To investigate the physical property of Fe7C3, we carried out in situ X-ray diffraction experiments using a Kawai-type multi-anvil apparatus and a diamond anvil cell up to 71.5 GPa and 1973 K. The ...carbide was found to be stable under these experimental conditions. However, we found anomalous behavior in its isothermal compression and thermal expansivity. These anomalies could be due to the magnetic phase transition in Fe7C3 from a ferromagnetic (fm) to a paramagnetic (pm) phase. The Curie temperature of 523 K at 1 bar (Tsuzuki et al. 1984) decreases with pressure, and the pressure-induced magnetic transition is estimated to occur at approximately 18 GPa and 300 K. The pressure-volume-temperature (P-V-T) data set for the pm-Fe7C3 was fitted by the Mie-Gruneisen-Debye (MGD) equation of state (EOS) and the following parameters were obtained: unit-cell volume V0=184.2±0.3 Å3, bulk modulus K0=253±7 GPa, the pressure derivative of bulk modulus K'0=3.6±0.2, Gruneisen parameter γ0=2.57±0.05, Debye temperature θ0=920±140 K, and q=2.2±0.5, respectively, at zero pressure. The calculated density for Fe7C3 provides a good explanation for the density of the Earth's inner core obtained from seismological observations.
The elastic compressional (P) and shear (S) wave velocities in NaCl were measured up to 12 GPa at 300 K, and up to 8 GPa at 473 and 673 K, by combining ultrasonic interferometry, in situ synchrotron ...X-ray diffraction, and X-ray radiographic techniques in a large-volume Kawai-type multi-anvil apparatus. The simultaneously measured sound velocity and density data at 300 K and high pressures up to 12 GPa were corrected to transform the adiabatic values to isothermal values and then used to estimate the 300 K equation of state (EOS) by a least-squares fit to the fourth-order Birch-Murnaghan finite strain equation, without pressure data. For a fixed isothermal bulk modulus KT0 of 23.7 GPa at 0 GPa and 300 K, we obtained the first and the second pressure derivatives of KT0, K'T0=5.14±0.05 and K"T0=-0.392±0.021 GPa-1, respectively. A high-temperature and high-pressure EOS of NaCl was then developed using the Mie-Gruneisen relation and the Debye thermal model. To accomplish this, the simultaneously measured sound velocities and densities up to 8 GPa at both 473 and 673 K, as well as previously reported volume thermal expansion data of NaCl at 0 GPa were included in the fit. This resulted in a q parameter of 0.96, while holding the Gruneisen parameter and the Debye temperature, both at 0 GPa and 300 K, fixed at 1.56 and 279 K, respectively. Our EOS model accurately modeled not only the present measured KT data at pressures up to 12 GPa and temperatures between 300 and 673 K, but also the previously reported volume thermal expansion and the temperature dependence of KT, both at 0 GPa. The new temperature-pressure-volume EOS for NaCl, presented here, provides a pressure-independent primary pressure standard at high temperatures and high pressures.
Background
Nivolumab improves overall survival (OS) in patients with platinum-refractory recurrent and metastatic head and neck squamous cell carcinoma (R/M HNSCC). In one study, however, ...Kaplan–Meier OS and progression-free survival (PFS) curves for the nivolumab and cytotoxic agent arms crossed at 3–6 months, suggesting that patients with initial resistance to immunotherapy might have better outcomes with cytotoxic treatment. Here, we explored the conditions and candidates which are predictive of nivolumab outcomes in R/M HNSCC.
Methods
We retrospectively reviewed the clinical records of 27 consecutive R/M HNSCC patients treated with nivolumab from 2014 to 2018. Tumor size was evaluated by RECIST ver.1.1. Tumor growth rate (Gr) was defined as 3
log(D
0
/D
pre
)/t
, where
D
0
and
D
pre
are the sum of the diameters of the target lesions (SumTLs) at baseline and pre-baseline, and
t
is time, with 1
t
defined as 4 weeks.
Results
Twenty-five patients were enrolled. Survival was significantly worse in patients with disease progression within 3 months. Outcomes appeared poorer in patients with higher pre-treatment Gr and bigger SumTLs at baseline. We therefore explored the association between prognosis, Gr and SumTLs. Recursive partitioning analysis showed that the characteristics of patients with disease progression after 3 months were Gr < 0.76 and SumTLs < 31.0 mm. Further, Gr < 0.76 and SumTLs < 31.0 mm was associated with significantly longer PFS (
p
= 0.01) and OS (
p
< 0.01).
Conclusions
These results suggest that Gr and SumTLs at baseline are significantly associated with OS and PFS in R/M HNSCC patients treated with nivolumab.
To comprehensively evaluate diagnostic algorithms for myocardial infarction using a high-sensitivity cardiac troponin I (hs-cTnI) assay.
