Remarkable stability of γ - N 2 and its prevalence in the nitrogen phase diagram.

Solid nitrogen exhibits a panoply of phenomena ranging from complex molecular crystalline configurations to polymerization and closing band gap at higher densities. Among the elemental molecular solids, nitrogen stands apart for having phases, which can only be stabilized following particular pressure-temperature pathways, indicative of metastability and kinetic barriers. Here, through the combination of Raman spectroscopy and dynamic compression techniques, we find that the appearance of the whole nitrogen phase diagram is determined by the P-T paths taken below 2 GPa. We reveal the existence of the path- and phase-dependent triple point between the ß - N 2 , δ loc - N 2 and γ - or ϵ - N 2 . We further show that the ß - N 2 towards γ - N 2 path below the triple point, that evades δ ( δ loc )- N 2 , results in the formation of γ - N 2 , which in turn becomes a dominant phase. We then demonstrate, that the ß - N 2 through δ ( δ loc )- N 2 above the triple point path leads to the formation of ϵ - N 2 and the "well-established" phase diagram. An additional pathway, which by-passes the rotationally inhibited modifications δ ( δ loc )- N 2 , via rapid compression is found to produce γ - N 2 at higher temperatures. We argue that the pathway and phase sensitive triple point and the compression rate dependent phase formation challenge our understanding of this archetypal dense molecular solid.

High-temperature concomitant metal-insulator and spin-reorientation transitions in a compressed nodal-line ferrimagnet Mn3Si2Te6.

Symmetry-protected band degeneracy, coupled with a magnetic order, is the key to realizing novel magnetoelectric phenomena in topological magnets. While the spin-polarized nodal states have been identified to introduce extremely-sensitive electronic responses to the magnetic states, their possible role in determining magnetic ground states has remained elusive. Here, taking external pressure as a control knob, we show that a metal-insulator transition, a spin-reorientation transition, and a structural modification occur concomitantly when the nodal-line state crosses the Fermi level in a ferrimagnetic semiconductor Mn3Si2Te6. These unique pressure-driven magnetic and electronic transitions, associated with the dome-shaped Tc variation up to nearly room temperature, originate from the interplay between the spin-orbit coupling of the nodal-line state and magnetic frustration of localized spins. Our findings highlight that the nodal-line states, isolated from other trivial states, can facilitate strongly tunable magnetic properties in topological magnets.

Pressure stabilizes ferrous iron in bridgmanite under hydrous deep lower mantle conditions.

Earth's lower mantle is a potential water reservoir. The physical and chemical properties of the region are in part controlled by the Fe3+/ΣFe ratio and total iron content in bridgmanite. However, the water effect on the chemistry of bridgmanite remains unclear. We carry out laser-heated diamond anvil cell experiments under hydrous conditions and observe dominant Fe2+ in bridgmanite (Mg, Fe)SiO3 above 105 GPa under the normal geotherm conditions corresponding to depth > 2300 km, whereas Fe3+-rich bridgmanite is obtained at lower pressures. We further observe FeO in coexistence with hydrous NiAs-type SiO2 under similar conditions, indicating that the stability of ferrous iron is a combined result of H2O effect and high pressure. The stability of ferrous iron in bridgmanite under hydrous conditions would provide an explanation for the nature of the low-shear-velocity anomalies in the deep lower mantle. In addition, entrainment from a hydrous dense layer may influence mantle plume dynamics and contribute to variations in the redox conditions of the mantle.

Synthesis and superconductivity in yttrium-cerium hydrides at high pressures.

Further increasing the critical temperature and/or decreasing the stabilized pressure are the general hopes for the hydride superconductors. Inspired by the low stabilized pressure associated with Ce 4f electrons in superconducting cerium superhydride and the high critical temperature in yttrium superhydride, we carry out seven independent runs to synthesize yttrium-cerium alloy hydrides. The synthetic process is examined by the Raman scattering and X-ray diffraction measurements. The superconductivity is obtained from the observed zero-resistance state with the detected onset critical temperatures in the range of 97-141 K. The upper critical field towards 0 K at pressure of 124 GPa is determined to be between 56 and 78 T by extrapolation of the results of the electrical transport measurements at applied magnetic fields. The analysis of the structural data and theoretical calculations suggest that the phase of Y0.5Ce0.5H9 in hexagonal structure with the space group of P63/mmc is stable in the studied pressure range. These results indicate that alloying superhydrides indeed can maintain relatively high critical temperature at relatively modest pressures accessible by laboratory conditions.

