Bimetallic H2 Addition and Intramolecular Caryl-H Activation Mediated by an Iron-Zinc Hydride.

Heteronuclear Fe(µ-H)Zn hydride Cp*Fe(1,2-Cy2PC6H4)HZnEt (3) undergoes reversible intramolecular Caryl-H reductive elimination through coupling of the cyclometalated phosphinoaryl ligand and the hydride, giving rise to a formal Fe(0)-Zn(II) species. Addition of CO intercepts this equilibrium, affording Cp*(Cy2PPh)(CO)Fe-ZnEt that features a dative Fe-Zn bond. Significantly, this system achieves bimetallic H2 addition, as demonstrated by the transformation of the monohydride Fe(µ-H)Zn to a deuterated dihydride Fe-(µ-D)2-Zn upon reaction with D2.

Metabolome of flue-cured tobacco is significantly affected by the presence of leaf stem.

BACKGROUND: Leaves of tobacco (Nicotiana tabacum L.) are flue-cured to use as a key industrial supply in various parts of the world. The quality of tobacco leaves is dependent on chemical components and their proportions. Generally, the stem attached to tobacco leaf is detached before curing. However, the leaf stem remains green for an extended period of time (as compared to leaf) during flue-curing. Hence, it is expected to affect the quality of tobacco's final product. RESULTS: To understand the impact of the green stem of leaf on the metabolome of flue-cured tobacco, we employed a broad targeted metabolomics approach. We selected two tobacco cultivars (Yun87 and K326) and cultivated them in five geographic locations in China. For flue-curing, leaves were harvested without a stem (L) or with an attached stem (SPL). After metabolome analysis, a total of 1027 metabolites were annotated in these samples. A variable number of metabolites were differentially accumulated between both types of leaves (depending on geographic location or cultivar) representing an influence of environment or genotype. Interestingly, only 68 metabolites were differentially accumulated between L and SPL samples irrespective of the cultivar or geographic location. These differentially accumulated metabolites belonged to major groups of primary and secondary metabolites. We have discussed the importance of identified metabolites in terms of carbon, nitrogen, and polyphenolic metabolism. CONCLUSION: The present research is the first comprehensive description of several metabolites in tobacco leaves related to the contribution of leaf stem. The current study opens novel prospects for investigating the potential of such metabolites in improving the quality of flue-cured tobacco.

Meningitis caused by oral anaerobes detected using mNGS tool: a case report and review of literature.

BACKGROUND: Bacterial meningitis is a central nervous system (CNS) infection disease of the meninges and brain parenchyma caused by the bacteria. Few cases of meningitis related to oral anaerobes have been reported in the literature. Here, we report a case of meningitis in a middle-aged woman, caused by oral anaerobes. CASE PRESENTATION: A 58-year-old woman was admitted to hospital with fever, headache for 21 days and left limb weakness for 2 days. The blood cell counts (11.73 × 109/L), neutrophil counts (9.22 × 109/L) and high-sensitivity C-reactive protein levels (> 5.00 mg/L) were elevated. The brain computerized tomography (CT) scanning indicated the new right thalamus infarct. The brain cranial-enhanced magnetic resonance imaging (MRI) showed the right lateral paraventricular and right thalamic infarct, and abnormal signal in occipital horns of bilateral lateral ventricles were increased. In addition, the brain enhanced nuclear magnetic resonance (NMR) scanning suggested that meninges were thickened and enhanced at the base of the brain, with meningitis changes. The neck CT angiography (CTA) revealed arteriosclerotic changes. The metagenomic next-generation sequencing (mNGS) revealed Eubacterium brachy, Porphyromonas gingivalis, Fusobacterium nucleatum and Torque teno virus in her cerebrospinal fluid (CSF). The patient was diagnosed with purulent meningitis caused by infection of oral anaerobes, and treated with mannitol, ceftriaxone and vancomycin. Her symptoms alleviated. Subsequently, she was transferred to the infectious department and treated with ceftriaxone plus metronidazole (anti-anaerobes) and mannitol (reduce intracranial pressure). Her symptoms improved and currently received rehabilitation treatment. CONCLUSION: We herein report a rare case involving meningitis caused by infection of oral anaerobes. The mNGS can accurately detect the pathogens of infectious diseases.

Development and validation of a random forest model to predict functional outcome in patients with intracerebral hemorrhage.

