raman (UVRR) spectroscopy represents a label-free method suitable for characterizing biomolecules. Using UVRR spectroscopy, we collected spectral fingerprints of UV absorbing cellular components, including proteins, nucleic acids, and unsaturated lipids. This knowledge was used to guide the assignment of spectra derived from intact human cell lines (i. e., HSC-3 and HaCaT) and from the apoptotic events induced by cisplatin. Notably, a jet-flow system was employed to generate flowing cell suspensions during UVRR measurements, minimizing UV-induced damage. A spectral marker is established based on the ratio of Raman intensities at 1488 and 1655 cm-1 ; this ratio correlates to the level of cell death due to apoptosis. Collectively, this work demonstrates that UVRR spectroscopy is a sensitive and informative probe of cellular physiology and molecular composition. The molecular insight obtained from UVRR measurements can be used to improve understanding of therapeutic treatment and to guide drug development and the choice of therapeutic agents.

Defect engineering in 1D Ti-W oxide nanotube arrays and their correlated photoelectrochemical performance.

Understanding the nature of interfacial defects of materials is a critical undertaking for the design of high-performance hybrid electrodes for photocatalysis applications. Theoretical and computational endeavors to achieve this have touched boundaries far ahead of their experimental counterparts. However, to achieve any industrial benefit out of such studies, experimental validation needs to be systematically undertaken. In this sense, we present herein experimental insights into the synergistic relationship between the lattice position and oxidation state of tungsten ions inside a TiO2 lattice, and the respective nature of the created defect states. Consequently, a roadmap to tune the defect states in anodically-fabricated, ultrathin-walled W-doped TiO2 nanotubes is proposed. Annealing the nanotubes in different gas streams enabled the engineering of defects in such structures, as confirmed by XRD and XPS measurements. While annealing under hydrogen stream resulted in the formation of abundant Wn+ (n < 6) ions at the interstitial sites of the TiO2 lattice, oxygen- and air-annealing induced W6+ ions at substitutional sites. EIS and Mott-Schottky analyses indicated the formation of deep-natured trap states in the hydrogen-annealed samples, and predominantly shallow donating defect states in the oxygen- and air-annealed samples. Consequently, the photocatalytic performance of the latter was significantly higher than those of the hydrogen-annealed counterparts. Upon increasing the W content, photoelectrochemical performance deteriorated due to the formation of WO3 crystallites that hindered charge transfer through the photoanode, as evident from the structural and chemical characterization. To this end, this study validates the previous theoretical predictions on the detrimental effect of interstitial W ions. In addition, it sheds light on the importance of defect states and their nature for tuning the photoelectrochemical performance of the investigated materials.

Unraveling the Nature of Anomalously Fast Energy Storage in T-Nb2O5.

While T-Nb2O5 has been frequently reported to display an exceptionally fast rate of Li-ion storage (similar to a capacitor), the detailed mechanism of the energy storage process is yet to be unraveled. Here we report our findings in probing the nature of the ultrafast Li-ion storage in T-Nb2O5 using both experimental and computational approaches. Experimentally, we used in operando Raman spectroscopy performed on a well-designed model cell to systematically characterize the dynamic evolution of vibrational band groups of T-Nb2O5 upon insertion and extraction of Li ions during repeated cycling. Theoretically, our model shows that Li ions are located at the loosely packed 4g atomic layers and prefer to form bridging coordination with the oxygens in the densely packed 4h atomic layers. The atomic arrangement of T-Nb2O5 determines the unique Li-ion diffusion path topologies, which allow direct Li-ion transport between bridging sites with very low steric hindrance. The proposed model was validated by computational and experimental vibrational analyses. A comprehensive comparison between T-Nb2O5 and other important intercalation-type Li-ion battery materials reveals the key structural features that lead to the exceptionally fast kinetics of T-Nb2O5 and the cruciality of atomic arrangements for designing a new generation of Li-ion conduction and storage materials.

Intracellular Assembly of Nuclear-Targeted Gold Nanosphere Enables Selective Plasmonic Photothermal Therapy of Cancer by Shifting Their Absorption Wavelength toward Near-Infrared Region.

Despite the important applications of near-infrared (NIR) absorbing nanomaterials in plasmonic photothermal therapy (PPT), their high yield synthesis and nonspecific heating during the active- and passive-targeted cancer therapeutic strategies remain challenging. In the present work, we systematically demonstrate that in situ aggregation of typical non-NIR absorbing plasmonic nanoparticles at the nuclear region of the cells could translate them into an effective NIR photoabsorber in plasmonic photothermal therapy of cancer due to a significant shift of the plasmonic absorption band to the NIR region. We evaluated the potential of nuclear-targeted AuNSs as photoabsorber at various stages of endocytosis by virtue of their inherent in situ assembling capabilities at the nuclear region of the cells, which has been considered as one of the most thermolabile structures within the cells, to selectively destruct cancer cells with minimal damage to healthy cells. Various plasmonic nanoparticles such as rods and cubes have been exploited to elucidate the role of plasmonic field coupling in assembled nanoparticles and their subsequent killing efficiency. The NIR absorbing capabilities of aggregated AuNSs have been further demonstrated both experimentally and theoretically using discrete dipolar approximation (DDA) techniques, which was in concordance with the observed results in plasmonic photothermal therapeutic studies. While the current work was able to demonstrate the utility of non-NIR absorbing plasmonic nanoparticles as a potential alternative for plasmonic photothermal therapy by inducing localized plasmonic heating at the nuclear region of the cells, these findings could potentially open up new possibilities in developing more efficient nanoparticles for efficient cancer treatment modalities.

