Enantiospecific Analysis of Carboxylic Acids Using Cinchona Alkaloid Dimers as Chiral Solvating Agents.

Cinchona alkaloid derivatives as Brønsted base catalysts have attracted considerable attention in the field of asymmetric catalysis. However, their potential application as chiral solvating agents has not been described. In this research, we investigated the use of the Cinchona alkaloid dimer, namely, (DHQ)2PHAL, as a chiral solvating agent for discerning various mandelic acid derivatives through 1H NMR spectroscopy. The addition of catalytic amounts of DMAP facilitated this process. Our experimental results demonstrate that dimeric (DHQ)2PHAL exhibits remarkable chiral discrimination properties regarding the diagnostic split protons of 1H NMR signals (including 24 examples, up to 0.321 ppm). Furthermore, it serves as an excellent chiral discriminating agent and provides good resolution for racemic chiral phosphoric acid as determined by 31P NMR spectroscopy. The quality of enantiodifferentiation has also been evaluated by means of the parameter "resolution (Rs)". Significantly, this class of CSAs based on (alkaloid)2linker systems with an azaaromatic linker can be directly employed, which is commercially available in an enantiopure form at very low cost and exhibits promising potential in determining the enantiopurity of α-hydroxy acids by chemoselective and biocatalytic reactions.

Scalable manufacturing of an amide-based nucleating agent for transparency and high heat resistance of polylactic acid.

The prevalent use of disposable plastic tableware presents notable environmental and health risks. An alternative, polylactic acid (PLA), often does not meet usage requirements due to its low crystallization rate. This research introduces an amide-based nucleating agent, BRE-T-100, developed through a straightforward method to enhance the heat resistance and crystallization rate of PLA. This study systematically investigates the impact of BRE-T-100 and other nucleating agents on the properties of PLA composites. The incorporation of 0.8 % BRE-T-100 increases the crystallization temperature of PLA from 109.6 °C to 131.9 °C. Further, the total crystallization time of PLA composites at 120 °C is reduced to <60 s, while maintaining good transparency. BRE-T-100 exhibits superior comprehensive properties compared to talcum, TMC-200, and TMC-300 and is nearly on par with LAK-301. Its application as a nucleating agent in PLA-based disposable tableware shows promise.

Swimming behavior indicates stress and adaptations to exercise.

Introduction: Behaviors of swimming rodents are not uniform, exhibiting large variations, which may underlie the individual differences in swimming exercise-induced benefits. The study aimed to monitor individualized swimming behavior and evaluate its biological significance. Methods: A swimming tank which can monitor individualized rodent swimming behavior during exercise was established. A total of 45 mice were subjected to swimming training for 1 month (1 h per day) and the swimming behaviors of each mouse were recorded. Results: The swimming behaviors of mice displayed considerable variations in aspects of distance, velocity, and area preference. For example, nearly one-third of mice preferred to swim in central area and most of the mice exhibited an even area distribution. Long-term exercise training improved cardiac systolic function and decreased blood pressure in mice, but hardly changed swimming behaviors. Analyses of the relationship between swimming behavior and cardiovascular adaptations to exercise training revealed that swimming behavior indicated the biological effects of swimming training. Specifically, mice which preferred swimming at the central zone or were trainable in behavior during 1-month training exhibited better outcomes in cardiac function and blood pressure post long-term exercise. Mechanistically, a centralized swimming behavior indicated a smaller stress during exercise, as evidenced by a milder activation of hypothalamic-pituitary-adrenal axis. Discussion: These results suggest that swimming behavior during training indicates individualized adaptations to long-term exercise, and highlight a biological significance of swimming behavior monitoring in animal studies.

Comparison of instrumented and stand-alone lateral lumbar interbody fusion for lumbar degenerative disease: a systematic review and meta-analysis.

