Rapid Pathogen Purge by Photosensitive Arginine-Riboflavin Carbon Dots without Toxicity.

Photo-activatable antipathogenic carbon dots (CDs) were prepared by carbonization of citric acid and arginine (Arg) via 3 min microwave treatment for use in the eradication of common microorganisms. Nitrogen-doped Arg CDs were spherical in shape with a size range of 0.5 to 5 nm. The Arg CDs were modified with fluorescent dyes, such as fluorescein sodium salt (FSS, as Arg-FSS) and riboflavin (RBF, as Arg-RBF), to improve antimicrobial potency by enhancing their application in photodynamic therapy. The modified Arg CDs afforded fluorescence emission properties at 520 nm in the green region in addition to excellent blue fluorescence intensity at 420 nm under 345 nm excitation upon their FSS and RBF conjugation, respectively. Although the cytotoxicity of Arg CDs was decreased for Arg-RBF CDs to 91.2 ± 0.7% cell viability for fibroblasts, the Arg-based CDs could be safely used for intravenous applications at 1000 µg/mL concentration. The Arg CDs showed broad-spectrum antimicrobial activity against common pathogens and the minimum inhibitory concentration of Arg CDs was almost two-fold decreased for the modified forms without UV light. However, faster and more effective antibacterial activity was determined for photosensitive Arg-RBF CDs, with total bacterial eradication upon UV-A light exposure for 30 min.

Shake It Off! Acoustic Manipulation of Lipid Vesicles for Mass Spectrometric Analysis.

Analyzing lipid assemblies, including liposomes and extracellular vesicles (EVs), is challenging due to their size, diverse composition, and tendency to aggregate. Such vesicles form with a simple phospholipid bilayer membrane, and they play important roles in drug discovery and delivery. The use of mass spectrometry (MS) allows for broad analysis of lipids from different classes; however, their release from the higher order structural aggregates is typically achieved by chemical means. Mechanical disruption by high frequency surface acoustic waves (SAW) is presented as an appealing alternative to preparing lipid vesicles for MS sampling. In this work, SAWs used to disrupt liposomes allow for the direct analysis of their constituent lipids by employing SAW nebulization with corona discharge (CD) ionization. We explore the effects of duration, frequency, and incorporation of nonpolar lipids, including cholesterol, on the SAW's ability to disrupt the liposome. We also report on the successful MS analysis of liposome-derived lipids along with cytochrome C in solution, thus demonstrating applications to aqueous samples and native MS conditions.

Combining plasmon-enhanced fluorescence with Rayleigh surface acoustic waves to quantify Carcinoembryonic Antigen from human plasma.

To improve the direct quantification of Carcinoembryonic Antigen (CEA) from body fluids by immunofluorescence, a surface acoustic wave (SAW) based biosensor was developed combined with an optimized silver nanostructure at the sensing region. Fluorescence signal amplification is achieved by patterning silver nanostructures using the rapid thermal annealing (RTA) method. In addition, the problem of background noise interference from nonspecific binding in human plasma is addressed by Rayleigh wave streaming at the immunoassay region, which shows a reduction in the limit of detection. The results show that the silver nanostructures significantly increase the sensor sensitivity by 49.99-fold and lower the limit of detection of CEA in phosphate buffered saline (PBS) solution to 101.94 pg/mL. The limit of detection of CEA biomarker in human plasma was successfully brought down to 11.81 ng/mL by reducing background noise using Rayleigh SAW streaming. This allows for a point-of-need sensor system to be realized in various clinical biosensing applications.

Fungal Keratitis Treatment Using Drug-Loaded Hyaluronic Acid Microgels.

