Deciphering the Microdroplet Acceleration Factors of Aza-Michael Addition Reactions.

Microdroplet chemistry is emerging as a great tool for accelerating reactions by several orders of magnitude. Several unique properties such as extreme pHs, interfacial electric fields (IEFs), and partial solvation have been reported to be responsible for the acceleration; however, which factor plays the key role remains elusive. Here, we performed quantum chemical calculations to explore the underlying mechanisms of an aza-Michael addition reaction between methylamine and acrylamide. We showed that the acceleration in methanol microdroplets results from the cumulative effects of several factors. The acidic surface of the microdroplet plays a dominating role, leading to a decrease of ∼9 kcal/mol in the activation barrier. We speculated that the dissociation of both methanol and trace water contributes to the surface acidity. An IEF of 0.1 V/Šcan further decrease the barrier by ∼2 kcal/mol. Partial solvation has a negligible effect on lowering the activation barrier in microdroplets but can increase the collision frequency between reactants. With acidity revealed to be the major accelerating factor for methanol droplets, reactions on water microdroplets should have even higher rates because water is more acidic. Both theoretically and experimentally, we confirmed that water microdroplets significantly accelerate the aza-Michael reaction, achieving an acceleration factor that exceeds 107. This work elucidates the multifactorial influences on the microdroplet acceleration mechanism, and with such detailed mechanistic investigations, we anticipate that microdroplet chemistry will be an avenue rich in opportunities in the realm of green synthesis.

Designer "Quasi-Benzyne": The Spontaneous Reduction of Ortho-Diiodotetrafluorobenzene on Water Microdroplets.

It has been widely shown that water microdroplets have a plethora of unique properties that are highly distinct from those of bulk water, among which an especially intriguing one is the strong reducing power as a result of the electrons spontaneously generated at the air-water interface. In this study, we take advantage of the reducing power of water microdroplets to reduce ortho-diiodotetrafluorobenzene (o-C6F4I2) into a C6F4I2•- radical anion. Photoelectron spectroscopy and density functional theory computations reveal that the excess electron in C6F4I2•- occupies the I-C1-C2-I linkage, which elongates the C-I bonds but surprisingly shortens the C1-C2 bond, making the bond order higher than a double bond, similar to the benzyne molecule, so we named it "quasi-benzyne". The C6F4I2•- anion was further successfully utilized in a Diels-Alder reaction, a typical reaction for benzyne. This study provides a good example of strategically utilizing the spontaneous properties of water microdroplets and generating an especially exotic anion, and we anticipate that microdroplet chemistry can be an avenue rich in opportunities for new catalyst-free organic reactions.

Identifying the personal characteristics of decent work perception for nursing students in China using latent profile analysis.

BACKGROUND: Given the importance of perceptions of decent work for nursing students' future career choices, we attempted to determine potential classifications and characteristics of nursing students' perceptions of decent work so that targeted interventions could be developed. METHODS: A convenience sample of 1004 s- to fourth-year nursing students completed the General Information Questionnaire, Self-Regulatory Fatigue Scale, Occupational Identity Questionnaire, and Decent Work Perceptions Scale in a cross-sectional survey in Heilongjiang Province, China, resulting in 630 valid questionnaires with a valid return rate of 62.75%. Nursing students' perceptions of decent work were defined using descriptive and regression analysis. RESULTS: Latent profile analysis (LPA) identified three subgroups: low perceived decent work group, medium perceived decent work group, and high perceived decent work group, accounting for 4.76%, 69.37%, and 25.87% of the sample, respectively. The results of unordered multiclass logistic regression show that nursing students with relatively low levels of perceived decent work are more likely to have a low professional identity, a lack of respect for nursing seniors, an involuntary choice of nursing major, and a low family income. CONCLUSION: Different types of nursing students have different perceptions of decent work, and these universities and related departments can use different educational guidance strategies.

Fetal hyperechoic kidney cohort study and a meta-analysis.

