Selectivity Control in the Direct CO Esterification over Pd@UiO-66: The Pd Location Matters.

The selectivity control of Pd nanoparticles (NPs) in the direct CO esterification with methyl nitrite toward dimethyl oxalate (DMO) or dimethyl carbonate (DMC) remains a grand challenge. Herein, Pd NPs are incorporated into isoreticular metal-organic frameworks (MOFs), namely UiO-66-X (X=-H, -NO2 , -NH2 ), affording Pd@UiO-66-X, which unexpectedly exhibit high selectivity (up to 99 %) to DMC and regulated activity in the direct CO esterification. In sharp contrast, the Pd NPs supported on the MOF, yielding Pd/UiO-66, displays high selectivity (89 %) to DMO as always reported with Pd NPs. Both experimental and DFT calculation results prove that the Pd location relative to UiO-66 gives rise to discriminated microenvironment of different amounts of interface between Zr-oxo clusters and Pd NPs in Pd@UiO-66 and Pd/UiO-66, resulting in their distinctly different selectivity. This is an unprecedented finding on the production of DMC by Pd NPs, which was previously achieved by Pd(II) only, in the direct CO esterification.

Characteristics of vertebral CT Hounsfield units in elderly patients with acute vertebral fragility fractures.

OBJECTIVE: To explore the characteristics of vertebral CT Hounsfield units (HU) in elderly patients with acute vertebral fragility fractures. METHODS: A total of 299 patients aged ≥ 65 years with acute vertebral fragility fractures were retrospectively reviewed, and 77 patients of them were age- and sex-matched with 77 control patients without any fractures. The vertebral HU value of L1(L1-HU) was measured, and T12 and L2 were used as alternatives for L1 in the case of L1 fracture. RESULTS: There were 460 thoracic and lumbar vertebral fractures in the 299 elderly patients, including 349 acute vertebral fragility fractures and 111 chronic fractures. The average L1-HU value was 66.0 ± 30.6 HU and showed significant difference among patients having different numbers of vertebral fractures (one fracture: 73.3 ± 27.0 HU, two fractures: 58.7 ± 32.5 HU, three or more fractures: 40.7 ± 28.8 HU; P < 0.001). As for the 1:1 age- and sex-matched patients, the L1-HU of the 77 patients with fractures was lower than that of the control patients (70.6 ± 23.4 HU vs. 101.5 ± 36.2 HU, P < 0.001). The area under the receiver operating characteristic curve of using L1-HU to differentiate patients with fractures from controls was 0.77(95% CI 0.70-0.85, P < 0.001). The cutoff value had high specificity of 90% or high sensitivity of 90% to identify patients with fractures of 60 HU and 100 HU, respectively. CONCLUSIONS: The elderly patients with acute vertebral fragility fractures have much lower HU values than those without fractures. Moreover, the lower the vertebral HU value is, the more likely the patients have more than one vertebral fracture. These slides can be retrieved under Electronic Supplementary Material.

[Correlation Research between Syndrome Elements of Chinese Medicine and KRAS, BRAF, NRAS Gene Mutations in Advanced Colorectal Cancer Patients].

Objective To study the correlation between syndrome elements of Chinese medicine (CM) and KRAS, BRAF, NRAS gene mutations in advanced colorectal cancer patients. Methods Syn- drome elements of CM, KRAS, BRAF, NRAS gene mutations (mutation " +" & wild type/non-mutation " --") were collected in 33 advanced colorectal cancer patients. The correlation between gene mutations and syndrome elements of CM was analyzed using binary Logistic regression. Results Wild type KRAS (KRAS-) was negatively correlated with Gan depression syndrome (P =0. 043, P <0. 05), while KRAS mutation (KRAS + ) was positively correlated with Gan depression syndrome (P =0. 043, P <0. 05). KRAS-and KRAS + had no significant relation with Pi deficiency, Fei deficiency, Shen deficiency, yang deficiency, yin deficiency, qi deficiency, blood deficiency, phlegm turbidity, qi stagnation, and blood sta- sis (P>0. 05). BRAF-and NRAS-had no significant relation with Gan stagnation, Pi deficiency, Fei defi- ciency, Shen deficiency, yang deficiency, yin deficiency, qi deficiency, blood deficiency, phlegm turbidi- ty, qi stagnation, and blood stasis (P >0. 05). Positive BRAF and NRAS were seldom found in this study, so they were not statistically analyzed. Conclusions There existed correlations between gene mutations and Gan stagnation. KRAS-was negatively correlated with Gan depression, while KRAS+ was positively correlated with Gan depression. Whether there exists mutation of BRAF or NRAS was not correlated with syndrome elements of CM.

