[Economic evaluation of porous metal cones in total knee arthroplasty]. / Étude de l'impact économique des cônes en métal poreux dans les arthroplasties totales du genou.

INTRODUCTION: The use of porous metal cones (PMC) to fill bone loss during knee replacements is increasing, but these medical devices are not reimbursed in addition to diagnosis related tariffs (DRTs). The economic impact of PMC may be significant for hospitals. MATERIAL AND METHODS: This multicenter observational study includes all patients who benefited of a total knee prosthesis, with reconstruction by PMC, between June 2014 and June 2019, in two French university hospitals. The costs of each diagnosis related group (DRG) was evaluated using the "étude nationale des coûts à méthodologie commune (ENC)". The PMC costs were compared with the amounts of DRG and with the fares perceived by the hospital from the French sickness fund (DRTs). RESULTS: 96 patients (103 stays) benefited from the implantation of 195 cones. The hospital incomes were 10,970±1401€ /stay. Spending associated with PMC represented 35% of DRGs and 44% of DRTs. The average additional cost related to the cones was 2709±1138€ /stay. If the reconstructions had been performed by allograft, the average gain for hospitals would have been 108€ /stay. CONCLUSION: If PMC have clinical benefits for surgeons in reducing the incidence of revision, this study shows the inadequacy of the funding of these devices for French hospitals. This suggests the need to expand the possibilities of supporting innovative technologies.

Reactivity of shape-controlled crystals and metadynamics simulations locate the weak spots of alumina in water.

The kinetic stability of any material in water relies on the presence of surface weak spots responsible for chemical weathering by hydrolysis. Being able to identify the atomistic nature of these sites and the first steps of transformation is therefore critical to master the decomposition processes. This is the challenge that we tackle here: combining experimental and modeling studies we investigate the stability of alumina in water. Exploring the reactivity of shape-controlled crystals, we identify experimentally a specific facet as the location of the weak spots. Using biased ab initio molecular dynamics, we recognize this weak spot as a surface exposed tetra-coordinated Al atom and further provide a detailed mechanism of the first steps of hydrolysis. This understanding is of great importance to heterogeneous catalysis where alumina is a major support. Furthermore, it paves the way to atomistic understanding of interfacial reactions, at the crossroad of a variety of fields of research.

Antibiotic-loaded tantalum may serve as an antimicrobial delivery agent.

AIMS: The aims of this study were to compare the mean duration of antibiotic release and the mean zone of inhibition between vancomycin-loaded porous tantalum cylinders and antibiotic-loaded bone cement at intervals, and to evaluate potential intrinsic antimicrobial properties of tantalum in an in vitro medium environment against methicillin-sensitive Staphylococcus aureus (MSSA). MATERIALS AND METHODS: Ten porous tantalum cylinders and ten cylinders of cement were used. The tantalum cylinders were impregnated with vancomycin, which was also added during preparation of the cylinders of cement. The cylinders were then placed on agar plates inoculated with MSSA. The diameter of the inhibition zone was measured each day, and the cylinders were transferred to a new inoculated plate. Inhibition zones were measured with a Vernier caliper and using an automated computed evaluation, and the intra- and interobserver reproducibility were measured. The mean inhibition zones between the two groups were compared with Wilcoxon's test. RESULTS: MSSA was inhibited for 12 days by the tantalum cylinders and for nine days by the cement cylinders. At day one, the mean zone of inhibition was 28.6 mm for the tantalum and 19.8 mm for the cement group (p < 0.001). At day ten, the mean zone of inhibition was 3.8 mm for the tantalum and 0 mm for the cement group (p < 0.001). The porous tantalum cylinders soaked only with phosphate buffered solution showed no zone of inhibition. CONCLUSION: Compared with cement, tantalum could release antibiotics for longer. Further studies should assess the advantages of using antibiotic-loaded porous tantalum implants at revision arthroplasty. Cite this article: Bone Joint J 2019;101-B:848-851.

Is anatomic acetabular orientation related to pelvic morphology? CT analysis of 150 healthy pelvises.