Objective: To investigate the positive rate of chromosomal and monogenic etiologies and pregnancy outcomes in fetuses with hyperechoic kidney, and to provide more information for genetic counseling and prognosis evaluation. Methods: We performed a retrospective analysis of 25 cases of hyperechoic kidney diagnosed prenatal in the Second Affiliated Hospital of Harbin Medical University and Harbin Red Cross Central Hospital (January 2017-December 2022). Furthermore, we conducted a meta-analysis of a series of hyperechoic kidneys (HEK) in the literature to assess the incidence of chromosomal and monogenic etiologies, mortality, and pooled odds ratio (OR) estimates of the association between the incidence of these outcomes and other associated ultrasound abnormalities. Results: 25 fetuses of HEK were enrolled in the cohort study, including 14 with isolated hyperechoic kidney (IHK) and 11 with non-isolated hyperechoic kidney (NIHK). Chromosomal aneuploidies were detected in 4 of 20 patients (20%). The detection rate of pathogenic or suspected pathogenic copy number variations (CNVs) was 29% (4/14) for IHK and 37% (4/11) for NIHK. Whole exome sequencing (WES) was performed in 5 fetuses, and pathogenic genes were detected in all of them. The rate of termination of pregnancy was 56% in HEK. 21 studies including 1,178 fetuses were included in the meta-analysis. No case of abnormal chromosome karyotype or (intrauterine death)IUD was reported in fetuses with IHK. In contrast, the positive rate of karyotype in NIHK was 22% and that in HEK was 20%, with the ORs of 0.28 (95% CI 0.16-0.51) and 0.25, (95% CI 0.14-0.44), respectively. The positive rate of (chromosome microarray analysis) CMA in IHK was 59% and that in NIHK was 32%, with the ORs of 1.46 (95% CI 1.33-1.62) and 0.48 (95% CI, 0.28-0.85), respectively. The positive rate of monogenic etiologies in IHK was 31%, with the OR of 0.80 (95% CI 0.25-2.63). In IHK, the termination rate was 21% and neonatal mortality was 13%, with the ORs of 0.26 (95% CI, 0.17-0.40), 1.72 (95% CI, 1.59-1.86), and that in NIHK was 63%, 0.15 (95% CI, 0.10-0.24); 11%, 0.12 (95% CI, 0.06-0.26), respectively. The intrauterine mortality in NIHK group was 2%, with the OR of 0.02 (95% CI, 0.01-0.05). HNF1B variant has the highest incidence (26%) in IHK. Conclusion: The positive rate of karyotype was 20% in HEK and 22% in NIHK. The positive rate of CMA was 32% in NIHK and 59% in IHK. The positive rate of IHK monogenic etiologies was 31%. HNF1B gene variation is the most common cause of IHK. The overall fetal mortality rate of NIHK is significantly higher than that of IHK. The amount of amniotic fluid, kidney size and the degree of corticomedullary differentiation have a great impact on the prognosis, these indicators should be taken into consideration to guide clinical consultation and decision-making.

Prenatal diagnosis of 46,XX testicular disorder of sex development with SRY-positive: A case report and review of the literature.

We report a case of a fetus with 46,XX testicular disorder of sex development detected prenatally. This fetus was found abnormally due to non-invasive prenatal testing. Amniocentesis revealed SRY gene on the X chromosome of the fetus. The related literature was reviewed, and the advantages and limitations of various prenatal diagnostic techniques were discussed. The combination of non-invasive prenatal testing and various prenatal diagnostic techniques has enabled more fetuses with sex reversal to be detected.

Facile Construction of Nanostructured Cermet Anodes with Strong Metal-Oxide Interaction for Efficient and Durable Solid Oxide Fuel Cells.

Nanostructured anodes generate massive reaction sites to oxidize fuels in solid oxide fuel cells (SOFCs); however, the nonexistence of a practically viable approach for the construction of nanostructures and the retention of these nanostructures under the harsh operating conditions of SOFCs poses a significant challenge. Herein, a simple procedure is reported for the construction of a nanostructured Ni-Gd-doped CeO2 anode based on the direct assembly of pre-formed nanocomposite powder with strong metal-oxide interaction. The directly assembled anode forms heterointerfaces with the electrolyte owing to the electrochemical polarization current and exhibits excellent structural robustness against thermal ripening. An electrolyte-supported cell with the directly assembled anode produces a peak power density of 0.73 W cm-2 at 800 °C, while maintaining stability for 100 h, which is in contrast to the drastic degradation of the cermet anode prepared using the conventional method. These findings provide clarity on the design and construction of durable nanostructured anodes and other electrodes for SOFCs.

