Targeting Manganese Amidinate and ß-Ketoiminate Complexes as Precursors for Mn-Based Thin Film Deposition.

With a focus on Mn based organometallic compounds with suitable physico-chemical properties to serve as precursors for chemical vapor deposition (CVD) and atomic layer deposition (ALD) of Mn-containing materials, systematic synthetic approaches with ligand variation, detailed characterization, and theoretical input from density functional theory (DFT) studies are presented. A series of new homoleptic all-nitrogen and mixed oxygen/nitrogen-coordinated Mn(II) complexes bearing the acetamidinate, formamidinate, guanidinate and ß-ketoiminate ligands have been successfully synthesized for the first time. The specific choice of these ligand classes with changes in structure and coordination sphere and side chain variations result in significant structural differences whereby mononuclear and dinuclear complexes are formed. This was supported by density functional theory (DFT) studies. The compounds were thoroughly characterized by single crystal X-ray diffraction, magnetic measurements, mass spectrometry and elemental analysis. To evaluate their suitability as precursors for deposition of Mn-based materials, the thermal properties were investigated in detail. Mn(II) complexes possessing the most promising thermal properties, namely Bis(N,N'-ditertbutylformamidinato)manganese(II) (IV) and Bis(4-(isopropylamino)pent-3-en-2-onato)manganese(II) (ßIII) were used in reactivity studies with DFT to explore their interaction with oxidizing co-reactants such as oxygen and water which will guide future CVD and ALD process development.

Electrochemical synthesis of 2D-silver nanodendrites functionalized with cyclodextrin for SERS-based detection of herbicide MCPA.

Surface enhanced Raman spectroscopy (SERS) is a powerful analytical technique that has found application in the trace detection of a wide range of contaminants. In this paper, we report on the fabrication of 2D silver nanodendrites, on silicon chips, synthesized by electrochemical reduction of AgNO3at microelectrodes. The formation of nanodendrites is tentatively explained in terms of electromigration and diffusion of silver ions. Electrochemical characterization suggests that the nanodendrites do not stay electrically connected to the microelectrode. The substrates show SERS activity with an enhancement factor on the order of 106. Density functional theory simulations were carried out to investigate the suitability of the fabricated substrate for pesticide monitoring. These substrates can be functionalized with cyclodextrin macro molecules to help with the detection of molecules with low affinity with silver surfaces. A proof of concept is demonstrated with the detection of the herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA).

Class IIa HDAC inhibition reduces breast tumours and metastases through anti-tumour macrophages.

Although the main focus of immuno-oncology has been manipulating the adaptive immune system, harnessing both the innate and adaptive arms of the immune system might produce superior tumour reduction and elimination. Tumour-associated macrophages often have net pro-tumour effects, but their embedded location and their untapped potential provide impetus to discover strategies to turn them against tumours. Strategies that deplete (anti-CSF-1 antibodies and CSF-1R inhibition) or stimulate (agonistic anti-CD40 or inhibitory anti-CD47 antibodies) tumour-associated macrophages have had some success. We hypothesized that pharmacologic modulation of macrophage phenotype could produce an anti-tumour effect. We previously reported that a first-in-class selective class IIa histone deacetylase (HDAC) inhibitor, TMP195, influenced human monocyte responses to the colony-stimulating factors CSF-1 and CSF-2 in vitro. Here, we utilize a macrophage-dependent autochthonous mouse model of breast cancer to demonstrate that in vivo TMP195 treatment alters the tumour microenvironment and reduces tumour burden and pulmonary metastases by modulating macrophage phenotypes. TMP195 induces the recruitment and differentiation of highly phagocytic and stimulatory macrophages within tumours. Furthermore, combining TMP195 with chemotherapy regimens or T-cell checkpoint blockade in this model significantly enhances the durability of tumour reduction. These data introduce class IIa HDAC inhibition as a means to harness the anti-tumour potential of macrophages to enhance cancer therapy.

A step toward correct interpretation of XPS results in metal oxides: A case study aided by first-principles method in ZnO.