Antifungal drug-loaded hyaluronic acid (HA) microgels using conjugation and encapsulation drug-loading techniques were utilized in the treatment of fungal keratitis. Natamycin (NAT) and amphotericin B (AMB) drugs were chemically linked to HA microgels by employing a chemical coupling agent to obtain conjugated (C-) HA:NAT and HA:AMB microgels. Also, these drugs were loaded into the HA microgel network during HA microgel preparation to attain encapsulated (E-) HA:NAT and HA:AMB microgels. The conjugation of drug molecules was confirmed by FT-IR spectra of bare and drug-loaded HA microgels. It was determined that the AMB loading amount was about 4-fold higher for E-HA:AMB in comparison to C-HA:AMB microgels. Furthermore, the antifungal activity of drug conjugated and encapsulated HA:NAT and HA:AMB microgels was tested on Fusarium sp. and compared with the effect of bare drug molecules as control for up to 15 days of incubation time by means of the disc diffusion technique. The antifungal activity of 200 µL at 20 mg/mL concentration of C-HA:NAT and C-HA:AMB microgels was not found to effectively inhibit Fusarium sp. growth after 1 day of incubation, whereas the same concentration of E-HA:NAT and E-HA:AMB microgels totally killed Fusarium sp. for up to 15 days. These E-HA:NAT and E-HA:AMB microgels show no cytotoxicity on the L929 fibroblast cells up to 1000 µg/mL concentration, whereas the free drug molecules destroy the cells even at 100 µg/mL concentration.

Removal of Non-Specifically Bound Proteins Using Rayleigh Waves Generated on ST-Quartz Substrates.

Label-free biosensors are plagued by the issue of non-specific protein binding which negatively affects sensing parameters such as sensitivity, selectivity, and limit-of-detection. In the current work, we explore the possibility of using the Rayleigh waves in ST-Quartz devices to efficiently remove non-specifically bound proteins via acoustic streaming. A coupled-field finite element (FE) fluid structure interaction (FSI) model of a surface acoustic wave (SAW) device based on ST-Quartz substrate in contact with a liquid loading was first used to predict trends in forces related to SAW-induced acoustic streaming. Based on model predictions, it is found that the computed SAW body force is sufficient to overcome adhesive forces between particles and a surface while lift and drag forces prevent reattachment for a range of SAW frequencies. We further performed experiments to validate the model predictions and observe that the excitation of Rayleigh SAWs removed non-specifically bound (NSB) antigens and antibodies from sensing and non-sensing regions, while rinsing and blocking agents were ineffective. An amplified RF signal applied to the device input disrupted the specific interactions between antigens and their capture antibody as well. ST-quartz allows propagation of Rayleigh and leaky SH-SAW waves in orthogonal directions. Thus, the results reported here could allow integration of three important biosensor functions on a single chip, i.e., removal of non-specific binding, mixing, and sensing in the liquid phase.

Polymer-Plasticizer Coatings for BTEX Detection Using Quartz Crystal Microbalance.

Sensing films based on polymer-plasticizer coatings have been developed to detect volatile organic compounds (VOCs) in the atmosphere at low concentrations (ppm) using quartz crystal microbalances (QCMs). Of particular interest in this work are the VOCs benzene, ethylbenzene, and toluene which, along with xylene, are collectively referred to as BTEX. The combinations of four glassy polymers with five plasticizers were studied as prospective sensor films for this application, with PEMA-DINCH (5%) and PEMA-DIOA (5%) demonstrating optimal performance. This work shows how the sensitivity and selectivity of a glassy polymer film for BTEX detection can be altered by adding a precise amount and type of plasticizer. To quantify the film saturation dynamics and model the absorption of BTEX analyte molecules into the bulk of the sensing film, a diffusion study was performed in which the frequency-time curve obtained via QCM was correlated with gas-phase analyte composition and the infinite dilution partition coefficients of each constituent. The model was able to quantify the respective concentrations of each analyte from binary and ternary mixtures based on the difference in response time (τ) values using a single polymer-plasticizer film as opposed to the traditional approach of using a sensor array. This work presents a set of polymer-plasticizer coatings that can be used for detecting and quantifying the BTEX in air, and discusses the selection of an optimum film based on τ, infinite dilution partition coefficients, and stability over a period of time.

Versatile Fluorescent Carbon Dots from Citric Acid and Cysteine with Antimicrobial, Anti-biofilm, Antioxidant, and AChE Enzyme Inhibition Capabilities.