Synthesis of superconducting phase of La0.5Ce0.5H10at high pressures.

Clathrate hydrideFm3-m-LaH10has been proven as the most extraordinary superconductor with the critical temperatureTcabove 250 K upon compression of hundreds of GPa in recent years. A general hope is to reduce the stabilization pressure and maintain the highTcvalue of the specific phase in LaH10. However, strong structural instability distortsFm3-mstructure and leads to a rapid decrease ofTcat low pressures. Here, we investigate the phase stability and superconducting behaviors ofFm3-m-LaH10with enhanced chemical pre-compression through partly replacing La by Ce atoms from both experiments and calculations. For explicitly characterizing the synthesized hydride, we choose lanthanum-cerium alloy with stoichiometry composition of 1:1. X-ray diffraction and Raman scattering measurements reveal the stabilization ofFm3-m-La0.5Ce0.5H10in the pressure range of 140-160 GPa. Superconductivity withTcof 175 ± 2 K at 155 GPa is confirmed with the observation of the zero-resistivity state and supported by the theoretical calculations. These findings provide applicability in the future explorations for a large variety of hydrogen-rich hydrides.

High pressure decomposition of a sandwich compound.

While it is widely recognized that purely organic molecular systems with multiple bonds undergo chemical condensation at sufficiently high pressures (from tenths to tens of GPa), the fate of organometallics at extreme conditions remains largely underexplored. We have investigated the high pressure (up to 41 GPa) chemical transformations in a simple molecular system known as nickelocene, (C5H5)2Ni, which serves as a representative example of a class of organometallics called sandwich compounds. Nickelocene decomposed above 13 GPa, at room temperature, while lower pressure thresholds have been observed at higher temperatures (295-573 K). The products were identified as nanocomposite materials, primarily composed of disordered, nickel-rich nanoparticles segregated within an extended, amorphous matrix of hydrogenated carbon (a-C:H). The investigation was conducted by means of diamond anvil cells in combination with optical spectroscopies and microscopy, synchrotron x-ray absorption spectroscopy and diffraction, as well as transmission electron microscopy. Our findings have the potential to stimulate further research into the high-pressure chemical reactivity of organometallics and open up new synthesis routes for the production of metal-based nanoparticles, which find a wide range of applications.

Nexus Evaluation Primary Trident II UNcemented shEll (NEPTUNE).

Aims: The primary aim of this study is to assess the survival of the uncemented hydroxyapatite (HA) coated Trident II acetabular component as part of a hybrid total hip arthroplasty (THA) using a cemented Exeter stem. The secondary aims are to assess the complications, joint-specific function, health-related quality of life, and radiological signs of loosening of the acetabular component. Methods: A single-centre, prospective cohort study of 125 implants will be undertaken. Patients undergoing hybrid THA at the study centre will be recruited. Inclusion criteria are patients suitable for the use of the uncemented acetabular component, aged 18 to 75 years, willing and able to comply with the study protocol, and provide informed consent. Exclusion criteria includes patients not meeting study inclusion criteria, inadequate bone stock to support fixation of the prosthesis, a BMI > 40 kg/m2, or THA performed for pain relief in those with severely restricted mobility. Results: Implant survival, complications, functional outcomes and radiological assessment up to ten years following index THA (one, two, five, seven, and ten years) will be performed. Functional assessment will include the Oxford Hip Score, Forgotten Joint Score, 12-Item Short Form Health Survey, EuroQol five-dimension health questionnaire, and pain and patient satisfaction. Radiological assessment with assess for acetabula lucent lines, lysis, and loosening according to DeLee and Charnley zones. Conclusion: This study is part of a stepwise introduction of a new device to orthopaedic practice, and careful monitoring of implants should be carried out as part of the Beyond Compliance principles. The results of this study will provide functional, radiological, and survival data to either support the ongoing use of the HA acetabulum or highlight potential limitations of this new implant before wide adoption.

Early muscle recovery following robotic-assisted unicompartmental knee arthroplasty.