Metal oxide semiconductors constitute a vast group of materials whose physical properties are greatly affected by native defects. For decades, x-ray photoelectron spectroscopy (XPS) has been widely used in defect analysis. However, correct interpretation of XPS results remains a difficult task. In this work, we present a detailed first-principles study on the core-level shift of the most stable and commonly cited crystal imperfections in ZnO, including O and -OH species at the surface with different coverages and bulk defects, including O interstitial (Oi), O vacancy in the +2 charge state (Vo2+), and the neutral vacancy (Vo0). The O1s core level spectrum is simulated and compared with experiments to understand the correlation between local atomic structures and features in the O1s spectrum. In particular, our results indicate that the widely adopted assignment in the defect analysis of ZnO, which links the defect peak in XPS to Vo, the most stable defect, is very likely a misinterpretation. Theoretical analysis indicates that there are no distinguishable XPS features arising from the Vo defect. Furthermore, we show that the commonly observed defect-related peak instead arises due to Oi or specific surface configurations. Given the importance of native defects in materials performance, misinterpretation of XPS results may lead to erroneous conclusions regarding materials properties. This work provides a first-principles basis for the analysis of oxide defects through XPS.

COVID-19 modifications to a first year medical human anatomy course: Effects on student performance on summative examinations.

The COVID-19 (COVID) pandemic forced changes in how medical curricula are organized and delivered. In addition to disease mitigation strategies, other curricular modifications were required to maintain educational effectiveness and student and faculty safety. While these changes appear to be successful in their primary goal, their effect on learning and other important educational outcomes is less well understood. We describe changes to our anatomy course and describe their effects on summative examination scores. We compared anatomy examination scores from 4 years prior to COVID with scores from the 2 years following COVID mandated changes in an effort to determine the effectiveness of our course modifications. Examination scores for the first of four successive Blocks of instruction following the implementation of curricular changes demonstrated a lower mean score and greater range of scores than for the four pre-COVID years. Pre-COVID and post-COVID scores for Blocks II, III, and IV were comparable. Our results indicate that our changes to the anatomy curriculum did not prevent a performance decline during the first Block of instruction only. However, students were able to successfully adapt to these changes during the remainder of the course. We discuss factors that may have accounted for the Block I performance decline and call attention to changes within the larger curriculum that may have affected student performance.

A method for rewarding collaborative efforts in preclinical assessments.

Student success in basic medical science courses is typically determined by their individual performance on examinations of various types. Previous research both within and outside medical education has shown that the use of educational assessment activities can increase learning as demonstrated by performance on subsequent examinations, a phenomenon known as the testing effect. Activities primarily designed and used for assessment and evaluation purposes can also be used as teaching opportunities. We developed a method for measuring and evaluating student accomplishment in a preclinical basic science course that incorporates both individual and collaborative efforts, encourages and rewards active participation, does not compromise the reliability of the assessment outcome and is perceived by the students as helpful and valuable. The approach involved a two-part assessment activity composed of an individual examination and a small group examination with each component differentially weighted in determining an overall examination score. We found that the method was successful in encouraging collaborative efforts during the group component and provided valid measures of student grasp of the subject matter. We describe the development and implementation of the method, provide data derived from its use in a preclinical basic science course and discuss factors to be addressed when utilizing this approach to ensure fairness and reliability of the outcome. We include brief summary comments from students regarding their impressions of the value of this method.

Horseshoe kidney: Morphologic features, embryologic and genetic etiologies, and surgical implications.

The horseshoe kidney (HSK) is the most common congenital abnormality of the upper urinary tract with an incidence of approximately 1 in 500 in the general population. Although individuals with HSK are often asymptomatic, they are at increased risk for neoplasms, infections, ureteropelvic obstruction secondary to lithiasis or vascular compression. Direct injury from trauma is increased in these individuals as is the risk of intraoperative complications secondary to damage involving the typically complex renal or adrenal vascular supply. We briefly review etiological factors including renal and urinary system embryology, genetic mutations, abnormalities related to faulty cell signaling, aberrant cell migration, and other possible causes including environmental exposures and trauma. In addition, we call attention to factors that might influence the success of surgical procedures in patients with HSK. We argue that an understanding of possible etiologies of the HSK and its different subtypes may be useful when planning surgical procedures or considering risk-benefit ratios associated with different surgical options. We briefly present the organization of a HSK in a 100-year-old male demonstrating an unusual vascular supply discovered during a dissection laboratory session in a medical school anatomy course. We describe the structure of the HSK, the position and relationships of the HSK to other structures within the abdomen, and the associated vascular relationships.