Nanostructured fluorescent particles derived from natural molecules were prepared by a green synthesis technique employing a microwave method. The precursors citric acid (CA) and cysteine (Cys) were used in the preparation of S- and N-doped Cys carbon dots (Cys CDs). Synthesis was completed in 3 min. The graphitic structure revealed by XRD analysis of Cys CDs dots had good water dispersity, with diameters in the range of 2-20 nm determined by TEM analysis. The isoelectric point of the S, N-doped CDs was pH value for 5.2. The prepared Cys CDs displayed excellent fluorescence intensity with a high quantum yield of 75.6 ± 2.1%. Strong antimicrobial capability of Cys CDs was observed with 12.5 mg/mL minimum bactericidal concentration (MBC) against gram-positive and gram-negative bacteria with the highest antimicrobial activity obtained against Staphylococcus aureus. Furthermore, Cys CDs provided total biofilm eradication and inhibition abilities against Pseudomonas aeruginosa at 25 mg/mL concentration. Cys CDs are promising antioxidant materials with 1.3 ± 0.1 µmol Trolox equivalent/g antioxidant capacity. Finally, Cys CDs were also shown to inhibit the acetylcholinesterase (AChE) enzyme, which is used in the treatment of Alzheimer's disease, even at the low concentration of 100 µg/mL.

Fluorescence Detection of miRNA-21 Using Au/Pt Bimetallic Tubular Micromotors Driven by Chemical and Surface Acoustic Wave Forces.

In this study, surface acoustic wave (SAW) systems are described for the removal of molecules that are unbound to micromotors, thereby lowering the detection limit of the cancer-related biomarker miRNA-21. For this purpose, in the first step, mass production of the Au/Pt bimetallic tubular micromotor was performed with a simple membrane template electrodeposition. The motions of catalytic Au/Pt micromotors in peroxide fuel media were analyzed under the SAW field effect. The changes in the micromotor speed were investigated depending on the type and concentration of surfactants in the presence and absence of SAW streaming. Our detection strategy was based on immobilization of probe dye-labeled single-stranded probe DNA (6-carboxyfluorescein dye-labeled-single-stranded DNA) to Au/Pt micromotors that recognize target miRNA-21. Before/after hybridization of miRNA-21 (for both w/o SAW and SAW streaming conditions), the changes in the speed of micromotors and their fluorescence intensities were studied. The response of fluorescence intensities was observed to be linearly varied with the increase of the miRNA-21 concentration from 0.5 to 5 nM under both w/o SAW and with SAW. The resulting fluorescence sensor showed a limit of detection of 0.19 nM, more than 2 folds lower compared to w/o SAW conditions. Thus, the sensor and behaviors of Au/Pt tubular micromotors were improved by acoustic removal systems.

Aldosterone up-regulates voltage-gated potassium currents and NKCC1 protein membrane fractions.

Na+-K+-2Cl- Cotransporter (NKCC1) is a protein that aids in the active transport of sodium, potassium, and chloride ions across cell membranes. It has been shown that long-term systemic treatment with aldosterone (ALD) can enhance NKCC1 protein expression and activity in the aging cochlea resulting in improved hearing. In the present work, we used a cell line with confirmed NKCC1 expression to demonstrate that in vitro application of ALD increased outward voltage-gated potassium currents significantly, and simultaneously upregulated whole lysate and membrane portion NKCC1 protein expression. These ALD-induced changes were blocked by applying the mineralocorticoid receptor antagonist eplerenone. However, application of the NKCC1 inhibitor bumetanide or the potassium channel antagonist Tetraethyl ammonium had no effect. In addition, NKKC1 mRNA levels remained stable, indicating that ALD modulates NKCC1 protein expression via the activation of mineralocorticoid receptors and post-transcriptional modifications. Further, in vitro electrophysiology experiments, with ALD in the presence of NKCC1, K+ channel and mineralocorticoid receptor inhibitors, revealed interactions between NKCC1 and outward K+ channels, mediated by a mineralocorticoid receptor-ALD complex. These results provide evidence of the therapeutic potential of ALD for the prevention/treatment of inner ear disorders such as age-related hearing loss.

A Mixed-Metal Porphyrinic Framework Promoting Gas-Phase CO2 Photoreduction without Organic Sacrificial Agents.

A photoactive porphyrinic metal-organic framework (MOF) has been prepared by exchanging Ti into a Zr-based MOF precursor. The resultant mixed-metal Ti/Zr porphyrinic MOF demonstrates much-improved efficiency for gas-phase CO2 photoreduction into CH4 and CO under visible-light irradiation using water vapor compared to the parent Zr-MOF. Insightful studies have been conducted to probe the photocatalysis processes. This work provides the first example of gas-phase CO2 photoreduction into methane without organic sacrificial agents on a MOF platform, thereby paving an avenue for developing MOF-based photocatalysts for application in CO2 photoreduction and other types of photoreactions.