BACKGROUND: Links between sagittal spinal alignment and acetabular orientation attract considerable research attention with the goal of optimising prosthetic cup position. However, whether pelvic incidence (PI) is related to anatomic acetabular orientation remains unknown. We therefore conducted a radiological study with the following objectives: to look for correlations between PI and anatomic acetabular parameters; to describe the sacro-pubic angle (SPA), defined by fixed bony pelvic landmarks, and its relations with acetabular anteversion; and to determine whether anatomical parameters (PI and SPA) correlate with demographic characteristics. HYPOTHESIS: PI correlates with anatomical acetabular parameters. MATERIALS AND METHODS: We conducted a computed tomography (CT) study of the pelvises of 150 patients free of degenerative disease. Three parameters were measured: anatomic acetabular orientation in the Lewinnek reference plane, PI, and the SPA subtended by the line connecting the midpoint of the sacral endplate to the pubic symphysis and the anterior pelvic plane. Statistical tests were performed to look for correlations among these parameters. RESULTS: Intra-observer and inter-observer reproducibility was considered highly satisfactory (inter-class correlation coefficient, >86% and >82%, respectively). Mean PI was 58.6°±10.2° (range, 32.8°-97.6°), with no significant differences between genders or across age groups. Mean SPA was 34.7°±5.5° (range, 18.3°-49.8°). Mean anatomic acetabular anteversion (AAA) was greater in females (23.4°; range, 11.5°-34.5°) than in males (20°; range, 7.5°-34.5°) (P<0.001). PI did not correlate with any of the acetabular parameters (PI/AAA, r=0.8 and P=0.33; PI/acetabular inclination on the horizontal, r=-0.96 and P=0.24). SPA correlated significantly with both PI (r=0.33 and P<0.001) and AAA (r=0.33 and P<0.001). DISCUSSION: This CT study of normal pelvises showed that AAA was significantly greater in females and that SPA correlated significantly with both PI and acetabular anteversion. SPA could serve to define the "theoretical" AAA of each individual patient and could thus be incorporated into surgical planning protocols or intra-operative guidance methods for hip replacement surgery. LEVEL OF EVIDENCE: IV, retrospective study with no control group.

Titania-Supported Catalysts for Levulinic Acid Hydrogenation: Influence of Support and its Impact on γ-Valerolactone Yield.

A series of titania-supported ruthenium and platinum catalysts was investigated in the levulinic acid hydrogenation towards γ-valerolactone, a key reaction for the catalytic transformation of biomass. It was shown that various morphologies and phases of titania strongly influence the physicochemical and catalytic properties of supported Ru and Pt catalysts in different ways. In the case of the catalyst supported on mixed TiO2 phases, Ru particles are exclusively located on the minority rutile crystallites, whereas such an effect was not observed for platinum. The platinum catalyst activity could be increased when the metal was dispersed on the large surface-area anatase, which was not the case for ruthenium as a result of its agglomeration on this support. The activity of ruthenium on anatase could be increased in two ways: a) when RuO2 formation during catalyst preparation was avoided; b) when pure anatase support material was modified so that it exhibited no microporosity. The obtained results allow a better understanding of the role of the support for Ru and Pt catalysts.

Comment on "Electronic properties and charge transfer phenomena in Pt nanoparticles on γ-Al2O3: size, shape, support, and adsorbate effects" by F. Behafarid et al., Phys. Chem. Chem. Phys., 2012, 14, 11766-11779.

We show how density functional theory (DFT) calculations rationalize the origin of high H/Pt ratio and the electronic properties of γ-alumina supported Pt nanoparticles as observed in Phys. Chem. Chem. Phys., 2012, 14, 11766-11779.

Understanding the HIV-1 protease reactivity with DFT: what do we gain from recent functionals?

The modeling of HIV-1 plays a crucial role in the understanding of its reactivity and its interactions with specific drugs. In this work, we propose a medium sized model to test the ability of a variety of quantum chemistry approaches to provide reasonable geometric parameters and energetics for this system. Although our model is large enough to include the main polarizing groups of the active site, it is small enough to be used within full quantum studies up to the second order Møller-Plesset (MP2) level with extrapolations to coupled cluster CCSD(T) level. These high level calculations are used as reference to assess the ability of electronic structure methods (semiempirical and DFT) to provide accurate geometries and energies for the HIV-1 protease reaction. All semiempirical methods fail to describe the geometry of the protease active site. Within DFT, pure generalized gradient approximation (GGA) functionals have difficulty in reproducing the reaction energy and underestimate the barrier. Hybrid and/or meta GGA approaches do not yield a consistent improvement. The best results are obtained with hybrid GGA B3LYP or X3LYP and with hybrid meta GGA functionals with a fraction of exact exchange around 30-40%, such as M06, B1B95, or BMK functionals. On the basis of these results, we propose an accurate and computationally efficient strategy, employing quantum chemistry methods. This is applied here to study the protonation state of the reaction intermediate and could be easily used in further QM/MM studies.

Mechanistic and spectroscopic identification of initial reaction intermediates for prenal decomposition on a platinum model catalyst.