We prospectively enrolled patients with suspected myocardial ...infarction without ST-segment elevation from nine emergency departments in Japan. The diagnostic algorithms evaluated: (i) based on hs-cTnI alone, such as the European Society of Cardiology (ESC) 0/1-h or 0/2-h and High-STEACS pathways; or (ii) used medical history and physical findings, such as the ADAPT, EDACS, HEART, and GRACE pathways. We evaluated the negative predictive value (NPV), sensitivity as safety measures, and proportion of patients classified as low or high-risk as an efficiency measure for a primary outcome of type 1 myocardial infarction or cardiac death within 30 days.
We included 437 patients, and the hs-cTnI was collected at 0 and 1 hours in 407 patients and at 0 and 2 hours in 394. The primary outcome occurred in 8.1% (33/407) and 6.9% (27/394) of patients, respectively. All the algorithms classified low-risk patients without missing those with the primary outcome, except for the GRACE pathway. The hs-cTnI-based algorithms classified more patients as low-risk: the ESC 0/1-h 45.7%; the ESC 0/2-h 50.5%; the High-STEACS pathway 68.5%, than those using history and physical findings (15-30%). The High-STEACS pathway ruled out more patients (20.5%) by hs-cTnI measurement at 0 hours than the ESC 0/1-h and 0/2-h algorithms (7.4%).
The hs-cTnI algorithms, especially the High-STEACS pathway, had excellent safety performance for the early diagnosis of myocardial infarction and offered the greatest improvement in efficiency.
Isothermal compression curves of face-centered cubic iron (γ-Fe) were determined at high temperatures (1273 and 1073 K) up to 27 GPa by in situ X-ray diffraction experiments using synchrotron ...radiation and the Kawai-type multi-anvil apparatus. Fits of the third-order Birch-Murnaghan equation of state to pressure-volume data yielded V0 = 48.997 ± 0.040 Å3, KT0 = 108.3 ± 2.4 GPa, and KT' = 5.8 ± 0.2 for 1273 K, and V0 = 48.600 ± 0.098 Å3, KT0 = 88.9 ± 5.1 GPa, and KT' = 8.9 ± 0.7 for 1073 K, where V0, KT0, and KT' are unit-cell volume, bulk modulus and its pressure derivative, respectively, at ambient pressure. The relatively large values of KT' are attributable to successive electronic spin state transitions from mixed-spin at lower pressures to low-spin at higher pressures. When discussing the constituents of Earth's (or other planets') solid inner core in terms of density and equations of state, one must carefully consider the influence of the electronic spin state.
First-order structural phase transitions are common in crystalline solids,
whereas first-order liquid-liquid phase transitions (that is, transitions
between two distinct liquid forms with different ...density and entropy) are
exceedingly rare in pure substances. But recent theoretical
and experimental studies have shown evidence for such a transition in several
materials, including supercooled water and liquid
carbon. Here we report an in situ X-ray diffraction
observation of a liquid-liquid transition in phosphorus, involving an
abrupt, pressure-induced structural change between two distinct liquid forms.
In addition to a known form of liquid phosphorus-a molecular liquid
comprising tetrahedral P4 molecules-we have found a polymeric
form at pressures above 1 GPa. Changing the pressure results in a reversible
transformation from the low-pressure molecular form into the high-pressure
polymeric form. The transformation is sharp and rapid, occurring within a
few minutes over a pressure range of less than 0.02 GPa. During the transformation,
the two forms of liquid coexist. These features are strongly suggestive of
a first-order liquid-liquid phase transition.
Assessment of renal function is important for safe cancer chemotherapy, and eligibility criteria for clinical trials often include creatinine clearance. However, creatinine clearance overestimates ...glomerular filtration rate, and various new formulae have been proposed to estimate glomerular filtration rate. Because these were developed mostly in patients with chronic kidney disease, we evaluated their validity in cancer patients without kidney disease.
Glomerular filtration rate was measured by inulin clearance in 45 Japanese cancer patients, and compared with creatinine clearance measured by 24-h urine collection as well as that estimated by the Cockcroft-Gault formula, Japanese estimated glomerular filtration rate developed in chronic kidney disease patients, the Modification of Diet in Renal Disease study equation and the Chronic Kidney Disease Epidemiology Collaboration equation. The Modification of Diet in Renal Disease study and Chronic Kidney Disease Epidemiology Collaboration equations were adjusted for the Japanese population by multiplying by 0.808 and 0.813, respectively.
The mean inulin clearance was 79.2 ± 18.7 ml/min/1.73 m(2). Bias values to estimate glomerular filtration rate for Japanese estimated glomerular filtration rate, the Cockcroft-Gault formula, creatinine clearance measured by 24-h urine collection, the 0.808 × Modification of Diet in Renal Disease study equation and the 0.813 × Chronic Kidney Disease Epidemiology Collaboration equation were 0.94, 9.75, 29.67, 5.26 and -0.92 ml/min/1.73 m(2), respectively. Precision (root-mean square error) was 14.7, 22.4, 39.8, 16.0 and 14.1 ml/min, respectively. Of the scatter plots of inulin clearance versus each estimation formula, the Japanese estimated glomerular filtration rate correlated most accurately with actual measured inulin clearance.