Hybrid Electro-Plasmonic Neural Stimulation with Visible-Light-Sensitive Gold Nanoparticles.

Biomedical prosthetics utilizing electrical stimulation have limited, effective spatial resolution due to spread of electrical currents to surrounding tissue, causing nonselective stimulation. So, precise spatial resolution is not possible for traditional neural prosthetic devices, such as cochlear implants. More recently, alternative methods utilize optical stimulation, mainly infrared, sometimes paired with nanotechnology for stimulating action potentials. Infrared stimulation has its own drawbacks, as it may cause collateral heating of surrounding tissue. In previous work, we employed a plasmonic method for stimulation of an electrically excitable neuroblastoma cell line, which had limited success. Here, we report the development of a hybrid electro-plasmonic stimulation platform for spatially and temporally precise neural excitation to address the above deficiencies. Primary trigeminal neurons were costimulated in vitro in a whole-cell patch-clamp configuration with subthreshold-level short-duration (1-5 ms) electrical and visible light pulses (1-5 ms). The visible light pulses were aimed at a gold-nanoparticle-coated nanoelectrode placed alongside the neuron, within 2 µm distance. Membrane action potentials were recorded with a 3-fold higher success rate and 5-fold better poststimulation cell recovery rate than with pure optical stimulation alone. Also, electrical stimulus current input was being reduced by up to 40%. The subthreshold levels of electrical stimuli in conjunction with visible light (532 nm) reliably triggered trains of action potentials. This single-cell hybrid activation was reliable and repeatable, without any damage as observed with pure optical stimulation. This work represents an empirical cellular study of the membrane action potential response produced by the cultured primary sensory trigeminal neurons when costimulated with plasmonic and electrical (hybrid) stimulation. Our hybrid neurostimulation method can be used toward development of high-acuity neural modulation prosthetic devices, tunable for individual needs, which would qualify as a preferred alternative over traditional electrical stimulation technologies.

Conformable surface acoustic wave biosensor for E-coli fabricated on PEN plastic film.

Over the last decades, great effort has gone into developing new biosensor technologies for applications in different fields such as disease diagnosis and detection of pollutants in water and food. Global developments in robotic, IoT technologies and in healthcare sensors require new flexible sensor technologies that are low cost and built from sustainable and reusable or recyclable materials. One of the most promising technologies is based on the development of surface acoustic wave (SAW) flexible biosensors, which are highly reproducible, reliable and wirelessly controllable. This work presents for the first time a novel aluminum nitride (AlN)-based conformable SAW immunosensor fabricated on recyclable polyethylene naphthalate. We apply it to the detection of E.Coli using a faster and innovative functionalization method that exploit Protein-A/antibody affinity. A higher sensitivity (Limit of detection-LoD, 6.54*105 CFU/ml) of the Lamb wave traveling on the polymeric device has been obtained in comparison with SAWs traveling on AlN on silicon substrate (LoD, 1.04*106 CFU/ml). Implementation of a finite element method allowed for the estimation of the single E.Coli mass of approximately 9*10-13 g. This work demonstrates the high biosensing potential of flexible polymeric SAW devices for bacteria contamination control in food chain, water and smart packaging.

Design of a Portable Orthogonal Surface Acoustic Wave Sensor System for Simultaneous Sensing and Removal of Nonspecifically Bound Proteins.

One challenge for current surface acoustic wave (SAW) biosensors is reducing nonspecific adsorption. A device propagating Rayleigh and shear horizontal surface acoustic waves in orthogonal directions fabricated in ST quartz has the capability of achieving simultaneous detection and nonspecific binding (NSB) protein removal. Current measurement methods for a SAW sensor system based on this device require large-size and expensive equipment such as a vector network analyzer (VNA), signal generator, and frequency counter, which are not suitable for portable, especially point-of-care, applications. In this work, a portable platform based on a direct digital synthesizer (DDS) is investigated for the orthogonal SAW sensor, integrating signal synthesis, gain control, phase/amplitude measurement, and data processing in a small, portable electronic system. This prototype was verified for both stability and repeatability, and the results matched very well with VNA measurements. Finally, system performance in real-time sensing and NSB removal was evaluated.

Intrinsically strained noble metal-free oxynitrides for solar photoreduction of CO2.

