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).

Update in Veterinary Radiation Oncology: Focus on Stereotactic Radiation Therapy.

Stereotactic radiotherapy (SRT) involves the precise delivery of highly conformal, dose-intense radiation to well-demarcated tumors. Special equipment and expertise are needed, and a unique biological mechanism distinguishes SRT from other forms of external beam radiotherapy. Families find the convenient schedules and minimal acute toxicity of SRT appealing. Common indications in veterinary oncology include nasal, brain, and bone tumors. Many other solid tumors can also be treated, including spinal, oral, lung, heart-base, liver, adrenal, and prostatic malignancies. Accessibility of SRT is improving, and new data are constantly emerging to define parameters for appropriate case selection, radiation dose prescription, and long-term follow-up.

A method for assessing student ability to apply anatomical knowledge within a traditional anatomy laboratory examination.

Fidelity between teaching activities and assessment methods is an important goal of knowledge and performance evaluations in medical education. Ideally, assessment methods provide evidence of learning that reflects the types of knowledge described in the learning objectives of the course. The most reliable assessments involve the same or similar tasks as those used during the instructional components of the course. Our preclinical human anatomy course includes, in addition to traditional lecture and cadaver-based laboratory learning activities, a series of applied human anatomy learning activities intended to emphasize human anatomy as it is encountered in living human individuals. The learning activities involve psychomotor behaviors including inspection, palpation, and auscultation, techniques used in the physical examination, as well as other activities designed to emphasize anatomical structures and tissues as they may be found in patient populations. We describe here our method for measuring student success in learning human anatomy in this manner, highlighting the direct linkage between the learning activities and the assessment tasks. We describe our performance scoring method and how we include this data in the calculation of an anatomy examination grade. As an indicator of our success with this approach, we include performance scores for the applied anatomy questions included on the laboratory component of our unit examinations for two successive academic years. We conclude with summary comments from students regarding the applied anatomy learning activities and assessment approach and offer suggestions for addressing specific challenges associated with the use of these types of assessment methods.

Self-reducing precursors for aluminium metal thin films: evaluation of stable aluminium hydrides for vapor phase aluminium deposition.

Thin films of Al as interconnect materials and those of AlN as wide bandgap semiconductor and piezoelectric material are of great interest for microelectronic applications. For the fabrication of these thin films via chemical vapor deposition (CVD) based routes, the available precursor library is rather limited, mostly comprising aluminium alkyls, chlorides, and few small amine-stabilized aluminium hydrides. Herein, we focused on rational precursor development for Al, their characterization and comparison to existing precursors comprising stabilized aluminium hydrides. We present and compare a series of potentially new and reported aluminium hydride precursors divided into three main groups with respect to their stabilization motive, and their systematic structural variation to evaluate the physicochemical properties. All compounds were comprehensively characterized by means of nuclear magnetic resonance spectroscopy (NMR), Fourier-transform infrared spectroscopy (FTIR), elemental analysis (EA), electron-impact ionization mass spectrometry (EI-MS) and thermogravimetric analysis (TGA). Promising representatives were further evaluated as potential single source precursors for aluminium metal formation in proof-of-concept experiments. Structure and reaction enthalpies with NH3 or H2 as co-reactants were calculated via first principles density functional theory simulations and show the great potential as atomic layer deposition (ALD) precursors for Al and AlN thin films.

A longitudinal analysis of the impact of nonsurgical and surgical treatment of peri-implantitis upon clinical parameters and implant stability quotient values. A 2-3-year follow-up.

OBJECTIVES: In this study, the aim was to investigate the medium- to long-term impact of peri-implantitis treatment upon clinical parameters and implant stability quotient values and to ascertain if magnetic resonance frequency analysis can be used as a diagnostic tool to demonstrate postoperative healing following treatment of peri-implantitis. MATERIALS AND METHODS: A total of n = 26 patients (n = 86 implants) diagnosed with peri-implantitis were recruited for this prospective cohort study and four different treatment modalities were used. Baseline measurements of a number of clinical parameters as well as implant stability measurements in the form of ISQ were recorded. These measurements were repeated at 6, 12, and 24-36 months following treatment. Analysis of variance was performed for all implants treated as well as separately for each treatment modality. A regression model was also used to determine factors affecting ISQ measurements over time. RESULTS: Treatment of peri-implantitis resulted in significant improvements of both average PPDs and BOP (p < .0001 and p < .01). ISQ values marginally improved initially for all treatment modalities, but improvement was only maintained for 2-3 years in treatment modalities I (+1.28), III (+1.49), and IV (+2.92). There was a statistically significant negative linear correlation between average PPD and the ISQ values recorded both at baseline (r = -.618, p < 0.0001) and at 2/3 years (r = -.604, p < 0.0001). CONCLUSION: Over the 2-3-year follow-up period, all four treatment modalities led to improved clinical and radiographic peri-implant parameters but implant stability posttreatment, as indicated by the fact that the recorded ISQ scores remained stable. As a result, use of MRFA as an adjunct to the traditionally used periodontal and radiographic tools for the evaluation of postoperative implant stability following the treatment of peri-implant disease cannot be recommended.