The prediction of a reaction mechanism and the identification of the corresponding chemical intermediates is a major challenge in surface science and heterogeneous catalysis, due to a complex network of elementary steps and surface species. Here we demonstrate how to overcome this difficulty by tracking the temperature dependent formation of the initial reaction intermediates and identifying the decomposition pathways in the case of prenal, an α,ß-unsaturated aldehyde, on the Pt(111) model catalyst surface by combining vibrational spectroscopy, thermal reaction/desorption spectroscopy (TPRS) experiments and detailed theoretical analysis. TPRS characterization of this reaction up to 600 K shows a series of desorption states of H(2) (∼280 K, 410 K and 473 K) and CO (∼414 K), giving valuable insights into the sequence of elementary steps suggesting that the loss of hydrogen and the carbonyl functions are among the first elementary steps. HREELS experiments recorded after annealing to specific temperatures result in complex spectra, which can be assigned to several subsequently formed and transformed surface intermediates. Starting from stable prenal adsorption structures, complementary DFT calculations allow the determination of the most likely reaction pathway for the initial decomposition steps and the identification of the corresponding intermediates by comparison with HREELS. The decomposition occurs from the strongly bonded prenal adsorption structures via a dehydro-η(3)-triσ(CCC)-H1 intermediate to the highly stable η(1)-isobutylidyne species at high temperatures.

A DFT comparative study of carbon adsorption and diffusion on the surface and subsurface of Ni and Ni3Pd alloy.

Carbon diffusion in transition metal nanoparticles is assumed to be a key factor in the catalyzed growth of carbon nanotubes (CNT). Aiming at designing more efficient catalysts, we have compared this carbon diffusion process in the near surface and in the bulk of Ni and Ni(3)Pd by means of density functional theory (DFT) calculations. Ni nanoparticles are indeed the most largely used catalysts and the alloying with Pd could modify and improve their properties. The alloy has the same crystal structure as pure Ni, with a slight lattice expansion due to the presence of palladium. For both systems, the subsurface octahedral site is the most stable adsorption site, but the thermodynamic trend favoring the penetration to the subsurface is larger on the alloy than on the Ni. As a result, in the conditions of temperature and pressure for nanotube growth, the population of the subsurface sites is a more exothermic process on the alloy. In addition, while on pure nickel the diffusion over the (111) surface is easy, on the alloy the vertical process leading the carbon to the subsurface is preferred. Palladium atoms have the double effect to expand the lattice parameter providing more adapted diffusion channels for the carbon and to create new adsorption sites less stable than the all-nickel ones. The results can be related to more selective formation of nanotubes on the alloy at low temperature, where Ni produces fibers.

First principles surface thermodynamics of industrial supported catalysts in working conditions.

Ever stronger environmental concerns prompt the research in the area of heterogeneous catalysis to play an ever more crucial role to produce ever cleaner fuel from the refining of petroleum effluents. The catalytic active phase is often used in a dispersed state over a porous oxide material. This paper is a review of recent progress brought by periodic density functional theory (DFT) calculations in the area of two relevant industrial supported catalysts. We focus on two important supports used in the refining industry: anatase-TiO(2) and γ-alumina. According to the various reaction conditions, the presence of H(2)O, H(2) and H(2)S may change the surface states of the support. In particular, it is crucial to know and control the hydroxylation state depending on temperature and partial pressure of reactants (H(2)O, H(2), H(2)S). The support effects on the catalytic active phases are presented for MoS(2) particles, used in hydrodesulfurization catalysis, and for Pd particles, used in hydrogenation catalysis. It is shown how the wetting property and equilibrium morphology of the active phase depend on the support. A discussion on the impact for catalytic activities is provided.

First-principles study of CO adsorption and vibration on Au surfaces.

A CO stretching frequency analysis is presented for the adsorption of CO on various Au(110) surfaces from density functional theory calculations. The structure sensitivity of the adsorption has been studied by considering the unreconstructed (1 x 1) surface, the missing-row reconstructed (1 x 2) surface, the vicinal stepped (20) surface, and the adsorption on adatoms deposited on the (110)-(1 x 2) surface. The calculated CO stretching frequencies are compared with infrared reflection-absorption spectroscopy (IRAS) measurements carried out at room temperature and pressure below 1 atm. The overall stability of the systems is discussed within the calculations of surface free energies at various coverages. At room temperature, the adsorption of CO on the ridge of the missing-row reconstructed surface competes in the high pressure regime with more complex adsorption structures where the molecule coadsorbs on the ridge and on adatoms located along the empty troughs of the reconstruction. This result is supported by the CO stretching frequency analysis.

A combined experimental and theoretical evaluation of the structure of hydrated microporous aluminophosphate AlPO4-18.

Water adsorption in the microporous aluminophosphate AlPO4-18 is studied by a combination of solid-state NMR, X-ray diffraction, and density functional theory calculations. The change of the framework structure upon hydration is moderate, and NMR gives local information on the environment of Al and P atoms. The structural distribution of water molecules in the channels has been explored by a combination of first-principle molecular dynamics simulations and of static geometry optimizations. Two starting points have been considered for the calculations. If the structure of the dehydrated aluminophosphate is used, the simulation result is not satisfactory with an incomplete hydration and no agreement with NMR results. Starting from a partial refinement of the aluminophosphate framework for the hydrated system, a structure with six tetrahedral and six octahedral Al atoms in the unit cell is obtained, involving twelve water molecules coordinated to Al atoms and twelve others in the channels, and in good agreement with experimental data.