Metal oxynitrides show promising activity for photocatalytic solar water splitting and CO2 reduction under solar irradiance. Precise control of cation ratios in oxynitrides is an inevitable challenge that needs to be overcome for achieving effective band gap tuning. Here we report the density functional theory-based calculations for the intricate structure-function relationships of Zn-Ga based oxynitrides and correlate the results with the experimental parameters. Crucial material property descriptors such as elemental composition, intrinsic lattice strain, and vacancy defects were exploited during the synthesis to achieve stable oxynitride photocatalysts that demonstrated CO2 conversion to CO under simulated solar light, without any noble metal impregnation. The highest CO production rate surpassed that of TiO2 under the same conditions. This work inspires future research on oxynitride materials with tailored optical properties and sustainable photocatalytic activity which enables their large scale applications.

Electron injection study of photoexcitation effects on supported subnanometer Pt clusters for CO2 photoreduction.

Using density functional theory, we study the effect of injected electrons (simulating photoexcited electrons) on the energetics, structures, and binding sites available to CO2 molecules on subnanometer Pt clusters decorated onto anatase TiO2(101) surfaces, shedding light on the first and key step of CO2 photoreduction. Upon the addition of one, two, or three electrons, the O-C-O angles of adsorbed CO2 become progressively smaller in binding sites that directly contact Pt clusters, while no significant change is found in the intra bond length of the adsorbed CO2 and in the bonding distances between the adsorbed CO2 and supported clusters. The extra electrons lead to the stabilization of adsorption sites identified on neutral slabs, including previously metastable configurations, suggesting the enhancement of accessible CO2 binding sites. Furthermore, supported clusters are able to populate the electronic states of adsorbed CO2 species, facilitating the formation of the CO2- anion. To help interpret experimentally observed frequencies, conversion factors are proposed to gain insight into the charge state and O-C-O angle of the adsorbed CO2. Interestingly, upon electron addition, cluster reconstruction may exist due to the bonding inclination between CO2 and atoms in the Pt cluster, further stabilizing the intermediate complexes. Finally, the rate-limiting step (C-O bond cleavage) in the CO2 dissociation to CO is slightly reduced by the introduction of an extra electron. Our results show that subnanometer metal cluster based photocatalysts are good candidates for CO2 photoreduction.

Integrating Metal-Enhanced Fluorescence and Surface Acoustic Waves for Sensitive and Rapid Quantification of Cancer Biomarkers from Real Matrices.

Metal-enhanced fluorescence (MEF) is utilized to lower the detection limit of carcinoembryonic antigen (CEA), a prognostic biomarker for colorectal cancer among others, in immunofluorescence assays. In addition, Rayleigh surface acoustic waves (SAWs) were utilized to remove nonspecifically bound proteins, improve mixing, and reduce incubation times. Fluorescence intensity was plasmonically enhanced by incubating silver nanocubes (AgNCs) of 50 nm edge-length on a SAW device. This increased sensor sensitivity by a factor of 6 and lowered the limit of detection to below 1 ng/mL in fluorescence detection of the antigen. Surface density of the AgNCs was optimized to produce the largest MEF, which increased the signal intensity by an order of magnitude. Acoustic streaming induced by Rayleigh SAWs was found to decrease antibody/antigen incubation times to 1/6th of the values without such micromixing, and to increase the fluorescence signal strength. Overall, the demonstrated results allow for construction of a sensor capable of detecting CEA rapidly in clinically relevant concentrations. Variables relevant for optimizing this sensor performance were identified, which will enable even better performance in immunofluorescence assays.

Nanoparticle-based Plasmonic Transduction for Modulation of Electrically Excitable Cells.

There is a compelling need for the development of new sensory and neural prosthetic devices which are capable of more precise point stimulation. Current prosthetic devices suffer from the limitation of low spatial resolution due to the non-specific stimulation characteristics of electrical stimulation, i.e., the spread of electric fields generated. We present a visible light stimulation method for modulating the firing patterns of electrically-excitable cells using surface plasmon resonance phenomena. In in-vitro studies using gold (Au) nanoparticle-coated nanoelectrodes, we show that this method (substrate coated with nanoparticles) has the potential for incorporating this new technology into neural stimulation prosthetics, such as cochlear implants for the deaf, with very high spatial resolution. Au nanoparticles (NPs) were coated on micropipettes using aminosilane linkers; and these micropipettes were used for stimulating and inhibiting the action potential firing patterns of SH-SY5Y human neuroblastoma cells and neonatal cardiomyocytes. Our findings pave the way for development of biomedical implants and neural testing devices using nanoelectrodes capable of temporally and spatially precise excitation and inhibition of electrically-excitable cellular activity.