The Spontaneous Electron-Mediated Redox Processes on Sprayed Water Microdroplets.

Water is considered as an inert environment for the dispersion of many chemical systems. However, by simply spraying bulk water into microsized droplets, the water microdroplets have been shown to possess a large plethora of unique properties, including the ability to accelerate chemical reactions by several orders of magnitude compared to the same reactions in bulk water, and/or to trigger spontaneous reactions that cannot occur in bulk water. A high electric field (∼109 V/m) at the air-water interface of microdroplets has been postulated to be the probable cause of the unique chemistries. This high field can even oxidize electrons out of hydroxide ions or other closed-shell molecules dissolved in water, forming radicals and electrons. Subsequently, the electrons can trigger further reduction processes. In this Perspective, by showing a large number of such electron-mediated redox reactions, and by studying the kinetics of these reactions, we opine that the redox reactions on sprayed water microdroplets are essentially processes using electrons as the charge carriers. The potential impacts of the redox capability of microdroplets are also discussed in a larger context of synthetic chemistry and atmospheric chemistry.

Spontaneous and Simultaneous Oxidation and Reduction of o-Quinones in Water Microdroplets.

Microdroplet chemistry has been an emerging new field for its large plethora of unique properties, among which an especially intriguing one is the strong oxidizing and reducing powers. The hydroxide ion in water microdroplets is considered to split into a hydroxyl radical and an electron at the air-water interface, and the former is responsible for the oxidizing capability while the latter is responsible for the reducing power, making a unity of opposites. However, to date there are only two examples showing that oxidation and reduction occur simultaneously to the same substrates, which might be a result of the redox properties of the substrate per se. In this study, we carefully chose a group of ο-quinone compounds as the substrates in water microdroplets and discovered that they can be both oxidized by the hydroxyl radical and reduced by the electron. These results keep pushing the limit of the unique redox properties of microdroplet chemistry.

Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO2.

Recent advances in microdroplet chemistry have shown that chemical reactions in water microdroplets can be accelerated by several orders of magnitude compared to the same reactions in bulk water. Among the large plethora of unique properties of microdroplets, an especially intriguing one is the strong reducing power that can be sometimes as high as alkali metals as a result of the spontaneously generated electrons. In this study, we design a catalyst-free strategy that takes advantage of the reducing ability of water microdroplets to reduce a certain molecule, and the reduced form of that molecule can convert CO2 into value-added products. By spraying the water solution of C6F5I into microdroplets, an exotic and fragile radical anion, C6F5I•-, is observed, where the excess electron counter-intuitively locates on the σ* antibonding orbital of the C-I bond as evidenced by anion photoelectron spectroscopy. This electron weakens the C-I bond and causes the formation of C6F5-, and the latter attacks the carbon atom on CO2, forming the pentafluorobenzoate product, C6F5CO2-. This study provides a good example of strategically making use of the spontaneous properties of water microdroplets, and we anticipate that microdroplet chemistry will be a green avenue rich in new opportunities in CO2 utilization.

PneuNet: deep learning for COVID-19 pneumonia diagnosis on chest X-ray image analysis using Vision Transformer.

A long-standing challenge in pneumonia diagnosis is recognizing the pathological lung texture, especially the ground-glass appearance pathological texture. One main difficulty lies in precisely extracting and recognizing the pathological features. The patients, especially those with mild symptoms, show very little difference in lung texture, neither conventional computer vision methods nor convolutional neural networks perform well on pneumonia diagnosis based on chest X-ray (CXR) images. In the meanwhile, the Coronavirus Disease 2019 (COVID-19) pandemic continues wreaking havoc around the world, where quick and accurate diagnosis backed by CXR images is in high demand. Rather than simply recognizing the patterns, extracting feature maps from the original CXR image is what we need in the classification process. Thus, we propose a Vision Transformer (VIT)-based model called PneuNet to make an accurate diagnosis backed by channel-based attention through X-ray images of the lung, where multi-head attention is applied on channel patches rather than feature patches. The techniques presented in this paper are oriented toward the medical application of deep neural networks and VIT. Extensive experiment results show that our method can reach 94.96% accuracy in the three-categories classification problem on the test set, which outperforms previous deep learning models.