BACKGROUND: Robotic-assisted unicompartmental knee arthroplasty (UKA) improves implant accuracy, however whether this translates to patient function is less clear. Various outcomes have been reported but muscle recovery has not been previously investigated. OBJECTIVE: To explore sequential change in lower limb muscle strength following robotic-assisted UKA with isokinetic dynamometry. RESULTS: 12 participants undergoing rUKA for medial compartment osteoarthritis were assessed pre-operatively, and at 6- and 12-weeks post-operatively. Maximal muscle strength changed over time in both quadriceps (p = 0.006) and hamstrings (p = 0.018) muscle groups. Quadriceps strength reduced from 88.52(39.86)Nm to 74.47(27.58)Nm by 6-weeks (p = 0.026), and then recovered to 90.41(38.76)Nm by 12-weeks (p = 0.018). Hamstring strength reduced from 62.45(23.18)Nm to 54.12(20.49)Nm by 6-weeks (p = 0.016), and then recovered to 55.07(17.99)Nm by 12-weeks (p = 0.028). By 12-weeks quadriceps strength was 70% and hamstrings 83% of the values achieved in the un-operated limb. Substantial improvement was seen in all other measures over time, with sequential positive change in Timed-up-and-go test (p = 0.015), 10 m walk test (p = 0.021), range of knee flexion (p = 0.016) and PROMs (p < 0.025).

Chemically Assisted Precompression of Hydrogen Molecules in Alkaline-Earth Tetrahydrides.

Through a series of high pressure diamond anvil experiments, we report the synthesis of alkaline earth (Ca, Sr, Ba) tetrahydrides, and investigate their properties through Raman spectroscopy, X-ray diffraction, and density functional theory calculations. The tetrahydrides incorporate both atomic and quasi-molecular hydrogen, and we find that the frequency of the intramolecular stretching mode of the H2δ- units downshifts from Ca to Sr and to Ba upon compression. The experimental results indicate that the larger the host cation, the longer the H2δ- bond. Analysis of the electron localization function (ELF) demonstrates that the lengthening of the H-H bond is caused by the charge transfer from the metal to H2δ- and by the steric effect of the metal host on the H-H bond. This effect is most prominent for BaH4, where the precompression of H2δ- units at 50 GPa results in bond lengths comparable to that of pure H2 above 275 GPa.

Compression rate of dynamic diamond anvil cells from room temperature to 10 K.

There is an ever increasing interest in studying dynamic-pressure dependent phenomena utilizing dynamic Diamond Anvil Cells (dDACs), devices capable of a highly controlled rate of compression. Here, we characterize and compare the compression rate of dDACs in which the compression is actuated via three different methods: (1) stepper motor (S-dDAC), (2) gas membrane (M-dDAC), and (3) piezoactuator (P-dDAC). The compression rates of these different types of dDAC were determined solely on millisecond time-resolved R1-line fluorescence of a ruby sphere located within the sample chamber. Furthermore, these different dynamic compression-techniques have been described and characterized over a broad temperature and pressure range from 10 to 300 K and 0-50 GPa. At room temperature, piezoactuation (P-dDAC) has a clear advantage in controlled extremely fast compression, having recorded a compression rate of ∼7 TPa/s, which is also found to be primarily influenced by the charging time of the piezostack. At 40-250 K, gas membranes (M-dDAC) have also been found to generate rapid compression of ∼0.5-3 TPa/s and are readily interfaced with moderate cryogenic and ultrahigh vacuum conditions. Approaching more extreme cryogenic conditions (<10 K), a stepper motor driven lever arm (S-dDAC) offers a solution for high-precision moderate compression rates in a regime where P-dDACs and M-dDACs can become difficult to incorporate. The results of this paper demonstrate the applicability of different dynamic compression techniques, and when applied, they can offer us new insights into matter's response to strain, which is highly relevant to physics, geoscience, and chemistry.

Formation and Stability of Dense Methane-Hydrogen Compounds.

Through a series of x-ray diffraction, optical spectroscopy diamond anvil cell experiments, combined with density functional theory calculations, we explore the dense CH_{4}-H_{2} system. We find that pressures as low as 4.8 GPa can stabilize CH_{4}(H_{2})_{2} and (CH_{4})_{2}H_{2}, with the latter exhibiting extreme hardening of the intramolecular vibrational mode of H_{2} units within the structure. On further compression, a unique structural composition, (CH_{4})_{3}(H_{2})_{25}, emerges. This novel structure holds a vast amount of molecular hydrogen and represents the first compound to surpass 50 wt % H_{2}. These compounds, stabilized by nuclear quantum effects, persist over a broad pressure regime, exceeding 160 GPa.