A Real-Time Surface Enhanced Raman Spectroscopy Study of Plasmonic Photothermal Cell Death Using Targeted Gold Nanoparticles.

Plasmonic nanoparticles are increasingly utilized in biomedical applications including imaging, diagnostics, drug delivery, and plasmonic photothermal therapy (PPT). PPT involves the rapid conversion of light into heat by plasmonic nanoparticles targeted to a tumor, causing hyperthermia-induced cell death. These nanoparticles can be passively targeted utilizing the enhanced permeability and retention effect, or actively targeted using proteins, peptides, or other small molecules. Here, we report the use of actively targeted spherical gold nanoparticles (AuNPs), both to induce PPT cell death, and to monitor the associated molecular changes through time-dependent surface enhanced Raman spectroscopy within a single cell. We monitored these changes in real-time and found that heat generated from the aggregated nanoparticles absorbing near-infrared (NIR) laser light of sufficient powers caused modifications in the protein and lipid structures within the cell and ultimately led to cell death. The same molecular changes were observed using different nanoparticle sizes and laser intensities, indicating the consistency of the molecular changes throughout PPT-induced cell death from actively targeted AuNPs. We also confirmed these observations by comparing them to reference spectra obtained by cell death induced by oven heating at 100 °C. The ability to monitor PPT-induced cell death in real-time will help understand the changes on a molecular level and offers us a basis to understand the molecular mechanisms involved in photothermal cancer cell death.

Hyperoxia Induces Intracellular Acidification in Neonatal Mouse Lung Fibroblasts: Real-Time Investigation Using Plasmonically Enhanced Raman Spectroscopy.

It is important to understand the molecular mechanisms underlying oxygen toxicity, which contributes to multiple human disorders. The archetype model of oxygen toxicity is neonatal lung injury induced by hyperoxia exposure. Here, we utilized plasmonically enhanced Raman spectroscopy (PERS) in combination with fluorescence and proteomic analysis to provide comprehensive information on hyperoxia-induced biomolecular modifications in neonatal mouse lung fibroblasts (nMLFs). During this study, we made the novel observation that hyperoxia induces intracellular acidification in nMLF, which we probed in real-time using label-free PERS. We found that intracellular acidification induces conformational modifications in proteins followed by significant changes in Raman vibrations corresponding to aromatic amino acids such as phenylalanine and tryptophan as well as cysteine moieties. Hyperoxia-induced intracellular pH changes and subsequent modifications in protein expression and associated post-translational modifications within the cells were further validated by fluorescence and proteomic analysis. These new insights may help identifying unique oxidant stress-induced mechanisms in disease processes and may guide the development of more efficient therapeutic strategies.

Photoexcited Surface Frustrated Lewis Pairs for Heterogeneous Photocatalytic CO2 Reduction.

In this study we investigated, theoretically and experimentally, the unique photoactive behavior of pristine and defected indium oxide surfaces providing fundamental insights into their excited state properties as well as an explanation for the experimentally observed enhanced activity of defected indium oxide surfaces for the gas-phase reverse water gas shift reaction, CO2 + H2 + hν→ CO + H2O in the light compared to the dark. To this end, a detailed excited-state study of pristine and defected forms of indium oxide (In2O3, In2O3-x, In2O3(OH)y and In2O3-x(OH)y) surfaces was performed using time dependent density functional theory (TDDFT) calculations, the results of which were supported experimentally by transient absorption spectroscopy and photoconductivity measurements. It was found that the surface frustrated Lewis pairs (FLPs) created by a Lewis acidic coordinately unsaturated surface indium site proximal to an oxygen vacancy and a Lewis basic surface hydroxide site in In2O3-x(OH)y become more acidic and basic and hence more active in the ES compared to the GS. This provides a theoretical mechanism responsible for the enhanced activity and reduced activation energy of the photochemical reverse water gas shift reaction observed experimentally for In2O3-x(OH)y compared to the thermochemical reaction. This fundamental insight into the role of photoexcited surface FLPs for catalytic CO2 reduction could lead to improved photocatalysts for solar fuel production.

