Cationic Foldamer-Catalyzed Asymmetric Synthesis of Inherently Chiral Cages.

The stereochemistry of shape-persistent molecular cages, particularly those resembling prisms, exerts significant influence on their application-specific functionalities. Although methods exist for fabricating inherently chiral prism-like cages, strategies for catalytic asymmetric synthesis of these structures in a diversity-oriented fashion remain unexplored. Herein, we introduce an unprecedented organocatalytic desymmetrization approach for the generation of inherently chiral prism-like cages via phosphonium-containing foldamer-catalyzed SNAr reactions. This methodology establishes a topological connection, enabling the facile assembly of a wide range of versatile stereogenic-at-cage building blocks possessing two highly modifiable groups. Furthermore, subsequent stereospecific transformations of the remaining chlorides and/or ethers afford convenient access to numerous functionally relevant chiral-at-cage molecules.

Gold-Catalyzed Intramolecular Hydroarylation and Transfer Hydrogenation of N-Aryl Propargylamines to Construct Tetrahydroquinolines and 5,6-Dihydro-4H-pyrrolo[3,2,1-ij]quinolines.

A novel protocol of gold-catalyzed N-aryl propargylamines to construct tetrahydroquinolines and 5,6-dihydro-4H-pyrrolo[3,2,1-ij]quinolines in moderate to good yields has been developed through the tandem reactions of intramolecular hydroarylation and transfer hydrogenation. The strategy has the advantages of easy access to raw materials, simple reaction conditions, good substrate compatibility, high efficiency, and excellent regioselectivity.

Discovery, Quantitative Recurrence, and Inhibition of Motion-Blur Hysteresis Phenomenon in Visual Tracking Displacement Detection.

Motion blur is common in video tracking and detection, and severe motion blur can lead to failure in tracking and detection. In this work, a motion-blur hysteresis phenomenon (MBHP) was discovered, which has an impact on tracking and detection accuracy as well as image annotation. In order to accurately quantify MBHP, this paper proposes a motion-blur dataset construction method based on a motion-blur operator (MBO) generation method and self-similar object images, and designs APSF, a MBO generation method. The optimized sub-pixel estimation method of the point spread function (SPEPSF) is used to demonstrate the accuracy and robustness of the APSF method, showing the maximum error (ME) of APSF to be smaller than others (reduced by 86%, when motion-blur length > 20, motion-blur angle = 0), and the mean square error (MSE) of APSF to be smaller than others (reduced by 65.67% when motion-blur angle = 0). A fast image matching method based on a fast correlation response coefficient (FAST-PCC) and improved KCF were used with the motion-blur dataset to quantify MBHP. The results show that MBHP exists significantly when the motion blur changes and the error caused by MBHP is close to half of the difference of the motion-blur length between two consecutive frames. A general flow chart of visual tracking displacement detection with error compensation for MBHP was designed, and three methods for calculating compensation values were proposed: compensation values based on inter-frame displacement estimation error, SPEPSF, and no-reference image quality assessment (NR-IQA) indicators. Additionally, the implementation experiments showed that this error can be reduced by more than 96%.

Towards Axially Chiral Pyrazole-Based Phosphorus Scaffolds by Dipeptide-Phosphonium Salt Catalysis.

Given the comparatively lower rotational barriers, the catalytic asymmetric construction of axially chiral biaryl structures, especially those containing a five-membered heterocycle, still remains a challenge. Herein, we described a general and modular protocol to access atropisomeric arylpyrazole scaffolds containing a phosphorus unit by a dipeptide phosphonium salt catalyzed reaction involving an oxidative central-to-axial chirality conversion. This reaction features excellent yields and enantioselectivities, broad substrate scope, and a low catalyst loading, delivering axially chiral phosphine compounds.

Cardiopulmonary exercise test-based assessment of the effects of sacubitril/valsartan on the blood pressure response to exercise in patients with acute myocardial infarction during hospitalization.