Higher tax and less work: reverse "Keep up with the Joneses" and rising inequality.

To counteract excessive effort due to relative income comparison among identical agents, the literature suggests a tax response equal to the negative externality. Assuming a general income distribution, we show that an optimal tax must be higher under a general social welfare function, to not only reduce inefficiency but also inequality. We recommend a practical tax response to stronger comparison - to hold employment constant, which does not require unrealistic information including unobservable comparison. Surprisingly, the tax response will dominate the comparison effect and reduce labour supply or reverse "keeping up with the Joneses" on intensive margins, and also reverse the otherwise rising inequality. Supplementary Information: The online version contains supplementary material available at 10.1007/s00712-023-00821-2.

An approach to determining, delivering, and assessing essential course content in a medical human anatomy course.

Learning objectives typically indicate subject matter judged to be important or that represents essential material to be learned during a course. We report here on our efforts to identify essential course content and determine our effectiveness teaching and assessing this content in our preclinical human anatomy course. Using a consensus driven approach, we identified anatomical structures, relationships, and functional concepts judged to represent essential material in our unit on the thorax that students were expected to be familiar with. We then determined performance on specific examination questions that focused directly on the essential material. Thirty-seven of 48 students (77%) correctly answered all 34 of 51 questions that directly focused on content we defined as essential. The remaining 11 students answered the majority of these questions correctly. The overall mean score was 86% (range 61%-98%). Our review of student performance on the End of Block thorax examination confirmed our belief that we were successful in helping students learn material we defined as essential. We found the process described here to be helpful in defining essential content and for helping focus and improve medical education and learning assessment based on that material. We believe the idea of defining essential content that can be efficiently taught and effectively learned within a proscribed period of time is an important and necessary objective. We believe the approach used here might be successfully utilized in other programs in efforts aimed at quality improvement.

Anatomy of the physical examination: A small group learning approach for increasing engagement and learning in a medical gross anatomy course.

The ability to perform and interpret the physical examination requires an understanding of human anatomy and how to apply that content in the clinical setting. Previous work has shown that students understand and retain information more effectively when they are actively engaged in the learning process and it is clearly linked to other coursework and their future needs. We developed a series of learning activities, based on the general physical examination, designed to enhance engagement and encourage durable learning of anatomical principles that are important in performing and interpreting the physical examination. Activities were designed for use in small group settings with faculty supervision and input as needed. We describe these activities and provide comments from students regarding the perceived value of these learning activities. Students reported that the applied anatomy learning activities were engaging and aided in their learning of human anatomy. Additionally, students appreciated the connection between the applied anatomy activities and the skills being learned in concurrent coursework focusing on the physical examination. We observed that applied human anatomy exercises modeled after components of the general physical examination and embedded in an anatomy course enhanced student engagement and helped students appreciate the importance of anatomical principles. We note that sensitivity to and acceptance of personal preferences and religious matters must be shown when using learning activities that involve close physical interactions to teach anatomical topics.

Small group learning/assessment sessions: A method using test enhanced learning to increase engagement in a basic medical science neuroanatomy course.

Previous research has shown that test-enhanced learning with structured feedback facilitates durable learning. We describe a small group learning/assessment activity using these approaches intended to increase engagement and engagement with the course material. We divided our class into six groups of seven students each that worked together in the activity. During each weekly session, course related multiple choice questions were projected and each group instructed to work independently to arrive at a consensus answer for each question. After each question is considered, a faculty facilitator then randomly selects one group to share their choice with the other groups and provide and rationale for their choice. A different group or groups are then called upon to share their choice. When differences emerge, the instructor then facilitates discussion among the groups in an effort to resolve confusion or incomplete or incorrect understanding that becomes evident. We found that attendance for these sessions was greater than for the more traditional lecture based session also included in the course and that students were actively engaged in this learning activity. The success of the small group learning/assessment session is dependent on several factors including the difficulty of the questions and their relatedness to the course objectives, the timing and placement of the session or sessions within the course and the skill of the faculty facilitator in encouraging active participation while ensuring a safe environment in which students can openly share their sometimes incomplete or incorrect understanding of the material.