BACKGROUND: Both instrumented and stand-alone lateral lumbar interbody fusion (LLIF) have been widely used to treat lumbar degenerative disease. However, it remains controversial as whether posterior internal fixation is required when LLIF is performed. This meta-analysis aims to compare the radiographic and clinical results between instrumented and stand-alone LLIF. METHODS: PubMed, EMBASE and Cochrane Collaboration Library up to March 2023 were searched for studies that compared instrumented and stand-alone LLIF in the treatment of lumbar degenerative disease. The following outcomes were extracted for comparison: interbody fusion rate, cage subsidence rate, reoperation rate, restoration of disc height, segmental lordosis, lumbar lordosis, visual analog scale (VAS) scores of low-back and leg pain and Oswestry Disability Index (ODI) scores. RESULTS: 13 studies involving 1063 patients were included. The pooled results showed that instrumented LLIF had higher fusion rate (OR 2.09; 95% CI 1.16-3.75; P = 0.01), lower cage subsidence (OR 0.50; 95% CI 0.37-0.68; P < 0.001) and reoperation rate (OR 0.28; 95% CI 0.10-0.79; P = 0.02), and more restoration of disc height (MD 0.85; 95% CI 0.18-1.53; P = 0.01) than stand-alone LLIF. The ODI and VAS scores were similar between instrumented and stand-alone LLIF at the last follow-up. CONCLUSIONS: Based on this meta-analysis, instrumented LLIF is associated with higher rate of fusion, lower rate of cage subsidence and reoperation, and more restoration of disc height than stand-alone LLIF. For patients with high risk factors of cage subsidence, instrumented LLIF should be applied to reduce postoperative complications.

Ratiometric electrochemical determination of hydroxyl radical based on graphite paper modified with metal-organic frameworks and impregnated with salicylic acid.

Hydroxyl radical (•OH) detection is pivotal in medicine, biochemistry and environmental chemistry. Yet, electrochemical method-specific detection is challenging because of hydroxyl radicals' high reactivity and short half-life. In this study, we aimed to modify the electrode surface with a specific recognition probe for •OH. To achieve this, we conducted a one-step hydrothermal process to fabricate a CoZnMOF bimetallic organic framework directly onto conductive graphite paper (Gp). Subsequently, we introduced salicylic acid (SA) and methylene blue (MB), which easily penetrated the pores of CoZnMOF. By selectively capturing •OH by SA and leveraging the electrochemical signal generated by the reaction product, we successfully developed an electrochemical sensor Gp/CoZnMOF/SA + MB. The prepared sensor exhibited a good linear relationship with •OH concentrations ranging from 1.25 to 1200 nM, with a detection limit of 0.2 nM. Additionally, the sensor demonstrated excellent reproducibility and accuracy due to the incorporation of an internal reference. It exhibited remarkable selectivity for •OH detection, unaffected by other electrochemically active substances. The establishment of this sensor provides a way to construct MOF-modified sensors for the selective detection of other reactive oxygen species (ROS), offering a valuable experimental basis for ROS-related disease research and environmental safety investigations.

Accuracy of the Cage Placement in Oblique Lumbar Interbody Fusion and its Effects on the Radiological Outcome in Lumbar Degenerative Disease.

STUDY DESIGN: A retrospective study. OBJECTIVES: This study aimed to check how accurately cages were inserted and how they affected the radiological results in oblique lumbar interbody fusion (OLIF) at L2-L5. METHODS: A total of 137 patients diagnosed with lumbar degenerative disease, 184 intervertebral discs were included. We used a new cage deviation classification system on magnetic resonance imaging (MRI) to determine cage insertion accuracy. Cage deviation angles (CDA) were classified into four groups based on the angle formed by the long axis of the cage and the horizontal axis of the vertebral body. Other radiological parameters on plain radiographs and MRI were compared based on this classification. RESULTS: Among 183 cages, 19 were in zone Ⅰ-Ⅱ (10.32%), 163 were in zone II-III (88.59%), and two were in zone III-IV (1.09%). The median cage deviation was 4.97°. No significant differences (H = 2.479, P = .290 > .05) of CDA were found among different segments. Posterior cage deviation accounted 94.57%. The minimal, mild, moderate, and severe cage deviation was 89 (48.4%), 51 (27.7%), 30 (16.3%), and 14 (7.6%) respectively. No differences in radiological parameter changes were noted among different cage obliquity categories. CONCLUSIONS: Approximately 98.91% of cages were placed in zones I-II and II-III. Most cages deviated posteriorly with CDA ranging minimal to moderate. Minimal to moderate cage deviation did not impact radiological outcomes significantly in OLIF at L2-L5. However, avoiding severe cage deviation is crucial to prevent contralateral traversing nerve root injuries.