OBJECTIVE: To investigate the effects of sacubitril/valsartan (S/V) on cardiopulmonary function and blood pressure response to exercise during hospitalization in patients with acute myocardial infarction (AMI) based on the cardiopulmonary exercise test (CPET). METHODS: A total of 265 AMI patients were treated with either perindopril or S/V within 24 hours of admission. CPET was completed for all patients before discharge. There were 182 cases in the perindopril group and 83 cases in the S/V group. RESULTS: The proportion of exercise oscillatory ventilation (EOV) was higher in the S/V group than in the perindopril group (10.8% vs 1.6%, X2 = 11.148, P = .001). The resting heart rate (HR), resting diastolic blood pressure (DBP), and warm-up DBP were lower in the S/V group than in the perindopril group (P < .05). The resting systolic blood pressure (SBP) was 9.0 mmHg lower (115.7 ± 17.5 vs 106.7 ± 15.0, P < .001), the SBP during warm-up was 9.5 mmHg lower (124.8 ± 23.7 vs 115.3 ± 22.5,P = .002), the SBP at the anaerobic threshold (AT) was 10.5 mmHg lower (135.3 ± 24.8 vs 127.1 ± 25.1,P = .021),the SBP at max watts was 11.5 mmHg lower (148.9 ± 26.4 vs 137.4 ± 26.4,P = .001), and the SBP during one-minute recovery was 12.3 mmHg lower (146.5 ± 27.1 vs 134.2 ± 24.4, P = .001)in the S/V group than in the perindopril group. The S/V group had a higher oxygen ventilation equivalent and carbon dioxide ventilation equivalent (VE/VCO2) at AT and a lower oxygen uptake-work rate relationship during max watts (P < .05). The differences in the oxygen pulse, stroke volume, peak oxygen uptake (VO2 peak), and VE/VCO2 slope were not statistically significant between the two groups. CONCLUSION: Treatment with S/V was able to reduce the exercise blood pressure in patients with AMI during hospitalization, but did not significantly improve the VO2 peak, VE/VCO2 slope, or exercise tolerance.

Atosiban Combined with Ritodrine for Late Threatened Abortion or Threatened Premature Labor Patients with No Response to Ritodrine: A Clinical Trial.

BACKGROUND Premature labor is an important cause of infant death and long-term disability. This study aimed to explore the safety and effectiveness of combining the tocolytic agents atosiban and ritodrine to extend gestation. MATERIAL AND METHODS The study included 52 patients with late threatened abortion and threatened premature labor between 20°â¸7 and 336⸍7 weeks' gestation who were administrated continuous tocolytic agents for 48 h. Patients were divided into a research group receiving ritodrine combined with atosiban, owing to having no response to ritodrine alone (n=30), and a control group receiving ritodrine alone (n=22). The mean infusion rate and duration of tocolytic administration, gestation extension, pregnancy outcomes, and adverse effects were recorded. Routine blood tests, including C-reactive protein, and cultures for leukorrhea, candida, and mycoplasma were performed before and 1 week after treatment. RESULTS Patients receiving ritodrine with atosiban had a mean gestation extension of 42.53±31.70 days. The extension of gestation of the research group was statistically shorter than that of the control group (P<0.05). The fetal loss rate, newborn birth weight, and Apgar score at 1 min were similar between the 2 groups (all, P>0.05). The research group had a lower incidence of palpitations than the control group (P<0.05). CONCLUSIONS For patients with late threatened abortion or threatened premature labor not controlled with ritodrine alone, ritodrine combined with atosiban extends gestation and improves pregnancy outcomes. For patients with abnormal uterine contractions, routine testing for reproductive tract infection should be performed. When infection is present, anti-infective therapy should be administered.

SO2 derivatives induce dysfunction in human trophoblasts via inhibiting ROS/IL-6/STAT3 pathway.