Outcomes of Stereotactic Radiation Therapy Versus Fractionated Radiation Therapy in 44 Dogs With Pituitary Masses: A Multi-Institutional Retrospective Study (2016-2022).

Although canine pituitary masses (PM) are increasingly treated with stereotactic radiotherapy (SRT), historical literature supports superior outcomes with conventional full-course fractionated radiation therapy (FRT). A multi-institutional retrospective study was performed, including dogs with PM treated from 2016 to 2022 with SRT (total dose 30 or 35 Gy in 5 daily fractions) or FRT (total dose 50-54 Gy in 19-20 daily fractions). The influence of potential prognostic/predictive factors was assessed, including pituitary: brain height, pituitary: brain volume, sex, age and endocrine status (functional [F] vs. nonfunctional [NF] PM). Forty-four dogs with PM were included (26 F, 14 NF, 4 unknown). All patients completed protocols as scheduled (SRT = 27, FRT = 17) and two dogs had suspected Grade 1 acute neurotoxicity. During the first 6 months after RT, 5/27 (19%) dogs treated with SRT (4 F, 1 NF) and 3/17 (18%) dogs treated with FRT (all F) died or were euthanised because of progressive neurologic signs. The overall median survival time was 608 days (95% CI, 375-840 days). Young age at the time of treatment was significant for survival (p = 0.0288); the overall median survival time was 753 days for dogs <9 years of age (95% CI, 614-892 days) and 445 days for dogs ≥9 years of age (95% CI, 183-707 days). Survival time was not associated with treatment type or any other factor assessed herein. A prospective study using standardised protocols would further validate the results of the present study and potentially elucidate the predictors of early death.

Tilting and Distortion in the Multiferroic Aurivillius Phase Bi6Ti3Fe1.5Mn0.5O18.

Aurivillius structured Bi6Ti3Fe1.5Mn0.5O18 (B6TFMO) has emerged as a rare room temperature multiferroic, exhibiting reversible magnetoelectric switching of ferroelectric domains under cycled magnetic fields. This layered oxide presents exceptional avenues for advancing data storage technologies owing to its distinctive ferroelectric and ferrimagnetic characteristics. Despite its immense potential, a comprehensive understanding of the underlying mechanisms driving multiferroic behavior remains elusive. Herein, we employ atomic resolution electron microscopy to elucidate the interplay of octahedral tilting and atomic-level structural distortions within B6TFMO, associating these phenomena with functional properties. Fundamental electronic features at varying bonding environments within this complex system are scrutinized using electron energy loss spectroscopy (EELS), revealing that the electronic nature of the Ti4+ cations within perovskite BO6 octahedra is influenced by position within the Aurivillius structure. Layer-by-layer EELS analysis shows an ascending crystal field splitting (Δ) trend from outer to center perovskite layers, with an average increase in Δ of 0.13 ± 0.06 eV. Density functional theory calculations, supported by atomic resolution polarization vector mapping of B-site cations, underscore the correlation between the evolving nature of Ti4+ cations, the extent of tetragonal distortion and ferroelectric behavior. Integrated differential phase contrast imaging unveils the position of light oxygen atoms in B6TFMO for the first time, exposing an escalating degree of octahedral tilting toward the center layers, which competes with the magnitude of BO6 tetragonal distortion. The observed octahedral tilting, influenced by B-site cation arrangement, is deemed crucial for juxtaposing magnetic cations and establishing long-range ferrimagnetic order in multiferroic B6TFMO.

A prospective evaluation of succinct prednisone tapering after brain tumor irradiation in dogs.