Income Status and Life Satisfaction.

The importance of both income rank and relative income, as indicators of status, has long been recognised in the literature on life satisfaction and happiness. Recently, several authors have made explicit comparisons of the relative importance of these two measures of income status, and concluded that rank dominates to the extent that reference income becomes insignificant in regressions including both these explanatory variables, and that even absolute or household income, otherwise always positively related to happiness, may lose statistical significance. Here we test this hypothesis with a large UK panel (British Household Panel Survey and Understanding Society) for 1996-2017, split by age and retirement status, and find, contrary to previous results, that rank, household income and reference income are all usually important explanatory variables, but with significant differences between subgroups. This finding holds when rank is in its often-used relative form, and also with absolute rank.

Rational Development of Guanidinate and Amidinate Based Cerium and Ytterbium Complexes as Atomic Layer Deposition Precursors: Synthesis, Modeling, and Application.

Owing to the limited availability of suitable precursors for vapor phase deposition of rare-earth containing thin-film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris-guanidinate and tris-amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C-substituents on the N-C-N backbone (Me, NMe2 , NEt2 , where Me=methyl, Et=ethyl) and the N-substituents from symmetrical iso-propyl (iPr) to asymmetrical tertiary-butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)3 ] 1 and [Yb(dpdmg)3 ] 6 (dpdmg=N,N'-diisopropyl-2-dimethylamido-guanidinate) highlight a monomeric nature in the solid-state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O2 ) and water (H2 O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)3 ] 1 was used for proof-of-principle ALD depositions of CeO2 thin films using water as co-reactant. The self-limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO2 films formed on Si(100) substrates. This study confirms that moving towards nitrogen-coordinated rare-earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials.

Early radiation-induced oral pain signaling responses are reduced with pentoxifylline treatment.

Radiation-induced acute oral mucositis is associated with inflammation and pain. In other realms of pain research, nociceptors are known to be activated by inflammatory cytokines; for example, tumor necrosis factor alpha (TNF-α) can activate transient receptor potential ion channels on sensory neurons. But there is an unclear relationship between inflammatory cytokines and molecular mediators of pain in radiation-induced mucositis (RIM) and radiation-associated pain (RAP). In this prospective, analytical, experimental pilot study, a common drug (pentoxifylline [PTX]) was used with the goal of inhibiting TNF-α signaling in mice that underwent lingual irradiation to induce severe acute oral RIM/RAP. Body weight and glossitis scores were recorded daily. Eye wiping behaviors were assayed as a surrogate measure of oral discomfort (which is possible due to cross-sensitization of the mandibular and ophthalmic branches of the trigeminal nerve). Quantitative real-time reverse transcription polymerase chain reaction was performed on irradiated tongue tissue to measure changes in expression of TNF-α, its receptor, nuclear factor kappa-light-chain-enhancer of activated B cells, transient receptor potential vanilloid type 1 (TRPV1), and transient receptor potential vanilloid type 4 (TRPV4). Responsiveness of afferent sensory trigeminal neurons to TNF-α, a TRPV1 agonist (capsaicin), and a partial TRPV4 agonist (histamine) was measured via calcium imaging. Although PTX treatment did not reduce glossitis severity or mitigate weight loss in mice with RIM/RAP, it did inhibit the upregulation of TNF-α's receptor that normally accompanies RIM, and it also reduced neuronal responsiveness to each of the aforementioned chemical stimuli. These results provide provisional evidence that inhibition of TNF-α signaling with PTX treatment may serve as a useful tool for reducing pain in head and neck cancer patients.

Monolayer Doping of Germanium with Arsenic: A New Chemical Route to Achieve Optimal Dopant Activation.