BACKGROUND: Epidemiological studies have revealed that sulfur dioxides (SO2) can increase the risk of pregnancy complications such as missed abortion in the first trimester, stillbirth, preterm birth, small for gestational age, gestational diabetes mellitus and preeclampsia, but the mechanisms underlying these findings remains unknown. What is known, however, is that trophoblasts, a type of fetal cell exerting vital immunologic functions to maintain a successful pregnancy, are usually involved in the pathogenic mechanism of pregnancy complications. OBJECTIVE: To study the effect of SO2 derivatives (bisulfite and sulfite, 1:3 M/M) on the function of trophoblasts. METHODS: Swan.71 trophoblast cells were treated with various concentrations of SO2 derivatives to determine the effect of SO2 derivatives on cellular viability by CKK8. Flow cytometry was performed to analyze the effect of SO2 derivatives on apoptosis, cell cycle and intracellular ROS. Wound healing assay and transwell assay were conducted to examine the migration and invasion of Swan.71 cells. Inflammation-related cytokines in the supernatant (IL-1ß, IL-6, IL-8, IL-10 and TNF-α) were measured by IMMULITE®1000 Systems (SIEMENS). The expression level of NLRP3, Caspase1, MMP9, MMP2, STAT3, and p-STAT3 were evaluated by Western Blotting. RESULTS: Exposure to SO2 derivatives significantly decreased cellular viability, arrested cell cycle at S/G2/M phase and induced cell apoptosis of Swan.71 trophoblasts. In addition, the migration and invasion of Swan.71 cell were significantly inhibited. SO2 derivatives also significantly increased IL-1ß secretion while it is NLRP3/Caspase1 independent. IL-6 secretion was significant inhibited accompanied by decreased STAT3 phosphorylation and expression of MMP2 and MMP9. The intracellular ROS level was significantly suppressed by SO2 derivatives. CONCLUSION: SO2 derivatives exert toxic effects on trophoblasts which results in: suppressing cellular viability and intracellular ROS level, interfering with cell proliferation through arresting cell cycle, inducing cell apoptosis, disturbing inflammation-related cytokines secretion and inhibiting motility. Decreased ROS/IL-6/STAT3 levels play a role in inhibited cell viability, cell cycle arrest, apoptosis and defective motility.

Inspection Method of Rope Arrangement in the Ultra-Deep Mine Hoist Based on Optical Projection and Machine Vision.

Due to the importance of safety detection of the drum's rope arrangement in the ultra-deep mine hoist and the current situation whereby the speed, accuracy and robustness of rope routing detection are not up to the requirements, a novel machine-vision-detection method based on the projection of the drum's edge is designed in this paper. (1) The appropriate position of the point source corresponding to different reels is standardized to obtain better projection images. (2) The corresponding image processing and edge curve detection algorithm are designed according to the characteristics of rope arrangement projection. (3) The Gaussian filtering algorithm is improved to adapt to the situation that the curve contains wavelet peak noise when extracting the eigenvalues of the edge curve. (4) The DBSCAN (density-based spatial clustering of applications with noise) method is used to solve the unsupervised classification problem of eigenvalues of rope arrangement, and the distance threshold is calculated according to the characteristics of this kind of data. Finally, we can judge whether there is a rope arranging fault just through one frame and output the location and number of the fault. The accuracy and robustness of the method are verified both in the laboratory and the ultra-deep mine simulation experimental platform. In addition, the detection speed can reach 300 fps under the premise of stable detection.

Enantiodivergent Kinetic Resolution of 1,1'-Biaryl-2,2'-Diols and Amino Alcohols by Dipeptide-Phosphonium Salt Catalysis Inspired by the Atherton-Todd Reaction.

A highly enantiodivergent organocatalytic method is disclosed for the synthesis of atropisomeric biaryls via kinetic resolution inspired by a dipeptide-phosphonium salt-catalyzed Atherton-Todd (A-T) reaction. This flexible approach led to both R- and S-enantiomers by fine-tuning of bifunctional phosphonium with excellent selectivity factors (s) of up to 1057 and 525, respectively. The potential of newly synthesized O-phosphorylated biaryl diols was illustrated by the synthesis of axially chiral organophosphorus compounds. Mechanistic investigations suggest that the bifunctional phosphonium halide catalyst differentiates between the in-situ-generated P-species in the A-T process, mainly involving phosphoryl chloride and phosphoric anhydride, thus leading to highly enantiodivergent O-phosphorylation reactions. Furthermore hydrogen bonding interactions between the catalysts and phosphorus molecules were crucial in asymmetric induction.

Rope Tension Fault Diagnosis in Hoisting Systems Based on Vibration Signals Using EEMD, Improved Permutation Entropy, and PSO-SVM.