Correcting intervertebral rotation and scoliosis simultaneously by oblique lumbar interbody fusion: a 3D analysis of EOS images.

Purpose: With advancements in minimally invasive techniques, oblique lumbar interbody fusion (OLIF) has gained widespread acceptance and is now commonly performed for adult degenerative scoliosis (ADS). The objective of this research paper is to evaluate three-dimensional (3D) intervertebral motions in EOS models before and after surgery and subsequently assess the efficacy of the 3D correction achieved through staged OLIF. Methods: In this retrospective study, 29 consecutive patients diagnosed with ADS were included, with a mean age of 63.6 years, who underwent staged OLIF surgery between 2018 and 2021. Spinopelvic parameters were assessed using EOS images, and 3D models were reconstructed to measure intervertebral motion angles (IMAs) in 70 surgical intervertebral segments, comprising wedge, lordosis, and axial rotation angles. Regression analysis was conducted to compare IMAs in different planes before and after the staged OLIF surgery. Results: Significant three-dimensional correction was observed in 70 intervertebral segments following the first-stage OLIF. The wedge angles decreased from 5.2°± 4.2° to 2.7°± 2.4° (P < 0.001). The lordosis angles increased from 5.1°± 5.9° to 7.8°± 4.6° (P = 0.014), while the axial rotation angles decreased from 3.8°± 2.6° to 2.3°± 2.1° (P < 0.001). Linear regression analysis revealed a positive correlation between wedge angles and axial angles preoperatively (P < 0.001, r = 0.43), as well as between corrected wedge angles and corrected axial angles (P < 0.001, r = 0.42). Conclusion: This study demonstrated that intervertebral motions had a correlation between coronal and axial planes in lumbar degenerative scoliosis. First-stage OLIF was efficient at correcting segmental scoliosis by inserting cages while correcting rotation deformity simultaneously, as well as improving the sagittal spinopelvic parameters.

Identification of Adolescent Menarche Status Using Biplanar X-ray Images: A Deep Learning-Based Method.

The purpose of this study is to develop an automated method for identifying the menarche status of adolescents based on EOS radiographs. We designed a deep-learning-based algorithm that contains a region of interest detection network and a classification network. The algorithm was trained and tested on a retrospective dataset of 738 adolescent EOS cases using a five-fold cross-validation strategy and was subsequently tested on a clinical validation set of 259 adolescent EOS cases. On the clinical validation set, our algorithm achieved accuracy of 0.942, macro precision of 0.933, macro recall of 0.938, and a macro F1-score of 0.935. The algorithm showed almost perfect performance in distinguishing between males and females, with the main classification errors found in females aged 12 to 14 years. Specifically for females, the algorithm had accuracy of 0.910, sensitivity of 0.943, and specificity of 0.855 in estimating menarche status, with an area under the curve of 0.959. The kappa value of the algorithm, in comparison to the actual situation, was 0.806, indicating strong agreement between the algorithm and the real-world scenario. This method can efficiently analyze EOS radiographs and identify the menarche status of adolescents. It is expected to become a routine clinical tool and provide references for doctors' decisions under specific clinical conditions.

Comparisons of oblique lumbar interbody fusion and transforaminal lumbar interbody fusion for degenerative spondylolisthesis: a prospective cohort study with a 2-year follow-up.

Objective: This study aimed to compare the clinical outcomes between oblique (OLIF) and transforaminal lumbar interbody fusion (TLIF) for patients with degenerative spondylolisthesis during a 2-year follow-up. Methods: Patients with symptomatic degenerative spondylolisthesis who underwent OLIF (OLIF group) or TLIF (TLIF group) were prospectively enrolled in the authors' hospital and followed up for 2 years. The primary outcomes were treatment effects [changes in visual analog score (VAS) and Oswestry disability index (ODI) from baseline] at 2 years after surgery; these were compared between two groups. Patient characteristics, radiographic parameters, fusion status, and complication rates were also compared. Results: In total, 45 patients were eligible for the OLIF group and 47 patients for the TLIF group. The rates of follow-up were 89% and 87% at 2 years, respectively. The comparisons of primary outcomes demonstrated no different changes in VAS-leg (OLIF, 3.4 vs. TLIF, 2.7), VAS-back (OLIF, 2.5 vs. TLIF, 2.1), and ODI (OLIF, 26.8 vs. TLIF, 30). The fusion rates were 86.1% in the TLIF group and 92.5% in the OLIF group at 2 years (P = 0.365). The OLIF group had less estimated blood loss (median, 200 ml) than the TLIF group (median, 300 ml) (P < 0.001). Greater restoration of disc height was obtained by OLIF (mean, 4.6 mm) than the TLIF group (mean, 1.3 mm) in the early postoperative period (P < 0.001). The subsidence rate was lower in the OLIF group than that in the TLIF group (17.5% vs. 38.9%, P = 0.037). The rates of total problematic complications were not different between the two groups (OLIF, 14.6% vs. TLIF, 26.2%, P = 0.192). Conclusion: OLIF did not show better clinical outcomes than TLIF for degenerative spondylolisthesis, except for lesser blood loss, greater disc height restoration, and lower subsidence rate.