Robotic-arm assisted total knee arthroplasty is associated with improved accuracy and patient reported outcomes: a systematic review and meta-analysis.

This systematic review and meta-analysis were conducted to compare the accuracy of component positioning, alignment and balancing techniques employed, patient-reported outcomes, and complications of robotic-arm assisted total knee arthroplasty (RATKA) with manual TKA (mTKA) and the associated learning curve. Searches of PubMed, Medline and Google Scholar were performed in October 2020 using PRISMA guidelines. Search terms included "robotic", "knee" and "arthroplasty". The criteria for inclusion were published clinical research articles reporting the learning curve for RATKA and those comparing the component position accuracy, alignment and balancing techniques, functional outcomes, or complications with mTKA. There were 198 articles identified, following full text screening, 16 studies satisfied the inclusion criteria and reported the learning curve of rTKA (n=5), component positioning accuracy (n=6), alignment and balancing techniques (n=7), functional outcomes (n=7), or complications (n=5). Two studies reported the learning curve using CUSUM analysis to establish an inflexion point for proficiency which ranged from 7 to 11 cases and there was no learning curve for component positioning accuracy. The meta-analysis showed a significantly lower difference between planned component position and implanted component position, and the spread was narrower for RATKA compared with the mTKA group (Femur coronal: mean 1.31, 95% confidence interval (CI) 1.08-1.55, p<0.00001; Tibia coronal: mean 1.56, 95% CI 1.32-1.81, p<0.00001). Three studies reported using different alignment and balancing techniques between mTKA and RATKA, two studies used the same for both group and two studies did not state the methods used in their RATKA groups. RATKA resulted in better Knee Society Score compared to mTKA in the short-to-mid-term follow up (95%CI [- 1.23, - 0.51], p=0.004). There was no difference in arthrofibrosis, superficial and deep infection, wound dehiscence, or overall complication rates. RATKA demonstrated improved accuracy of component positioning and patient-reported outcomes. The learning curve of RATKA for operating time was between 7 and 11 cases. Future well-powered studies on RATKAs should report on the knee alignment and balancing techniques utilised to enable better comparisons on which techniques maximise patient outcomes.Level of evidence III.

In-situ abiogenic methane synthesis from diamond and graphite under geologically relevant conditions.

Diamond and graphite are fundamental sources of carbon in the upper mantle, and their reactivity with H2-rich fluids present at these depths may represent the key to unravelling deep abiotic hydrocarbon formation. We demonstrate an unexpected high reactivity between carbons' most common allotropes, diamond and graphite, with hydrogen at conditions comparable with those in the Earth's upper mantle along subduction zone thermal gradients. Between 0.5-3 GPa and at temperatures as low as 300 °C, carbon reacts readily with H2 yielding methane (CH4), whilst at higher temperatures (500 °C and above), additional light hydrocarbons such as ethane (C2H6) emerge. These results suggest that the interaction between deep H2-rich fluids and reduced carbon minerals may be an efficient mechanism for producing abiotic hydrocarbons at the upper mantle.

Superionicity, disorder, and bandgap closure in dense hydrogen chloride.

Hydrogen bond networks play a crucial role in biomolecules and molecular materials such as ices. How these networks react to pressure directs their properties at extreme conditions. We have studied one of the simplest hydrogen bond formers, hydrogen chloride, from crystallization to metallization, covering a pressure range of more than 2.5 million atmospheres. Following hydrogen bond symmetrization, we identify a previously unknown phase by the appearance of new Raman modes and changes to x-ray diffraction patterns that contradict previous predictions. On further compression, a broad Raman band supersedes the well-defined excitations of phase V, despite retaining a crystalline chlorine substructure. We propose that this mode has its origin in proton (H+) mobility and disorder. Above 100 GPa, the optical bandgap closes linearly with extrapolated metallization at 240(10) GPa. Our findings suggest that proton dynamics can drive changes in these networks even at very high densities.

High-Pressure Structural Evolution of Disordered Polymeric CS2.