Fault diagnosis of rope tension is significantly important for hoisting safety, especially in mine hoists. Conventional diagnosis methods based on force sensors face some challenges regarding sensor installation, data transmission, safety, and reliability in harsh mine environments. In this paper, a novel fault diagnosis method for rope tension based on the vibration signals of head sheaves is proposed. First, the vibration signal is decomposed into some intrinsic mode functions (IMFs) by the ensemble empirical mode decomposition (EEMD) method. Second, a sensitivity index is proposed to extract the main IMFs, then the de-noised signal is obtained by the sum of the main IMFs. Third, the energy and the proposed improved permutation entropy (IPE) values of the main IMFs and the de-noised signal are calculated to create the feature vectors. The IPE is proposed to improve the PE by adding the amplitude information, and it proved to be more sensitive in simulations of impulse detecting and signal segmentation. Fourth, vibration samples in different tension states are used to train a particle swarm optimization-support vector machine (PSO-SVM) model. Lastly, the trained model is implemented to detect tension faults in practice. Two experimental results validated the effectiveness of the proposed method to detect tension faults, such as overload, underload, and imbalance, in both single-rope and multi-rope hoists. This study provides a new perspective for detecting tension faults in hoisting systems.

Laser micro-structured pressure sensor with modulated sensitivity for electronic skins.

Micro-structured pressure sensors with broad pressure sensing range, high sensitivity and rapid response speeds are highly desired for epidermal electronic skin. The widely used methods to fabricate micro-structured pressure sensors are lithography and biomaterial-replicating, which are either complex in preparation procedure or uncontrollable in micro-structure morphology. In this work, laser micro-structured wearable pressure sensors with high-performance are developed for epidermal electronic skin. Laser micro-engineering, with scalability, high-efficiency, and controllability, is employed to prepare a series of micro-structures on elastomers for modulating and enhancing the sensitivity of the sensors. The device with micro-domes owns a sensitivity of -1.82 kPa-1, which is approximately 17 times better than the one based on long micro-ridges. Due to the reduced viscous properties of the elastomers by laser micro-engineering, the sensor based on micro-domes demonstrates rapid response/relaxation speeds of 0.036 and 0.052 s, respectively, and a detection limit of 0.001 kPa. Additionally, the device has a good durability (6,000 cycles) with a repeatability deviation of 1.44%, confirming its stability. Combined with near field communication technology, the sensor has been investigated as epidermal electronic skin for health monitoring.

Highly Enantioselective Synthesis of Fused Tri- and Tetrasubstituted Aziridines: aza-Darzens Reaction of Cyclic Imines with α-Halogenated Ketones Catalyzed by Bifunctional Phosphonium Salt.

The first enantioselective aza-Darzens reaction of cyclic imines with α-halogenated ketones was realized under mild reaction conditions by using amino-acid-derived bifunctional phosphonium salts as phase-transfer promoters. A variety of structurally dense tri- and tetrasubstituted aziridine derivatives, containing benzofused heterocycles as well as spiro-structures, were readily synthesized in high yields with excellent diastereo- and enantioselectivities (up to >20:1 d.r. and >99.9 % ee). The highly functionalized aziridine products could be easily transformed into different classes of biologically active compounds.

A wearable pressure sensor based on ultra-violet/ozone microstructured carbon nanotube/polydimethylsiloxane arrays for electronic skins.

Pressure sensors with high performance (e.g., a broad pressure sensing range, high sensitivities, rapid response/relaxation speeds, temperature-stable sensing), as well as a cost-effective and highly efficient fabrication method are highly desired for electronic skins. In this research, a high-performance pressure sensor based on microstructured carbon nanotube/polydimethylsiloxane arrays was fabricated using an ultra-violet/ozone (UV/O3) microengineering technique. The UV/O3 microengineering technique is controllable, cost-effective, and highly efficient since it is conducted at room temperature in an ambient environment. The pressure sensor offers a broad pressure sensing range (7 Pa-50 kPa), a sensitivity of âˆ¼ -0.101 ± 0.005 kPa-1 (<1 kPa), a fast response/relaxation speed of ∼10 ms, a small dependence on temperature variation, and a good cycling stability (>5000 cycles), which is attributed to the UV/O3 engineered microstructures that amplify and transfer external applied forces and rapidly store/release the energy during the PDMS deformation. The sensors developed show the capability to detect external forces and monitor human health conditions, promising for the potential applications in electronic skin.