Reported here is a new chemical route for the wet chemical functionalization of germanium (Ge), whereby arsanilic acid is covalently bound to a chlorine (Cl)-terminated surface. This new route is used to deliver high concentrations of arsenic (As) dopants to Ge, via monolayer doping (MLD). Doping, or the introduction of Group III or Group V impurity atoms into the crystal lattice of Group IV semiconductors, is essential to allow control over the electronic properties of the material to enable transistor devices to be switched on and off. MLD is a diffusion-based method for the introduction of these impurity atoms via surface-bound molecules, which offers a nondestructive alternative to ion implantation, the current industry doping standard, making it suitable for sub-10 nm structures. Ge, given its higher carrier mobilities, is a leading candidate to replace Si as the channel material in future devices. Combining the new chemical route with the existing MLD process yields active carrier concentrations of dopants (>1 × 1019 atoms/cm3) that rival those of ion implantation. It is shown that the dose of dopant delivered to Ge is also controllable by changing the size of the precursor molecule. X-ray photoelectron spectroscopy (XPS) data and density functional theory (DFT) calculations support the formation of a covalent bond between the arsanilic acid and the Cl-terminated Ge surface. Atomic force microscopy (AFM) indicates that the integrity of the surface is maintained throughout the chemical procedure, and electrochemical capacitance voltage (ECV) data shows a carrier concentration of 1.9 × 1019 atoms/cm3 corroborated by sheet resistance measurements.

Highly Sensitive SERS Detection of Neonicotinoid Pesticides. Complete Raman Spectral Assignment of Clothianidin and Imidacloprid.

The use of surface enhanced Raman spectroscopy in the development of low cost, portable sensor devices that can be used in the field for nitroguanidine neonicotinoid insecticide detection is appealing. However, a key challenge to achieving this goal is the lack of detailed analysis and vibrational assignment for the most popular neonicotinoids. To make progress toward this goal, this paper presents an analysis of the bulk Raman and SERS spectra of two neonicotinoids, namely clothianidin and imidacloprid. Combined with first-principles simulations, this allowed assignment of all Raman spectral modes for both molecules. To our knowledge, this is the first report of SERS analysis and vibrational assignment of clothianidin, and a comprehensive assignment and analysis is provided for imidacloprid. Silver nanostructured surfaces were fabricated for qualitative SERS analysis, which provides the characteristic spectra of the target molecules and demonstrates the ability of SERS to sense these molecules at concentrations of 1 ng/mL. These concentrations are on par with high-end chromatographic-mass spectroscopy laboratory methods. These SERS sensors thus allow for the selective and sensitive detection of neonicotinoids and provide complementary qualitative data for the molecules. Furthermore, this technique can be adapted to portable devices for remote sensing applications. Further work focuses on integrating our device with an electronics platform for truly portable residue detection.

The role of Ru passivation and doping on the barrier and seed layer properties of Ru-modified TaN for copper interconnects.

Size reduction of the barrier and liner stack for copper interconnects is a major bottleneck in further down-scaling of transistor devices. The role of the barrier is to prevent diffusion of Cu atoms into the surrounding dielectric, while the liner (also referred to as a seed layer) ensures that a smooth Cu film can be electroplated. Therefore, a combined barrier + liner material that restricts the diffusion of Cu into the dielectric and allows for copper electro-deposition is needed. In this paper, we have explored barrier + liner materials composed of 1 and 2 monolayers (MLs) of Ru-passivated ϵ-TaN and Ru doped ϵ-TaN and focused on their interactions with Cu through the adsorption of small Cu clusters with 1-4 atoms. Moreover, different doping patterns for Ru doping in TaN are investigated to understand how selective doping of the ϵ-TaN surface influences surface stability. We found that an increased concentration of Ru atoms in the outermost Ta layer improves the adhesion of Cu. The strongest binding of the Cu atoms was found on the 100% Ru doped surface followed by the 1 ML Ru passivated surface. These two surfaces are recommended for the combined barrier + liner for Cu interconnects. The closely packed arrangements of Cu were found to exhibit weak Cu-slab and strong Cu-Cu interactions, whereas the sparse arrangements of Cu exhibit strong Cu-slab and weak Cu-Cu interactions. The Cu atoms seem to bind more favorably when they are buried in the doped or passivated surface layer due to the increase in their coordination number. This is facilitated by the surface distortion arising from the ionic radius mismatch between Ta and Ru. We also show that the strong Cu-Cu interaction alone cannot predict the association of Cu atoms as a few 2D Cu clusters showed stronger Cu-Cu interaction than the 3D clusters, highlighting the importance of Cu-surface interactions.