Abnormalities of the Halogen Bonds in the Complexes between Y2CTe (Y = H, F, CH3) and XF (X = F, Cl, Br, I).

In this work, the hydrogen bonds and halogen bonds in the complexes between Y2CTe (Y = H, F, CH3) and XF (X = F, Cl, Br, I) have been studied by quantum chemical calculations. We found three interesting abnormalities regarding the interactions. Firstly, the strength of halogen bonds increases in the order of IF < BrF < ClF < F2. Secondly, the halogen bonds formed by F2 are very strong, with an interaction energy in the range between −199.8 and −233.1 kJ/mol. Thirdly, all the halogen bonds are stronger than the hydrogen bonds in the systems we examined. All these results are against the general understanding of halogen bonds. These apparent abnormal properties are reconciled with the high polarizability of the Te atom and the strong inducing effect of F on the Te atom of Y2CTe. These findings provide a new perspective on halogen bonds. Additionally, we also proposed bonding distance-based methods to compare the strength of halogen/hydrogen bonds formed between different donor atoms and the same acceptor atom.

Sprayed water microdroplets containing dissolved pyridine spontaneously generate pyridyl anions.

The anion of pyridine, C5H5N−, has been thought to be short lived in the gas phase and was only previously observed indirectly. In the condensed phase, C5H5N− is known to be stabilized by solvation with other molecules. We provide in this study striking results for the formation of isolated C5H5N− from microdroplets of water containing dissolved pyridine observed in the negative ion mass spectrum. The gas-phase lifetime of C5H5N− is estimated to be at least 50 ms, which is much longer than previously thought. The generated C5H5N− captured CO2 molecules to form a stable (Py-CO2)− complex, further confirming the existence of C5H5N−. We propose that the high electric field at the air­water interface of a microdroplet helps OH− to transfer an electron to pyridine to form C5H5N− and the hydroxyl radical •OH. Oxidation products of the Py reacting with •OH are also observed in the mass spectrum recorded in positive mode, which further supports this mechanism. The present study pushes the limits of the reducing and oxidizing power of water microdroplets to a new level, emphasizing how different the behavior of microdroplets can be from bulk water. We also note that the easy formation of C5H5N− in water microdroplets presents a green chemistry way to synthesize value-added chemicals.

Gold Nanoclusters Grown on MoS2 Nanosheets by Pulsed Laser Deposition: An Enhanced Hydrogen Evolution Reaction.

Au nanoparticles were decorated on a 2H MoS2 surface to form an Au/MoS2 composite by pulse laser deposition. Improved HER activity of Au/MoS2 is evidenced by a positively shifted overpotential (-77 mV) at a current density of -10 mA cm-2 compared with pure MoS2 nanosheets. Experimental evidence shows that the interface between Au and MoS2 provides more sites to combine protons to form an active H atom. The density functional theory calculations found that new Au active sites on the Au and MoS2 interface with improved conductivity of the whole system are essential for enhancing HER activity of Au/MoS2.

An overview of surface-enhanced Raman scattering substrates by pulsed laser deposition technique: fundamentals and applications.

Metallic nanoparticles (NPs), as an efficient substrate for surface-enhanced Raman scattering (SERS), attract much interests because of their various shapes and sizes. The appropriate size and morphology of metallic NPs are critical to serve as the substrate for achieving an efficient SERS. Pulsed laser deposition (PLD) is one of the feasible physical methods employed to synthesize metallic NPs with controllable sizes and surface characteristics. It has been recognized to be a successful tool for the deposition of SERS substrates due to its good controllability and high reproducibility in the manufacture of metallic NPs. This review provides an overview about the recent advances for the preparation of SERS substrates by PLD technique. The influences of parameters on the sizes and morphologies of metallic NPs during the deposition processes in PLD technique including laser output parameters, gas medium, liquid medium, substrate temperature, and properties of 3D substrate are presented. The applications of SERS substrates produced by PLD in the environmental monitoring and biomedical analysis are summarized. This knowledge could serve as a guideline for the researchers in exploring further applications of PLD technique in the production of SERS substrate.

Potential of thrombospondin-1 in treatment of polycystic ovary syndrome rat model: a preliminary study.