Highly sensitive strain sensors based on fragmentized carbon nanotube/polydimethylsiloxane composites.

Wearable strain sensors based on nanomaterial/elastomer composites have potential applications in flexible electronic skin, human motion detection, human-machine interfaces, etc. In this research, a type of high performance strain sensors has been developed using fragmentized carbon nanotube/polydimethylsiloxane (CNT/PDMS) composites. The CNT/PDMS composites were ground into fragments, and a liquid-induced densification method was used to fabricate the strain sensors. The strain sensors showed high sensitivity with gauge factors (GFs) larger than 200 and a broad strain detection range up to 80%, much higher than those strain sensors based on unfragmentized CNT/PDMS composites (GF < 1). The enhanced sensitivity of the strain sensors is ascribed to the sliding of individual fragmentized-CNT/PDMS-composite particles during mechanical deformation, which causes significant resistance change in the strain sensors. The strain sensors can differentiate mechanical stimuli and monitor various human body motions, such as bending of the fingers, human breathing, and blood pulsing.

Meta-analysis of the association between plasminogen activator inhibitor-1 4G/5G polymorphism and recurrent pregnancy loss.

BACKGROUND: The association between plasminogen activator inhibitor-1 (PAI-1) 4G/5G polymorphism and recurrent pregnancy loss (RPL) risk is still contradictory. We thus performed a meta-analysis. MATERIAL AND METHODS: Relevant studies were searched for in PubMed, Web of Science, Embase, and Cochrane Library. An odds ratio (OR) with a 95% confidence interval (CI) was used to assess the association between PAI-1 4G/5G polymorphism and RPL risk. RESULTS: A total of 22 studies with 4306 cases and 3076 controls were included in this meta-analysis. We found that PAI-1 4G/5G polymorphism was significantly associated with an increased RPL risk (OR=1.89; 95% CI 1.34-2.67; P=0.0003). In the subgroup analysis by race, PAI-1 4G/5G polymorphism was significantly associated with an increased RPL risk in Caucasians (OR=2.23; 95% CI 1.44-3.46; P=0.0003). However, no significant association was observed in Asians (OR=1.47; 95% CI 0.84-2.59; P=0.18). CONCLUSIONS: In conclusion, this meta-analysis suggests that PAI-1 4G/5G polymorphism might be associated with RPL development in Caucasians.

Double-balloon catheter vs. dinoprostone vaginal insert for induction of labor with an unfavorable cervix.

PURPOSE: To compare a double-balloon catheter and dinoprostone vaginal insert for induction of labor with an unfavorable cervix. METHODS: Patients with a Bishop score of ≤6 requiring labor induction at term received either a double-balloon catheter or a dinoprostone vaginal insert. The primary outcome was vaginal delivery rate within 24 h, and the secondary outcome was cesarean section rate. RESULTS: A total of 155 women were included; 76 received induction with a double-balloon catheter and 79 with the dinoprostone vaginal insert. The groups were similar with respect to maternal age, body mass index, gravidity, parity, baseline Bishop score, and indications for induction. Gestational age at induction was similar between the groups (double balloon 40.52 ± 0.86 weeks; dinoprostone 40.60 ± 0.79 weeks, P = 0.516). There was no difference in the vaginal delivery rate within 24 h (50 vs. 53.2 %, P = 0.694) or the cesarean section rate (39.5 vs. 31.6 %, P = 0.185) between the groups. More patients in the double-balloon catheter group required oxytocin administration than in the dinoprostone group (75 vs. 31.65 %, respectively, P < 0.001), but uterine hyperstimulation was less frequent in the double-balloon catheter group (0 vs. 10.1 %, respectively, P = 0.007). Neonatal outcomes were similar between the groups. CONCLUSION: Double-balloon catheter and dinoprostone vaginal insert are associated with similar vaginal delivery and cesarean section rates and neonatal outcomes.

The frequencies of the presence of embryonic pole and cardiac activity in early miscarriages with abnormal karyotypes.