The Japanese estimated glomerular filtration rate and the 0.813 × Chronic Kidney Disease Epidemiology Collaboration equation estimated glomerular filtration rate with lower bias and higher precision than the other formulae. We therefore propose Japanese estimated glomerular filtration rate for the estimation of glomerular filtration rate in Japanese cancer patients.
Static compression data of (Mg0.83,Fe0.17)O and (Mg0.75,Fe0.25)O ferropericlases have been measured up to 58 GPa along 300, 700, and 1100 K isotherms, using synchrotron powder X-ray diffraction ...experiments combined with a kawai-type, multi-anvil, high-pressure apparatus and sintered diamond anvils. High-temperature and high-pressure equations of state for these two ferropericlases, which have high-spin Fe2+ ions, were developed using measured compression data below 47 GPa, based on the Mie-Grüneisen relation and the Debye thermal model, combined with the 300 K Birch-Murnaghan equation. When the isothermal bulk modulus (K0T) and the Debye temperature (Θ0) are fixed at 160 GPa and 500 K, respectively, the optimized equation-of-state parameters for these two phases are as follows: the pressure derivative of the bulk modulus (K0T), the Grüneisen constant (γ0), and the q parameter are 4.08 ± 0.02, 1.53 ± 0.04, and 0.7 ± 0.2, respectively, for (Mg0.83,Fe0.17)O; and 4.22 ± 0.03, 1.64 ± 0.04, and 0.7 ± 0.2, respectively, for (Mg0.75,Fe0.25)O. We found that calculated pressures with these equation-of-state parameters accurately reproduce the measured pressures of each ferropericlase below approximately 50 GPa for the isotherms of 300, 700, and 1100 K. Furthermore, the compression curve indicates that for each ferropericlase at each isothermal compression of 300, 700, and 1100 K, an abrupt volume reduction occurs at approximately 50 GPa. This volume reduction becomes more pronounced with increasing pressure, as a result of the progressive transition from high-spin to low-spin of the Fe2+ ions in each ferropericlase.
In situ X-ray diffraction experiments on FeS up to 22
GPa and 1600
K were carried out using large volume multianvil apparatus, combined with synchrotron radiation at SPring-8. We investigated phase ...stability relationships of FeS and determined the straight phase boundaries between FeS III (monoclinic phase) and FeS IV (hexagonal phase) to be
T
(
K)=20P
(GPa)+170 and between FeS IV and FeS V (NiAs-type phase) to be
T
(
K)=39.6P
(
GPa)+450
. We also found anomalous behavior in the
c/
a ratio, thermal expansion, and isothermal compression of FeS V as well as FeS IV, in the pressure range 4–12
GPa. These anomalies in FeS can be attributed to the spin-pairing transition of Fe, and divides FeS IV and FeS V into the high-spin low-pressure phase (LPP) and the possibly low-spin high-pressure phase (HPP). In order to investigate the internal structure of Mars, we evaluated the equations of state for FeS IV (HPP) and FeS V (HPP). A least square fit to the experimental data yielded
K
0
T
=62.5±0.9
GPa at
T=600
K and (d
K
0/d
T)
P
=−0.0208±0.0028
GPa/K for FeS IV (HPP), and
K
0
T
=54.3±1.0
GPa at
T=1000
K and (d
K
0/d
T)
P
=−0.0117±0.0015
GPa/K for FeS V (HPP) with fixed
K′=4. Thermal expansion coefficients were
α=7.16×10
−5+6.08×10
−8
T for FeS IV (HPP) and
α=10.42×10
−5 for FeS V (HPP), respectively. Using these equations of state, we examined the internal structure of Mars that has a model mantle composition Meteoritics 20 (1985) 367 and Fe–FeS core. Our models show that an Mg-silicate perovskite-rich lower mantle is stable only with the Fe-rich core having less than 20
wt.% sulfur. The polar moment of inertia factor
C derived from Mars Pathfinder data Science 278 (1997) 1749 is consistent with any compositions between Fe and FeS for the Martian core, but it excludes the presence of a crust thicker than 100
km.
Transparent nanocrystalline bulk alumina obtained at 7.7 GPa and 800 C had an average grain size of about 150 nm and an in-line transmission of 71% for a wavelength of 640 nm and a thickness of 0.8 ...mm. This is thought to be the lowest temperature at which highly transparent alumina has been obtained. The values of microhardness and fracture toughness were 25.5 plus or minus 0.3 GPa and 2.9 plus or minus 0.3 MPa.m1/2, respectively. The hardness value was consistent with the previously determined Hall-Petch relation and fracture toughness was independent of grain size.
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