OBJECTIVE: Polycystic ovary syndrome (PCOS) is a common gynecological endocrine disease in reproductive women, and the endocrine levels are also affected by diseases. The aim of this study was to determine the effect of thrombospondin-1 (TSP-1) on PCOS rat model. METHODS: We established the PCOS rat model, the serum hormones including TSP-1 expression were determined and morphological characteristics were investigated to evaluate the model. These above endocrine and morphological features were investigated again to evaluate the effect of TSP-1 treatment. RESULTS: In the PCOS model group, the serum hormones change (higher luteinizing hormone, testosterone and estrogen) and decreased TSP-1 expression levels were found compared with the control group. Besides, the morphological characteristics of PCOS were also observed in the model group. After TSP-1 treatment, the higher TSP-1, ANGPT2, PDGFB and PDGFD expression levels, the lower LH and T levels, decreased vessel density as well as VEGFA and ANGPT1 expression levels were found compared with the control group, and the ovary morphological changes were also observed in the TSP-1 experimental group. CONCLUSIONS: TSP-1 delivery system might be an alternative therapy for PCOS treatment.

Relation of Heterogeneity and Gas-Bearing Capacity of Tight Sandstone: A Case Study of the Upper Paleozoic Tight Gas Sandstone Reservoir in the Southeast of the Ordos Basin.

Compared to conventional reservoirs, only a few studies were carried out on the heterogeneity of unconventional tight sandstone reservoirs. This paper focuses on the Upper Paleozoic tight gas sandstone reservoir in the southeast of the Ordos Basin. The reservoir heterogeneity is studied through thin section and scanning electron microscope observations, cathode luminescence, mercury intrusion, and logging data analysis. The results show that the dissolution pore and microfracture is the dominant pathway for the migration of natural gas. The distribution of gas and water within the sand body is affected by the rhythmic change of sandstone, and this rhythmicity is variable with the changing of particle size. It shows "water wrapping gas" for the positive rhythm, "gas wrapping water" for the reverse rhythm, and both of these features for the compound rhythm. Interlayers act as a cap rock or carrier bed on gas distribution. Along with the variation of breakthrough pressure of the interlayer and saturation pressure of the reservoir, the single sand body shows different distribution features of gas and water. The vertical differentiation of natural gas is caused by the barrier layer, and the more barrier layers exist, the worse the capacity of the reservoir to store natural gas. However, the existence of the barrier layer will make the reservoir close to the source area to be the favorable zone for oil and gas accumulation. In this study, the relationship between heterogeneity and gas as well as water distribution of tight sandstone is identified, which can provide guidance to the exploration and exploitation of tight gas in the future.

EEG-derived pain threshold index for prediction of postoperative pain in patients undergoing laparoscopic urological surgery: a comparison with surgical pleth index.

Recently a novel pain recognition indicator derived from electroencephalogram(EEG) signals, pain threshold index(PTI) has been developed. The aim of this study was to determine whether PTI can be used for prediction of postoperative acute pain while surgical pleth index(SPI) applied as control. Eighty patients undergoing laparoscopic urological surgery under general anesthesia were enrolled. Data of SPI, PTI and a sedative index-wavelet index(WLI) were recorded within last 10 min at the end of surgery. The postoperative pain scores (NRS, numerical rating scale) were obtained. The Bland-Altman analysis was used for evaluation of consistency between PTI and SPI, whereas receiver-operating characteristic (ROC) curves was used for the mean values of PTI, SPI, and WLI to distinguish between mild (NRS 0-3) and moderate-severe (NRS 4-10) pain, and calculate their "best-fit" cut-off values. Data from 76 patients were included for final analysis. There was a good agreement between SPI and PTI values at the end of surgery. The ROC analysis showed a cut-off PTI value of 53 to discriminate between mild and moderate-to-severe pain, while SPI is 44 for this discrimination. Further analysis indicated that PTI had a best predictive accuracy reflected by highest area under curve (AUC)(0.772, 95% CI: 0.661-0.860)with sensitivity(62.50%) and specificity(90.91%) and a best positive predictive value(83.3%,95% CI: 68.4-98.2%). PTI obtained at the end of surgery, which have better predictive accuracy for postoperative pain than SPI, could differentiate the patients with moderate-to-severe pain from those with mild pain after they awaken from anesthesia.Clinical trial registration Chinese Clinical Trials Registry: ChiCTR1900024789.