AIMS: The objective of this study was to compare the frequencies of the presence of an embryonic pole and cardiac activity in miscarriages with normal and abnormal embryonic karyotypes. MATERIALS AND METHODS: From January 2008 to December 2012, 405 patients with early miscarriage were evaluated during pregnancy by regular ultrasound, and karyotyping was performed on chorionic villus tissue after curettage. The frequencies of the presence of an embryonic pole and cardiac activity were compared between patients with a normal embryonic karyotype and patients with an abnormal embryonic karyotype. RESULTS: Of the 405 samples, 224 cases (55.3%) had an abnormal karyotype, and 181 cases (44.7%) had a normal karyotype. The frequencies of the presence of an embryonic pole and cardiac activity in miscarriages with normal embryonic chromosomes (71.8% and 57.5%, respectively) were similar to those of miscarriages with abnormal embryonic chromosomes (74.1% and 62.1%, respectively). The frequencies of the presence of an embryonic pole and cardiac activity were higher in miscarriages with viable autosomal trisomies (trisomies 21, 13, and 18), monosomy X, and triploidy than in miscarriages with a normal karyotype or other abnormal karyotypes. CONCLUSIONS: The frequencies of the presence of an embryonic pole and cardiac activity are higher in miscarriages with viable autosomal trisomies, monosomy X, and triploidy than in miscarriages with a normal karyotype or other abnormal karyotypes.

Welding-induced corrosion and protective measures for clad rebars in neutral chloride environments.

Corrosion-resistant steel plays a vital role in marine steel structures. This study developed an SS304/HRB400 stainless-steel-clad rebar for application in a cross-sea bridge in Zhejiang Province. CO2 gas shielded welding was employed in the prefabricated steel structure, with SS304 steel as the welding wire. This study investigated the welding on the corrosion resistance of clad rebars and explored corrosion protection measures for welded joints.The results indicated that refined grains appeared in both stainless steel and carbon steel due to distinct dynamic recrystallization (DRX) during welding. The corrosion resistance, as determined by potentiodynamic polarization curve analysis of the material's interaction with the solution ranked as follows: clad rebar (polished) > clad rebar welding (CRW) > painting the clad rebar after welding (PCRW) > clad rebar (unpolished) > carbon-steel welding (CSW) > carbon-steel bar > cold spraying zinc after clad rebar welding (ZCRW). However, an accelerated corrosion test with four samples for 600 s with a corrosion current of 0.8 A revealed minimal corrosion damage on zinc-coated surfaces. Hence, welding joints for clad steel structures are considered feasible and must be subject to cold zinc spraying after polishing to enhance their corrosion resistance.

Synergistically activating nucleophile strategy enabled organocatalytic asymmetric P-addition of cyclic imines.

Herein, we present an attractive organocatalytic asymmetric addition of P-nucleophiles to five-membered cyclic N-sulfonyl imines facilitated by phosphonium salt catalysis, enabling the highly enantioselective synthesis of tri- and tetra-substituted cyclic phosphorus-containing benzosultams. With this protocol, various cyclic α-aminophosphonates were efficiently synthesized with high yields and exceptional enantioselectivities (up to >99% ee) under mild reaction conditions. The utility and practicality of this method were demonstrated through gram-scale reactions and straightforward elaborations. Notably, the success of this approach relies on the deliberate selection of a synergistic organocatalytic system, which helps circumvent foreseeable side effects while handling secondary phosphine oxides (SPOs). Systematic mechanistic studies, incorporating experiments and DFT calculations, have revealed the critical importance of judiciously selecting bifunctional phosphonium salt catalysts for effectively activating P-nucleophiles while stereoselectively controlling the P-attack process.

[2,6-Bis(5-eth-oxy-1,3-oxazol-2-yl)-4-meth-oxy-phenyl-κ(3) N,C (1),N']bromidopalladium(II).

In the title compound, [PdBr(C17H17N2O5)], the Pd(II) atom is coordinated by an N,C(1),N'-tridentate pincer ligand and a Br atom in a distorted square-planar geometry. In the crystal, mol-ecules are connected by C-H⋯Br and C-H⋯O hydrogen bonds, and π-π inter-actions between the oxazole and benzene rings [centroid-centroid distance = 3.7344 (19) Å], resulting in a three-dimensional supra-molecular structure.