Carbon disulfide is an archetypal double-bonded molecule belonging to the class of group IV-group VI, AB2 compounds. It is widely believed that, upon compression to several GPa at room temperature and above, a polymeric chain of type (-(C═S)-S-)n, named Bridgman's black polymer, will form. By combining optical spectroscopy and synchrotron X-ray diffraction data with ab initio simulations, we demonstrate that the structure of this polymer is different. Solid molecular CS2 polymerizes at ∼10-11 GPa. The polymer is disordered and consists of a mixture of 3-fold (C3) and 4-fold (C4) coordinated carbon atoms with some C═C double bonds. The C4/C3 ratio continuously increases upon further compression to 40 GPa. Upon decompression, structural changes are partially reverted, while the sample also undergoes partial disproportionation. Our work uncovers the nontrivial high-pressure structural evolution in one of the simplest molecular systems exhibiting molecular as well as polymeric phases.

High-temperature phase transitions in dense germanium.

Through a series of high-pressure x-ray diffraction experiments combined with in situ laser heating, we explore the pressure-temperature phase diagram of germanium (Ge) at pressures up to 110 GPa and temperatures exceeding 3000 K. In the pressure range of 64-90 GPa, we observe orthorhombic Ge-IV transforming above 1500 K to a previously unobserved high-temperature phase, which we denote as Ge-VIII. This high-temperature phase is characterized by a tetragonal crystal structure, space group I4/mmm. Density functional theory simulations confirm that Ge-IV becomes unstable at high temperatures and that Ge-VIII is highly competitive and dynamically stable at these conditions. The existence of Ge-VIII has profound implications for the pressure-temperature phase diagram, with melting conditions increasing to much higher temperatures than previous extrapolations would imply.

Revisiting the anatomy of the monocot cambium, a novel meristem.

MAIN CONCLUSION: The monocot cambium is semi-storied, and its cells do not undergo rearrangement. The monocot cambium is a lateral meristem responsible for secondary growth in some monocotyledons of Asparagales. It is an unusual meristem, not homologous with the vascular cambia of gymnosperms and non-monocotyledonous angiosperms. Owing to the limited information available on the characteristics of this meristem, the aim of this study was to survey the structure of the monocot cambium in order to clarify the similarities and dissimilarities of this lateral meristem to the vascular cambium of trees. Using the serial sectioning analysis, we have studied the monocot cambium of three species of arborescent monocotyledons, i.e., Quiver Tree Aloe dichotoma, Dragon Tree Dracaena draco, and Joshua Tree Yucca brevifolia, native to different parts of the world. Data showed that in contrast to the vascular cambium, the monocot cambium is composed of a single type of short initials that vary in shape, and in tangential view display a semi-storied pattern. Furthermore, the cells of the monocot cambium do not undergo rearrangement. The criteria used in identifying monocot cambium initial cell are also discussed.

Robotic arm-assisted versus manual total hip arthroplasty : a systematic review and meta-analysis.

AIMS: The aims of this systematic review were to assess the learning curve of semi-active robotic arm-assisted total hip arthroplasty (rTHA), and to compare the accuracy, patient-reported functional outcomes, complications, and survivorship between rTHA and manual total hip arthroplasty (mTHA). METHODS: Searches of PubMed, Medline, and Google Scholar were performed in April 2020 in line with the Preferred Reporting Items for Systematic Review and Meta-Analysis statement. Search terms included "robotic", "hip", and "arthroplasty". The criteria for inclusion were published clinical research articles reporting the learning curve for rTHA (robotic arm-assisted only) and those comparing the implantation accuracy, functional outcomes, survivorship, or complications with mTHA. RESULTS: There were 501 articles initially identified from databases and references. Following full text screening, 17 articles that satisfied the inclusion criteria were included. Four studies reported the learning curve of rTHA, 13 studies reported on implant positioning, five on functional outcomes, ten on complications, and four on survivorship. The meta-analysis showed a significantly greater number of cases of acetabular component placement in the safe zone compared with the mTHA group (95% confidence interval (CI) 4.10 to 7.94; p < 0.001) and that rTHA resulted in a significantly better Harris Hip Score compared to mTHA in the short- to mid-term follow-up (95% CI 0.46 to 5.64; p = 0.020). However, there was no difference in infection rates, dislocation rates, overall complication rates, and survival rates at short-term follow-up. CONCLUSION: The learning curve of rTHA was between 12 and 35 cases, which was dependent on the assessment goal, such as operating time, accuracy, and team working. Robotic arm-assisted total hip arthroplasty was associated with improved accuracy of component positioning and functional outcome, however no difference in complication rates or survival were observed at short- to mid-term follow-up. Overall, there remains an absence of high-quality level I evidence and cost analysis comparing rTHA and mTHA. Cite this article: Bone Joint J 2021;103-B(6):1009-1020.