A dual-ligand lanthanide-based metal-organic framework for highly selective and sensitive colorimetric detection of Fe2.

Accumulation of heavy metals in humans and mammals causes health problems due to their abundance as transition metal ions. Iron (Fe2+) serves significantly in numerous biological processes as a heavy metal ion. In this study, we have designed and prepared a metal-organic framework (MOF) utilizing a one-step solvothermal process, incorporating a dual-ligand combination of terephthalic acid (H2BDC) and α,α',α''-tert-pyridine (TPY) with Eu3+ as the metal node. For this MOF, we termed it Eu-BDC/TPY. Eu-BDC/TPY has superior selectivity over other metal cations. It provides an accurate, sensitive, broad linear range colorimetric method for detecting Fe2+ in a concentration range of 1-50 µM with a modest limit of detection (0.33 µM). Eu-BDC/TPY detects the absence of Fe2+ quickly (within 5 seconds), which is very valuable in practical applications. In addition, the results can be used to create a digital image colorimetric card (DIC) using colorimetric software, enabling instantaneous detection of Fe2+ concentration using a smartphone.

Identification and Validation of Glomeruli Cellular Senescence-Related Genes in Diabetic Nephropathy by Multiomics.

Accumulating evidence indicates that cellular premature senescence of the glomerulus, including endothelial cells, mesangial cells, and podocytes leads to diabetic nephropathy (DN), and DN is regarded as a clinical model of premature senescence. However, the role of cellular senescence-associated genes in the glomerulus in DN progression remains unclear. Therefore, this work aims to identify and validate potential cellular aging-related genes in the glomerulus in DN to provide novel clues for DN treatment based on anti-aging. The microarray GSE96804 dataset, including 41 diabetic glomeruli and 20 control glomeruli, is retrieved from the Gene Expression Omnibus (GEO) database and cellular senescence-related genes (CSRGs) are obtained from the GeneCards database and literature reports. Subsequently, PPI, GO, and KEGG enrichment are analyzed by screening the intersection between differentially expressed genes (DEGs) and CSRGs. scRNA-seq dataset GSE127235 is used to verify core genes expression in glomerulocytes of mice. Finally, db/db mice are utilized to validate the hub gene expression in the glomeruli, and high glucose-induced mesangial cells are used to confirm key gene expression. This study reveals that FOS and ZFP36 may play an anti-aging role in DN to ameliorate cell intracellular premature aging in mesangial cells of glomeruli.

Polyarylisocyanides Derived from an Alkyne-Pd(II) Catalyst as Robust Alignment Media with Excellent Enantiodiscimination.

The development of chiral alignment media for measuring anisotropic NMR parameters provides an opportunity to determine the absolute configuration of chiral molecules without the need for derivatization. However, chiral alignment media with a high and robust enantiodiscriminating property for a wide range of chiral molecules are still scarce. In this study, we synthesized cholesterol-end-functionalized helical polyisocyanides from a chiral monomer using a cholesterol-based alkyne-Pd(II) initiator. These stereoregular polyisocyanides form stable and weak anisotropic lyotropic liquid crystals (LLCs) in dichloromethane systems, exhibiting highly optical activities in both single left- and right-handed helices. The preparation process of the media was straightforward, and the aligning property of the LLCs could be controlled by adjusting the concentration and temperature. Using the chiral polyisocyanides, we extracted the residual dipolar coupling for an enantiomeric pair of isopinocampheol (IPC), as well as a number of pharmaceutical molecules, demonstrating excellent enantiodiscriminating properties for a broad range of chiral compounds.

Finite element analysis of the knee joint stress after partial meniscectomy for meniscus horizontal cleavage tears.