Simultaneous Time-Dependent Surface-Enhanced Raman Spectroscopy, Metabolomics, and Proteomics Reveal Cancer Cell Death Mechanisms Associated with Gold Nanorod Photothermal Therapy.

In cancer plasmonic photothermal therapy (PPTT), plasmonic nanoparticles are used to convert light into localized heat, leading to cancer cell death. Among plasmonic nanoparticles, gold nanorods (AuNRs) with specific dimensions enabling them to absorb near-infrared laser light have been widely used. The detailed mechanism of PPTT therapy, however, still remains poorly understood. Typically, surface-enhanced Raman spectroscopy (SERS) has been used to detect time-dependent changes in the intensity of the vibration frequencies of molecules that appear or disappear during different cellular processes. A complete proven assignment of the molecular identity of these vibrations and their biological importance has not yet been accomplished. Mass spectrometry (MS) is a powerful technique that is able to accurately identify molecules in chemical mixtures by observing their m/z values and fragmentation patterns. Here, we complemented the study of changes in SERS spectra with MS-based metabolomics and proteomics to identify the chemical species responsible for the observed changes in SERS band intensities during PPTT. We observed an increase in intensity of the bands at around 1000, 1207, and 1580 cm-1, which were assigned in the literature to phenylalanine, albeit with dispute. Our metabolomics results showed increased levels of phenylalanine, its derivatives, and phenylalanine-containing peptides, providing evidence for more confidence in the SERS peak assignments. To better understand the mechanism of phenylalanine increase upon PPTT, we combined metabolomics and proteomics results through network analysis, which proved that phenylalanine metabolism was perturbed. Furthermore, several apoptosis pathways were activated via key proteins (e.g., HADHA and ACAT1), consistent with the proposed role of altered phenylalanine metabolism in inducing apoptosis. Our study shows that the integration of the SERS with MS-based metabolomics and proteomics can assist the assignment of signals in SERS spectra and further characterize the related molecular mechanisms of the cellular processes involved in PPTT.

Gold Nanorods as Drug Delivery Vehicles for Rifampicin Greatly Improve the Efficacy of Combating Mycobacterium tuberculosis with Good Biocompatibility with the Host Cells.

TB remains a challenging disease to control worldwide. Nanoparticles have been used as drug carriers to deliver high concentrations of antibiotics directly to the site of infection, reducing the duration of treatment along with any side effects of off-target toxicities after systemic exposure to the antibiotics. Herein we have developed a drug delivery platform where gold nanorods (AuNRs) are conjugated to rifampicin (RF), which is released after uptake into macrophage cells (RAW264.7). Due to the nature of the macrophage cells, the nanoparticles are actively internalized into macrophages and release RF after uptake, under the safety frame of the host cells (macrophage). AuNRs without RF conjugation exhibit obvious antimicrobial activity. Therefore, AuNRs could be a promising antimycobacterial agent and an effective delivery vehicle for the antituberculosis drug Rifampicin for use in tuberculosis therapy.

Efficacy and toxicity of plasmonic photothermal therapy (PPTT) using gold nanorods (GNRs) against mammary tumors in dogs and cats.

Plasmonic photothermal therapy (PPTT) was introduced as a promising treatment of cancer. This work was conducted to evaluate the cytotoxic effect of intratumoral (IT) injection of 75µg gold nanorods (GNRs)/kg of body weight followed by direct exposure to 2 w/cm2 near infra-red laser light for 10min on ablation of mammary tumor in 10 dogs and 6 cats. Complete blood count (CBC), liver and kidney function were checked before the start of treatment and one month after injection of GNRs. Results showed that 62.5% (10/16), 25% (4/16) and 12.5% (2/16) of treated animals showed complete remission, partial remission and no response, respectively. Tumor was relapsed in 4 cases of initially responding animals (25%). Overall survival rate was extended to 315.5±20.5days. GNRs have no toxic effect on blood profile, liver or kidney functions. In conclusion, GNRs can be safely used for treatment of mammary tumors in dogs and cats.

The Coupling between Gold or Silver Nanocubes in Their Homo-Dimers: A New Coupling Mechanism at Short Separation Distances.

Using the DDA method, we investigated the near-field coupling between two excited Au or Ag 42 nm nanocubes in a face-to-face dimer configuration at small separation distances where the exponential coupling behavior distinctly changes. This could be due to the failure of the dipole approximation at short distances or a change in the electromagnetic field distribution between the adjacent monomers. A detailed calculation of the plasmonic field distribution strongly suggests that the latter mechanism is responsible for the failure of the expected exponential coupling behavior at small separation distances. The results suggest that the observed optical properties of the pair of Au or Ag nanocubes separated by distances larger than 6 nm, result from the electromagnetic coupling between the oscillating dipoles at the corners of the adjacent facets of the nanocubes. At separations smaller than 6 nm, the distribution of the plasmonic dipoles along both the facets and the corners of the adjacent monomers control the plasmonic spectra and the distance dependent optical properties of the dimer.