A room-temperature X-ray-induced photochromic material for X-ray detection.

A color change: X-ray-induced photochromic species are rare and can be used for detection of X-rays. A highly robust X-ray-sensitive material with the discrete structure of a metal-organic complex has been found to show both soft and hard X-ray-induced photochromism at room temperature. A new ligand-to-ligand electron-transfer mechanism was proposed to elucidate this photochromic phenomenon.

Pear-Shaped Disk as a Risk Factor for Intraoperative End Plate Injury in Oblique Lumbar Interbody Fusion.

BACKGROUND: Intraoperative end plate injury can result in late-onset cage subsidence in oblique lumbar interbody fusion (OLIF). This study aimed to identify risk factors for intraoperative end plate injury and investigate whether a pear-shaped disk correlated with intraoperative end plate injury in OLIF. METHODS: We retrospectively reviewed 102 levels in 82 patients (mean age 60.1 ± 10.0 years) who underwent OLIF for degenerative lumbar diseases. Intraoperative end plate injury was evaluated using midline sagittal computed tomography views at 3 days postoperatively and defined as cage breaching into an adjacent cortical end plate >2 mm. Patient demographics, surgical parameters, radiographic parameters, and cage-related parameters were recorded in all surgical levels. Evaluation of risk factors associated with intraoperative end plate injury was performed. Patient-reported outcome, fusion status, and late-onset cage subsidence were analyzed at a minimum of 1 year after the surgery. RESULTS: Intraoperative end plate injury was observed in 26 levels (25.5%). Multivariate logistic regression analysis identified that bone mineral density (odds ratio [OR] = 0.978), preoperative segmental lordosis (OR = 0.790), and pear-shaped disk were risk factors (OR = 5.837) for intraoperative end plate injury. Intraoperative end plate injury occurred in 45.5% of levels with a pear-shaped disk compared with 16.0% of levels with no pear-shaped disk (P < 0.01). Late-onset cage subsidence was significantly more frequent in the injury group than the no-injury group. Patient-reported outcome and fusion status were unrelated to intraoperative end plate injury. CONCLUSIONS: A pear-shaped disk is the greatest risk factor for intraoperative end plate injury following OLIF.

Boosting Interfacial Electron Transfer between Pd and ZnTi-LDH via Defect Induction for Enhanced Metal-Support Interaction in CO Direct Esterification Reaction.

Strong metal-support interaction is crucial to the stability of catalysts in heterogeneous catalysis. However, reports on boosting interfacial electron transfer between metal and support via defect induction for enhanced metal-support interaction are limited. In this work, ultrathin reducible ZnTi-layered double hydroxide (LDH) nanosheets with rich oxygen defects were synthesized to stabilize Pd clusters, and the rich oxygen defects promoted Pd cluster bonding with Zn and Ti atoms in supports, thereby forming a metal-metal bond. Electron spin resonance (ESR), X-ray absorption fine spectra (XAFS), and density functional theory (DFT) calculations demonstrate remarkable interfacial electron transfer (0.62 e). The Pd/ZnTi-LDH catalyst shows superior catalytic stability for CO direct esterification to dimethyl oxalate. By contrast, the nonreducible Pd/ZnAl-LDH catalyst with a few oxygen defects shows minimal interfacial electron transfer (0.08 e), which leads to relatively poor catalytic stability. This work provides a deep insight into promoting the stability of catalysts by boosting interfacial electron transfer via defect induction.

Enhanced metal-support interaction between Pd and hierarchical Nb2O5via oxygen defect induction to promote CO oxidative coupling to dimethyl oxalate.