OBJECTIVE: To establish a finite element model of meniscus horizontal cleavage and partial resection, to simulate the mechanical changes of knee joint under 4 flexion angles, and to explore what is the optimal surgical plan. METHODS: We used Mimics Research, Geomagic Wrap, and SolidWorks computer software to reconstruct the 3D model of the knee joint, and then produced the horizontal cleavage tears model of the internal and lateral meniscus, the suture model, and the partial meniscectomy model. These models were assembled into a complete knee joint in SolidWorks software, and corresponding loads and boundary constraints were added to these models in ANSYS software to simulate the changing trend of pressure and shear force on femoral condylar cartilage, meniscus, and tibial cartilage under the flexion angles of 0°, 10°, 20°, 30° and 40° of the knee joint. At the same time, the difference of force area between medial interventricular and lateral interventricular of knee joint under four states of bending the knee was compared, to explore the different effects of different surgical methods on knee joint after horizontal meniscus tear. RESULTS: Within the four medial meniscus injury models, the lowest peak internal pressure and shear force of the knee joint was observed in the meniscal suture model; the highest values were found in the bilateral leaflet resection model and the inferior leaflet resection model; the changes of pressure, shear force and stress area in the superior leaflet resection model were the most similar to the changes of the knee model with the meniscal suture model. CONCLUSION: Suture repair is the best way to maintain the force relationship in the knee joint. However, resection of the superior leaflet of the meniscus is also a reliable choice when suture repair is difficult.

Two and three-dimensional halogen-bonded frameworks: self-assembly influenced by crystallization solvents.

In this paper, two types of solid phase 2D and 3D XBOFs were selectively constructed from identical building blocks of tetraphenylmethane tetrapyridine derivative and 1,4-diiodotetrafluorobenzene by changing the crystallization solvent. This 3D XBOF is a novel hybrid supramolecular organic framework with the synergistic control of hydrogen and halogen bonds.

Comparison between OLIF and MISTLIF in degenerative lumbar stenosis: an age-, sex-, and segment-matched cohort study.

To compare outcomes after oblique lateral interbody fusion (OLIF) versus minimally invasive transforaminal lumbar interbody fusion (MISTLIF) with bilateral decompression via unilateral approach for treating mild to moderate symptomatic degenerative lumbar spinal stenosis (DLSS). We retrospectively compared patients who underwent single-level (L4/5) OLIF with an age-, sex-, and segment-matched MISTLIF with bilateral decompression via unilateral approach cohort. Perioperative data were collected for the operative time, intraoperative blood loss, drainage in the first postoperative day, postoperative hospital stay, cost, intraoperative fluoroscopy, and complications. Lumbar radiographs were measured for changes in posterior intervertebral space height (PISH), intervertebral space foramen height (IFH), intervertebral foramen area (IFA), and area of the spinal canal (ASC). Clinical and psychological outcomes included the visual analog scale (VAS), Oswestry Disability Index (ODI), and hospital anxiety and depression scale (HADS). 35 OLIF patients were compared with 35 MISTLIF patients in L4/5 DLSS. The OLIF group had shorter bedtime, postoperative hospital stays, less intraoperative and postoperative blood loss (all P < 0.05), but had more times of intraoperative fluoroscopy, longer operative time, and higher cost (all P < 0.05). The complication rates were equivalent (OLIF vs MISTLIF: 22.86% vs 17.14%). PISH (11.94 ± 1.78 mm vs 9.42 ± 1.94 mm, P < 0.05), IFH (23.87 ± 3.05 mm vs 21.41 ± 2.95 mm, P < 0.05), and IFA (212.14 ± 51.82 mm2 vs 177.07 ± 51.73 mm2, P < 0.05) after surgery were significantly increased in the OLIF group. The ASC was increased significantly after the operation in both groups, but the ASC in the MISTLIF group was increased significantly more than that in the OLIF group (450.04 ± 66.66 mm2 vs 171.41 ± 58.55 mm2, P < 0.05). The lumbar VAS scores at 1 month (1.89 ± 0.87 vs 2.34 ± 0.84, P = 0.028) and 6 months (1.23 ± 0.97 vs 1.80 ± 0.99, P = 0.018) after operation in the OLIF group were significantly lower. There were no significant differences in lower extremity VAS and ODI scores between the two groups. Compared with MISTLIF group, HADS scores on postoperative day 3 (2.91 ± 1.46 vs 4.89 ± 1.78, P < 0.05) and prior to hospital discharge (PTD) (2.54 ± 1.38 vs 3.80 ± 1.78, P = 0.002) in the OLIF group were decreased significantly. OLIF showed more advantages of less surgical invasion, lower incidence of postoperative low back pain, faster postoperative recovery, and less anxiety compared with MISTLIF. Regardless of cost, OLIF seems to be a better option to treat mild to moderate symptomatic DLSS.