Methylene blue reduces incidence of early postoperative cognitive disorders in elderly patients undergoing major non-cardiac surgery: An open-label randomized controlled clinical trial.

STUDY OBJECTIVE: The purpose of the present study was to investigate whether methylene blue (MB) could reduce the incidences of postoperative delirium (POD) and early postoperative cognitive dysfunction (POCD) in elderly patients undergoing major non-cardiac surgery. DESIGN: Prospective, randomized, open-label clinical trial. SETTING: University-affiliated hospital. PATIENTS: Two hundred and forty-eight elderly patients scheduled for non-cardiac surgery. INTERVENTIONS: Elderly patients undergoing non-cardiac major surgery were randomly assigned to MB group (n = 124), who receiving intravenous infusion of 2 mg/kg MB within 60 min immediately after anesthetic induction, or control group (n = 124), who receiving equal volume saline in the same way. MEASUREMENTS: All patients were evaluated with delirium and neuropsychological batteries before and after surgery, as well as perioperative adverse events. Two plasma biomarkers superoxide dismutase (SOD) and homocysteine (HCY) were measured pre- and post-operatively. MAIN RESULTS: There were total 39 cases(15.7%)experienced POD. The incidence of POD in MB group was significantly less than that in control group (7.3% vs. 24.2%, OR = 0.24, 95%CI: 0.11-0.53, p < 0.001). The incidence of early POCD at postoperative 7th day in MB group was also less than that in control group (16.1% vs. 40.2%, OR = 0.30, 95% CI: 0.16-0.57, p < 0.001). The adverse events were comparable in both groups. In addition, there was no significant correlation between POD/POCD and levels of SOD or HCY. CONCLUSION: We conclude that intraoperative intravenous 2 mg/kg MB could significantly reduce the incidences of POD and early POCD in elderly surgical patients, while not remarkably increase incidence of perioperative adverse events, suggesting MB may be clinically effective and safe for prevention of early postoperative neurocognitive disorders.

Nasopharyngeal carcinoma­associated gene 6 inhibits cell viability, migration, invasion and induces apoptosis in osteosarcoma cells by inactivating the Wnt/ß­catenin signaling pathway.

Nasopharyngeal carcinoma­associated gene 6 (NGX6) is associated with the Wnt/ß­catenin signaling pathway in a number of different types of cancer, including colorectal cancer (CRC). The present study is aimed to determine the functional role of NGX6 in osteosarcoma (OS) and to investigate the underlying mechanism associated with the Wnt/ß­catenin signaling pathway. NGX6 expression levels in tissues derived from patients with OS and cell lines (MG­63, Saos­2, U2OS and HOS) was analyzed using reverse transcription­quantitative PCR. NGX6 expression levels were subsequently overexpressed through transfection of the pcDNA3.1 (pcDNA)­NGX6 overexpression vector into U2OS and HOS cells. BML284 was utilized to activate the Wnt/ß­catenin signaling pathway. MTT, wound healing, Transwell and flow cytometry assays were performed to analyze cell viability, migration, invasion and apoptosis, respectively. Western blotting was also used to analyze the protein expression levels of ß­catenin, c­Jun and c­Myc. A xenograft model was constructed by injecting pcDNA­NGX6­transfected U2OS cells into nude mice (BALB/c). The results of the present study revealed that the expression levels of NGX6 were downregulated in OS tissues and cell lines. The transfection of pcDNA­NGX6 into OS cells significantly inhibited the cell viability, and migratory and invasive abilities, and induced the apoptosis of U2OS and HOS cells. The expression levels of ß­catenin, c­Jun and c­Myc were also significantly downregulated in pcDNA­NGX6­transfected U2OS and HOS cells. Notably, the treatment of transfected cells with BML284 significantly reversed the inhibitory effect of pcDNA­NGX6 on the viability, migration and invasion, and the promoting effect on apoptosis in U2OS cells. Furthermore, NGX6 overexpression also discovered to inhibit the growth of xenograft tumors in vivo by inhibiting the Wnt/ß­catenin signaling pathway. In conclusion, the findings of the present study suggested that NGX6 may suppress the viability, migration and invasion, while facilitating the apoptosis of OS cells via blocking the Wnt/ß­catenin signaling pathway.