Production of ethylene glycol from coal is a particularly interesting route as it is an economic alternative to the petrochemical-based route. In this process, effectively generating dimethyl oxalate (DMO) is a crucial step by CO oxidative coupling reaction under Pd-based catalysts. However, the aggregation of Pd species over the support is still an issue that relates to the deterioration of catalytic activity and stability. To this end, enhancing the metal-support interaction is urgently required. In this work, hierarchical Nb2O5 (H-Nb2O5) microspheres with abundant oxygen defects were synthesized to anchor the Pd species thus promoting the electron transfer between Pd species and Nb species associated with the generation of interfacial Pd-NbOx sites. Besides, the thinned electron density of Pd species resulting from the electron-withdrawing effect of Nb species is beneficial for activating the adsorbed CO molecules, leading to superior catalytic activity. The Pd/H-Nb2O5 catalyst exhibited 63.1% of CO conversion (theoretical maximum conversion: 64.3%) and 92.9% of DMO selectivity, with a DMO weight time yield of 1297.9 g kgcat.-1 h-1, and remained robust even after 50 h of time on stream evaluation. Current work provides a deep insight into the CO activation mechanism and helps improve the catalytic stability by boosting interfacial electron interaction via oxygen defects induction, and also sheds light on the design and synthesis of high-performance catalysts in other heterogeneous catalysis fields.

CO direct esterification to dimethyl oxalate and dimethyl carbonate: the key functional motifs for catalytic selectivity.

The direct esterification of CO involves processes using CO as the starting material and ester chemicals as products. Dimethyl oxalate (DMO) and dimethyl carbonate (DMC) are two different products of the direct CO esterification reaction. However, the effective control of the reaction pathway and direct synthesis of DMO and DMC are challenging. In this review, we summarize the recent research progress on the direct esterification of CO to DMO/DMC and reveal the functional motifs responsible for the catalytic selectivity. Firstly, we discuss the microstructure of catalysts for the direct esterification of CO to DMO and DMC, including the valence state and the aggregate state of Pd. Then, the influence of characteristics of the support on the selectivity is analyzed. Importantly, the aggregate state of the active component, Pd is deemed as a vital functional motif for catalytic selectivity. The isolated Pd is conducive for the formation of DMC, while the aggregated Pd is beneficial for the formation of DMO. This review will provide rational guidance for the direct esterification of CO to DMO and DMC.

CeO2-x quantum dots with massive oxygen vacancies as efficient catalysts for the synthesis of dimethyl carbonate.

CeO2-x quantum dots with massive oxygen vacancies are obtained by a one-step single molecular synthesis strategy. The yield of dimethyl carbonate from CO2 and methanol is more than 5 times that for commercial CeO2 nanoparticles.

Zn2+ stabilized Pd clusters with enhanced covalent metal-support interaction via the formation of Pd-Zn bonds to promote catalytic thermal stability.

Pd-Based heterogeneous catalysts have been demonstrated to be efficient in numerous heterogeneous reactions. However, the effect of the support resulting in covalent metal-support interaction (CMSI) has not been researched sufficiently. In this work, a Lewis base is modulated over MgAl-LDH to investigate the support effects and it is further loaded with Pd clusters to research the metal-support interactions. MgAl-LDH with ultra-low Pd loading (0.0779%) shows CO conversion (55.0%) and dimethyl oxalate (DMO) selectivity (93.7%) for CO oxidative coupling to DMO, which was gradually deactivated after evaluation for 20 h. To promote the stability of Pd/MgAl-LDH, Zn2+ ions were introduced into the MgAl-LDH support to strengthen the CMSI by forming Pd-Zn bonds, which further increased the adsorption energy of the Pd clusters on ZnMgAl-LDH, and this was verified by X-ray absorption fine structure (XAFS) measurements and density functional theory (DFT) calculations. The stability of the Pd/ZnMgAl-LDH catalyst could be maintained for at least 100 h. This work highlights that covalent metal-support interactions can be strengthened by forming new metal-metal bonds, which could be extended to other systems for the stabilization of noble metals over supports.

An ultra-low Pd loading nanocatalyst with high activity and stability for CO oxidative coupling to dimethyl oxalate.

A Pd/α-Al2O3 nanocatalyst with ultra-low Pd loading exhibits high activity and stability for CO oxidative coupling to dimethyl oxalate, which was prepared by a Cu(2+)-assisted in situ reduction method at room temperature. The small size and high dispersion of Pd nanoparticles facilitated by Cu(2+) ions are responsible for the excellent catalytic activity.