Construction of N-Ferrocene Substituted Benzodihydrooxazoles via a Catalyst-Free Aza-Michael Addition/C(sp3)-O Bond Formation Tandem Reaction.

A catalyst-free aza-Michael addition/C(sp3)-O bond formation tandem reaction of substituted amino ferrocenes with quinone esters was developed, which provided a green and efficient strategy for the construction of a C(sp3)-O bond from C(sp3)-H, and a series of N-ferrocene-substituted benzodihydrooxazoles were smoothly produced in moderate to excellent yields (up to >99% yield). The mechanism experiments showed that quinone esters performed as both substrate and oxidant. The salient features of this transformation include good functional group tolerance, broad substrate scope and mild conditions.

Catalyst-Controlled Direct Oxysulfonylation of Alkenes by Using Sulfonylazides as the Sulfonyl Radical.

A copper/cobalt-catalyzed difunctionalization of alkenes with sulfonylazides and tert-butyl hydroperoxide has been achieved. This protocol provides an efficient and direct oxysulfonylation approach to ß-ketosulfones and ß-sulfonyl peroxides in moderate to good yields under mild conditions. This methodology applies sulfonylazides as a new sulfonyl radical source and features a wide substrate scope and good functional group tolerance.

A Convex Optimization Approach to Multi-Robot Task Allocation and Path Planning.

In real-world applications, multiple robots need to be dynamically deployed to their appropriate locations as teams while the distance cost between robots and goals is minimized, which is known to be an NP-hard problem. In this paper, a new framework of team-based multi-robot task allocation and path planning is developed for robot exploration missions through a convex optimization-based distance optimal model. A new distance optimal model is proposed to minimize the traveled distance between robots and their goals. The proposed framework fuses task decomposition, allocation, local sub-task allocation, and path planning. To begin, multiple robots are firstly divided and clustered into a variety of teams considering interrelation and dependencies of robots, and task decomposition. Secondly, the teams with various arbitrary shape enclosing intercorrelative robots are approximated and relaxed into circles, which are mathematically formulated to convex optimization problems to minimize the distance between teams, as well as between a robot and their goals. Once the robot teams are deployed into their appropriate locations, the robot locations are further refined by a graph-based Delaunay triangulation method. Thirdly, in the team, a self-organizing map-based neural network (SOMNN) paradigm is developed to complete the dynamical sub-task allocation and path planning, in which the robots are dynamically assigned to their nearby goals locally. Simulation and comparison studies demonstrate the proposed hybrid multi-robot task allocation and path planning framework is effective and efficient.

Utilizing Ultra-homogeneous SiOx and Defects to Achieve Interlayer Protection for Lithium Metal Anodes.

The uncontrollable growth and uneven nucleation of lithium metal can be addressed by utilizing spatial confinement structures in conjunction with lithiophilic sites. However, their complex fabrication technique and the inhomogeneous dispersion of lithiophilic sites make the application ineffective. In this work, ultra-uniformly dispersed SiOx seeds and defects are produced in situ to achieve the spatially restricted protection within the reduced graphene oxide (rGO) layer. The in situ formed SiOx and defects during annealing double constrain lithium nucleation and growth behaviors thanks to the superlithiophilic characteristic, while both provide the fast Li+ transport channel to utilize the interlayer protection of rGO in limiting lithium dendrite growth. Furthermore, XANES and XPS analyze the SiOx seeds that are dominated by various valence states, and theoretical calculations further verify the control on the nucleation of lithium atoms. Benefiting from the optimum average valence of three for the "control site", the host realizes steady circulation. In asymmetric cells, the host demonstrates excellent coulombic efficiency of 99.1% and stable lifespans over 1250 h at 1 mA cm-2 . When assembled in LiFePO4 full cells, it retains a favorable capacity of 116.2 mA h g-1 after 170 cycles.

Ginsenoside Rg1 attenuates cerebral ischemia-reperfusion injury through inhibiting the inflammatory activation of microglia.