On the use of DFT+U to describe the electronic structure of TiO2 nanoparticles: (TiO2)35 as a case study.

One of the main drawbacks in the density functional theory (DFT) formalism is the underestimation of the energy gaps in semiconducting materials. The combination of DFT with an explicit treatment of the electronic correlation with a Hubbard-like model, known as the DFT+U method, has been extensively applied to open up the energy gap in materials. Here, we introduce a systematic study where the selection of the U parameter is analyzed considering two different basis sets: plane-waves and numerical atomic orbitals (NAOs), together with different implementations for including U, to investigate the structural and electronic properties of a well-defined bipyramidal (TiO2)35 nanoparticle. This study reveals, as expected, that a certain U value can reproduce the experimental value for the energy gap. However, there is a high dependence on the choice of basis set and on the U parameter employed. The present study shows that the linear combination of the NAO basis functions, as implemented in Fritz Haber Institute ab initio molecular simulation (FHI-aims), requires, requires a lower U value than the simplified rotationally invariant approach, as implemented in the Vienna ab initio simulation package (VASP). Therefore, the transfer of U values between codes is unfeasible and not recommended, demanding initial benchmark studies for the property of interest as a reference to determine the appropriate value of U.

Identification of Swimmers in Distress Using Unmanned Aerial Vehicles: Experience at the Mont-Tremblant IRONMAN Triathlon.

Background: This preliminary report describes our experience using unmanned aerial vehicles (UAVs) to identify swimmers in distress at the 2018 Mont-Tremblant IRONMAN triathlon (Quebec, Canada). Methods: In a prospective pilot study, we sought to determine whether UAV surveillance could identify swimmers showing signs of distress quicker than conventional methods (i.e., lifeguards on the ground and on watercraft). In addition, we investigated the feasibility of using UAVs for medical surveillance at a triathlon event in terms of operations, costs, safety, legal parameters, and added value. Prior to the race, we screened participants for medical conditions that could elevate their risk of injury during the swim portion of the triathlon. Athletes deemed to be at increased risk were given a yellow swimming cap to enhance their surveillance by trained observers watching a live video feed from the UAVs. Results: On race day, a total of 3 UAVs (2 mobile, 1 tethered) were launched over Lake Tremblant and provided 3 observers with live video of the swimmers. Of the 2,473 race participants, there were 25 athletes with pre-identified medical conditions who wore a yellow cap during the swim. We did not detect any signs of distress among swimmers wearing yellow caps. Among the remaining 2,448 athletes, there were 5 swimmers who demonstrated signs of distress and required mobilization of water rescue boats; UAV surveillance identified 1 of these 5 distress events before it was seen by lifeguards on rescue boats. None of the athletes in the IRONMAN suffered an adverse event while swimming. Several technical and safety issues related to UAV surveillance arose including poor visibility, equipment loss, and flight autonomy. Conclusion: While our preliminary findings suggest that using UAVs to identify distressed swimmers during an IRONMAN race is feasible and safe, more research is necessary to determine how to optimize UAV surveillance at mass sporting events and integrate this technology within the existing emergency response teams.

Direct Visualization of Independent Ta Centers Supported on Two-Dimensional TiO2 Nanosheets.

Highly dispersed, supported oxides are ubiquitous solid catalysts but can be challenging to characterize with atomic precision. Here, it is shown that crystalline anatase TiO2 nanosheets (∼5 nm thick) are ideal supports for imaging highly dispersed active sites. Ta cations were deposited by several routes, and high-resolution high angle annular dark-field scanning transmission electron microscopy was used to determine the location of Ta with respect to the TiO2 lattice and quantify Ta-Ta distances. In the best case, it is shown that >80% of Ta atoms are isolated from one another, whereas other techniques are blind to this critical catalytic property or give only qualitative estimates. TiO2 nanosheets may prove to be a useful platform for other types of catalysis studies.