BACKGROUND: To ameliorate anticipated or ongoing neurological deficits, dogs undergoing brain tumor irradiation often are prescribed lengthy courses of prednisone PO during and after radiotherapy (RT). This practice can contribute to unwanted corticosteroid-associated morbidity and may be unnecessary. OBJECTIVE: Determine whether long-term corticosteroid dependency can be minimized by use of succinct prednisone tapering. ANIMALS: Fifty-five pet dogs undergoing brain tumor irradiation. METHODS: Nineteen dogs were treated using a "rapid-taper" protocol wherein corticosteroid dose reduction began 0 to 20 days after completing RT. Outcomes were compared with a retrospectively studied control group ("slow-taper"; N = 36 dogs) in which corticosteroids were tapered more slowly according to individual clinician recommendations. RESULTS: Patient demographics were similar between groups. Mean time to lowest prednisone dose was 41 days postirradiation in the rapid-taper group and 117 days in the slow-taper group (P = .003). In the rapid-taper group, 15 of 19 dogs (84%) were completely tapered off prednisone, vs 18 of 36 (50%) in the slow-taper group (P = .04). Rates at which corticosteroids had to be reinstituted later were similar for the 2 groups (approximately 1 in 3 dogs). Adverse effect rates were similar for the 2 groups. Although no comparable questionnaire-derived data were available for the "slow-taper" group, overall and neurologic quality of life remained stable after RT in the rapid-taper group. CONCLUSIONS AND CLINICAL IMPORTANCE: For many dogs, lengthy courses of PO prednisone are avoidable after intracranial RT. Future efforts should aim to identify which dogs benefit most from accelerated prednisone tapering.

A sustainable CVD approach for ZrN as a potential catalyst for nitrogen reduction reaction.

In pursuit of developing alternatives for the highly polluting Haber-Bosch process for ammonia synthesis, the electrocatalytic nitrogen reduction reaction (NRR) using transition metal nitrides such as zirconium mononitride (ZrN) has been identified as a potential pathway for ammonia synthesis. In particular, specific facets of ZrN have been theoretically described as potentially active and selective for NRR. Major obstacles that need to be addressed include the synthesis of tailored catalyst materials that can activate the inert dinitrogen bond while suppressing hydrogen evolution reaction (HER) and not degrading during electrocatalysis. To tackle these challenges, a comprehensive understanding of the influence of the catalyst's structure, composition, and morphology on the NRR activity is required. This motivates the use of metal-organic chemical vapor deposition (MOCVD) as the material synthesis route as it enables catalyst nanoengineering by tailoring the process parameters. Herein, we report the fabrication of oriented and facetted crystalline ZrN thin films employing a single source precursor (SSP) MOCVD approach on silicon and glassy carbon (GC) substrates. First principles density functional theory (DFT) simulations elucidated the preferred decomposition pathway of SSP, whereas ab initio molecular dynamics simulations show that ZrN at room temperature undergoes surface oxidation with ambient O2, yielding a Zr-O-N film, which is consistent with compositional analysis using Rutherford backscattering spectrometry (RBS) in combination with nuclear reaction analysis (NRA) and X-ray photoelectron spectroscopy (XPS) depth profiling. Proof-of-principle electrochemical experiments demonstrated the applicability of the developed ZrN films on GC for NRR and qualitatively hint towards a possible activity for the electrochemical NRR in the sulfuric acid electrolyte.

The geology and evolution of the Near-Earth binary asteroid system (65803) Didymos.

Images collected during NASA's Double Asteroid Redirection Test (DART) mission provide the first resolved views of the Didymos binary asteroid system. These images reveal that the primary asteroid, Didymos, is flattened and has plausible undulations along its equatorial perimeter. At high elevations, its surface is rough and contains large boulders and craters; at low elevations its surface is smooth and possesses fewer large boulders and craters. Didymos' moon, Dimorphos, possesses an intimate mixture of boulders, several asteroid-wide lineaments, and a handful of craters. The surfaces of both asteroids include boulders that are large relative to their host body, suggesting that both asteroids are rubble piles. Based on these observations, our models indicate that Didymos has a surface cohesion ≤ 1 Pa and an interior cohesion of ∼10 Pa, while Dimorphos has a surface cohesion of <0.9 Pa. Crater size-frequency analyzes indicate the surface age of Didymos is 40-130 times older than Dimorphos, with likely absolute ages of ~ 12.5 Myr and <0.3 Myr, respectively. Solar radiation could have increased Didymos' spin rate leading to internal deformation and surface mass shedding, which likely created Dimorphos.