It is recognized that the cerebral ischemia/reperfusion (I/R) injury triggers inflammatory activation of microglia and supports microglia-driven neuronal damage. Our previous studies have shown that ginsenoside Rg1 had a significant protective effect on focal cerebral I/R injury in middle cerebral artery occlusion (MCAO) rats. However, the mechanism still needs further clarification. Here, we firstly reported that ginsenoside Rg1 effectively suppressed the inflammatory activation of brain microglia cells under I/R conditions depending on the inhibition of Toll-likereceptor4 (TLR4) proteins. In vivo experiments showed that the ginsenoside Rg1 administration could significantly improve the cognitive function of MCAO rats, and in vitro experimental data showed that ginsenoside Rg1 significantly alleviated neuronal damage via inhibiting the inflammatory response in microglia cells co-cultured under oxygen and glucose deprivation/reoxygenation (OGD/R) condition in gradient dependent. The mechanism study showed that the effect of ginsenoside Rg1 depends on the suppression of TLR4/MyD88/NF-κB and TLR4/TRIF/IRF-3 pathways in microglia cells. In a word, our research shows that ginsenoside Rg1 has great application potential in attenuating the cerebral I/R injury by targeting TLR4 protein in the microglia cells.

Brønsted Acid-Catalyzed Reaction of N-arylnaphthalen-2-amines with Quinone Esters for the Construction of Carbazole and C-N Axially Chiral Carbazole Derivatives.

We demonstrated here an efficient synthetic method of carbazole derivatives from readily available N-arylnaphthalen-2-amines and quinone esters catalyzed by Brønsted acid. With this strategy, a series of carbazole derivatives were obtained in good to excellent yields (76 to >99) under mild conditions. Large scale reaction illustrated the synthetic utility of this protocol. Meanwhile, a series of C-N axially chiral carbazole derivatives were also constructed in moderate to good yields (36-89% yield) with moderate to excellent atroposelectivities (44-94% ee) by using chiral phosphoric acid as a catalyst, which provides a novel strategy for the atroposelective construction of C-N axially chiral compounds and a new member of the C-N atropisomers.

Comparison of denosumab and oral bisphosphonates for the treatment of glucocorticoid-induced osteoporosis: a systematic review and meta-analysis.

BACKGROUND: Both denosumab and bisphosphonates have been demonstrated effective for glucocorticoid-induced osteoporosis. However, evidence-based medicine is still lacking to prove the clinical results between denosumab and bisphosphonates. This meta-analysis aims to compare the efficacy and safety between denosumab and oral bisphosphonates for the treatment of glucocorticoid-induced osteoporosis through evidence-based medicine. METHODS: MEDLINE, EMBASE, and the Cochrane library databases were searched up to June 2022 for randomized controlled trials that compared denosumab and oral bisphosphonates in the treatment of glucocorticoid-induced osteoporosis. The following outcomes were extracted for comparison: percentage change in bone mineral density from baseline at the lumbar spine, total hip, femoral neck, and ultra-distal radius; percentage change from baseline in serum concentration of bone turnover markers; and incidence of treatment-emergent adverse events. RESULTS: Four randomized controlled trials involving 714 patients were included. The pooled results showed that denosumab was superior to bisphosphonates in improving bone mineral density in lumbar spine (mean difference (MD) 1.70; 95% confidence interval (CI) 1.11-2.30; P < 0.001) and ultra-distal radius (MD 0.87; 95% CI 0.29-1.45; P = 0.003), and in suppressing C-terminal telopeptide of type 1 collagen (MD -34.83; 95% CI -67.37--2.28; P = 0.04) and procollagen type 1 N-terminal propeptide (MD -14.29; 95% CI -23.65- -4.94; P = 0.003) at 12 months. No significant differences were found in percentage change in total hip or femoral neck bone mineral density at 12 months, or in the incidence of treatment-emergent adverse events or osteoporosis-related fracture. CONCLUSIONS: Compared with bisphosphonates, denosumab is superior in improving bone mineral density in lumbar spine and ultra-distal radius for glucocorticoid-induced osteoporosis. Further studies are needed to prove the efficacy of denosumab.