Gold nanoparticle-based low limit of detection Love wave biosensor for carcinoembryonic antigens.

In this work, a Love wave biosensing platform is described for detecting cancer-related biomarker carcinoembryonic antigen (CEA). An ST 90°-X quartz Love wave device with a layer of SiO2 waveguide was combined with gold nanoparticles (Au NPs) to amplify the mass loading effect of the acoustic wave sensor to achieve a limit of detection of 37pg/mL. The strategy involves modifying the Au NPs with anti-CEA antibody conjugates to form nanoprobes in a sandwich immunoassay. The unamplified detection limit of the Love wave biosensor is 9.4ng/mL. This 2-3 order of magnitude reduction in the limit of detection brings the SAW platform into the range useful for clinical diagnosis. Measurement electronics and microfluidics are easily constructed for acoustic wave biosensors, such as the Love wave device described here, allowing for robust platforms for point of care applications for cancer biomarkers in general.

Concentration-dependent effects of alendronate and pamidronate functionalized gold nanoparticles on osteoclast and osteoblast viability.

Severe osteoporotic diseases, such as Paget's disease, Osteogenesis Imperfecta, and Legg Calve Perthes disease, lack treatments that address the pathobiology of the diseases, as well as, long-term and prospective studies. Bisphosphonates, which are known to dramatically hinder the viability of osteoclast cells, along with gold nanoparticles (GNP) are a potential theranostic for osteoporotic diseases. We evaluated GNP functionalized with two different bisphosphonates, namely, alendronate and pamidronate. RANKL differentiated murine pre-osteoclasts (Raw 264.7) and murine osteoblasts (7F2) were treated with varying concentrations ranging from 0.1-5 µM of free and GNP bound bisphosphonates. GNPs with an average size of ∼15 nm were functionalized with alendronate and pamidronate through surface modification by self-assembly. MTT viability assay results show no changes in viability of the osteoclasts when treated with free bisphosphonates in the range of 1-5 µM, but significant decrease on treatment with functionalized GNP at concentrations above the range of 0.1-1 µM depending on the bisphosphonate. Osteoblast cell viability is maintained at all but the highest concentrations used. Qualitative and quantitative characterization by Western Blot for RANKL expression in the osteoblast cell line shows that expression is largely maintained. These results provide a basis for methods that use bisphosphonate functionalized GNP in the treatment of osteoporotic bone diseases. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 21-29, 2017.

The effect of the morphology of supported subnanometer Pt clusters on the first and key step of CO2 photoreduction.

Using density functional theory calculations, we investigate the influence of size-dependent cluster morphology on the synergistic catalytic properties of anatase TiO2(101) surfaces decorated with subnanometer Pt clusters. Focusing on the formation of the key precursor in the CO2 photoreduction reaction (bent CO2(-)), we find that flatter (2D-like) Pt clusters that "wet" the TiO2 surface offer significantly less benefit than 3D-like Pt clusters. We attribute the differences to three factors. First, the 3D clusters provide a greater number of accessible Pt-TiO2 interfacial sites with geometries that can aid CO2 bond bending and charge transfer processes. Second, binding competition among each Pt-CO2 bonding interaction mitigates maximum orbital overlaps, leading to insufficient CO2 binding. Third and also most interestingly, the 3D clusters tend to possess higher structural fluxionality than the flatter clusters, which is shown to correlate positively with CO2 binding strength. The preferred morphology adopted by the clusters depends on several factors, including the cluster size and the presence of oxygen vacancies on the TiO2 surface; this suggests a strategy for optimizing the synergistic effect between Pt clusters and TiO2 surfaces for CO2 photocatalysis. Clusters of ∼6-8 atoms should provide the largest benefit, since they retain the desired 3D morphology, yet are small enough to exhibit high structural fluxionality. Electronic structure analysis provides additional insight into the electronic motivations for the enhanced binding of CO2 on TiO2-supported 3D Pt clusters, as well as suppressed binding on flattened, 2D-like clusters.