Understanding the high activity of a nanostructured catalyst obtained by a deposit of Pd on Ni: first principle calculations.

The catalytic activity of a 4 monolayer deposit of Pd on a Ni(110) surface toward the hydrogenation of ethylene is investigated by using gradient-corrected periodic density functional calculations. The Pd/Ni(110) surface is strongly nanostructured, due to the anisotropic stress induced by the Ni(110) substrate on the Pd layer. A kinetic analysis, based on the investigation of the optimal reaction pathway for the hydrogenation of ethylene to ethane, is presented, allowing a comparison between Pd/Ni(110) and pure Pd(110) surfaces. The calculated activation energies allow one to reproduce the experimental result, which shows that the Pd/Ni(110) surface is about 30 times more active than the pure Pd(110) surface. This marked increase of the catalytic activity is a consequence of the specific nanostructure of the Pd/Ni(110) surface. By examining the structure of the adsorbed species and of the transition states and by analyzing the electronic properties, we show that this rate increase can be associated to the fact that the ethylene adsorption energy in the first hydrogenation step and the ethyl-hydrogen coadsorption energy in the second step are both much lower on Pd/Ni(110) than on pure Pd(110).

Highly strained structure of a four-layer deposit of Pd on Ni(110): a coupled theoretical and experimental study.

The structure of a four monolayer deposit of Pd on Ni(110) has been determined by a combination of x-ray diffraction experiments and density-functional theory calculations. This Pd film presents, after annealing at 500 K, a (Nx2) reconstruction associated with a large enhancement of its catalytic activity. The N superstructure, along the dense [11;0] direction, comes from periodic edge dislocations initiated by a vacancy in the first Pd layer. In the perpendicular direction, the doubling of the period originates in a pairing-buckling displacement of the rows. This study evidences a new Pd atoms arrangement with quasi-four-fold hollow sites on the surface, which could play an important role in the exceptional catalytic activity.

Surface temperature dependence of rotational excitation of H(2) scattered from Pd(111).

Classical dynamics simulations are performed to study rotational excitation of H(2) scattered from Pd(111), taking into account energy exchange with surface phonons through a 3D surface oscillator model. We show that dynamic trapping, identified recently in the study of dissociation dynamics, plays a prominent role. The corresponding long interaction time due to several recollisions allows an efficient energy exchange between H(2) molecules and surface phonons. This microscopic mechanism explains the puzzling experimental finding on the role of surface temperature in H(2)(nu = 0,J = 1-->3) excitation.

Stability of chiral domains produced by adsorption of tartaric acid isomers on the Cu(110) surface: a periodic density functional theory study.

In the present work the interaction of different bitartrate isomers on the Cu(110) surface has been investigated systematically by using the Vienna Ab-initio Simulation Package (VASP), which performs periodical density functional theory (DFT) calculations. Among all bitartrate isomers the R,R-configuration is the most stable under the (3 1, 1 2) domain on the Cu surface. Its optical isomer, the S,S-bitartrate, is 10 kJ mol(-)(1) less stable in the same domain. This energy difference is sufficient to produce the distinct chiral assemblies observed after the adsorption of each optical isomer on the Cu surface. The calculations also showed that these domains are not formed due to intermolecular H-bonds, in contrast with the previous proposal by Raval et al.(Nature 2000, 23, 376). In fact, there is a formation of optimal intramolecular H-bonds in the chemisorption structures. A favorable packing orientation is also needed for the respective chiral domains. For instance, the S,S-configuration suffers from a destabilizing packing energy of 21 kJ mol(-)(1) under the same domain, due to a short contact between the H atoms of the hydroxy groups. These intramolecular H-bonds cause also some distortions on the bitartrate molecule, which appear to be dependent on the relative position of the alpha-hydroxy groups. The stability of the extended asymmetric domains, when the surface is modified by a chiral additive, might have important consequences for understanding and optimizing the properties of enantioselective heterogeneous catalysts.

Imaging the surface and the interface atoms of an oxide film on Ag111 by scanning tunneling microscopy: experiment and theory

High-resolution images of the vacuum oxide surface atomic structure of Ag111-p(4x4)-O reveal large terraces of a perfect (4x4) reconstruction. Under certain conditions, the surface Ag atoms at the interface between the reconstructed oxide layer and the underlying Ag111 lattice are also imaged, providing the structural registry. Scanning tunneling microscopy simulations reveal a strong sensitivity to structure and comparison with the experimental images, therefore providing an atom-by-atom model for the entire metal-oxide-vacuum structure.