OBJECTIVE: To develop and validate a machine learning (ML)-based model to predict functional outcome in Chinese patients with intracerebral hemorrhage (ICH). METHODS: This retrospective cohort study enrolled patients with ICH between November 2017 and November 2020. The follow-up period ended in February 2021. The study population was divided into training and testing sets with a ratio of 7:3. All variables were included in the least absolute shrinkage and selection operator (LASSO) regression for feature selection. The selected variables were incorporated into the random forest algorithm to construct the prediction model. The predictive performance of the model was evaluated via the area under the curve (AUC), accuracy, sensitivity, specificity, positive predictive value (PPV), negative predictive value (NPV), and calibration curve. RESULTS: A total of 412 ICH patients were included, with 288 in the training set, and 124 in the testing set. Twelve attributes were selected: neurological deterioration, Glasgow Coma Scale (GCS) score at 24 h, baseline GCS score, time from onset to the emergency room, blood glucose, diastolic blood pressure (DBP) change in 24 h, hematoma volume change in 24 h, systemic immune-inflammatory index (SII), systolic blood pressure (SBP) change in 24 h, serum creatinine, serum sodium, and age. In the testing set, the accuracy, AUC, sensitivity, specificity, PPV, and NPV of the model were 0.895, 0.964, 0.872, 0.906, 0.810, and 0.939, respectively. The calibration curves showed a good calibration capability of the model. CONCLUSION: This developed random forest model performed well in predicting 3-month poor functional outcome for Chinese ICH patients.

Signet-Ring-Shaped Octaphosphorus-Cobalt Complexes: Synthesis, Structure, and Functionalization Reactions with Carbene Analogs.

White phosphorus activation with low-valent metal species has proved to be very effective in converting P4 into small Pn-containing molecules with n ≤ 4. Much less developed are metal-mediated P4-coupling reactions that can yield selectively large polyphosphorus clusters. Herein, we report P4-activation reactions with three-coordinate N-heterocyclic carbene(NHC)-cobalt(0)-alkene complexes, which produce the P8 complexes of cobalt [(NHC)2Co2(µ-η6:η6-P8)] (NHC = 1,3-dimesitylimidazol-2-ylidene (IMes), 1; 1,3-bis(2,6-diethylphenyl)imidazol-2-ylidene (IDep), 2) in high yields. The P8 ligand in 1 and 2 exhibits a signet-ring type structure that was predicted by theoretical study but has never been obtained in synthetic molecules. Theoretical studies suggest that [(NHC)2Co2(µ-η6:η6-P8)] is best described as a Co0-[P8]0-Co0 complex featuring a Co-Co σ-bond and discernible Co-to-P8 back-donation. By treating with N-heterocyclic silylene, phosphinidene precursor, organic azides, and NHCs, complex 1 was transformed into [(IMes)2Co2(µ-η6:η6-P8X)] (X = 1,3-bis(tert-butyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene, 3; PNMe2, 4), [(IMes)2Co2(σ:(µ-η4:η6)-RNPPP6)] (R = SO2-C6H4-p-Me, 5; C(CF3)2Ph, 6), and [(IMes)2Co2(µ-η2:η2-cyclo-P4P(IPri2))(µ-η3:η3-P3)] (7), respectively. Complexes 3-7 can be viewed as the adducts of 1 with the corresponding carbene analogous SiR2, PR, NR, and CR2, but their core structures are distinct. Under similar conditions, white phosphorus is inert toward these reagents. These cage functionalization reactions showcase the enhanced reactivity of the P8 ligand in [(NHC)2Co2(µ-η6:η6-P8)] over that of P4, and indicate the amphiphilicity of the P8 ligand toward electrophiles and nucleophiles.

Diethylenetriamine modified biological waste for disposing oily wastewater.

Oily wastewater produced in the process of oil extraction has a potential threat to the environment. In this paper, diethylenetriamine was used to modify rice straw powder (RSP) by a solvent-free strategy, and the obtained product (AM-RSP) was utilized to dispose oily wastewater. AM-RSP was characterized by Field emission scanning electron microscope (FE-SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectroscope (FT-IR) and BET. The factors affecting the demulsification performance (DP) such as dosage, salinity and pH value were detailly investigated. The results indicated that light transmittance (ET) and oil removal rate (ER) of separated water could reach 93.5% and 96.5%, respectively, within 40 min with 150 mg/L of AM-RSP at room temperature. Also, AM-RSP had a good salt resistance. In addition, three-phase contact angle (TCA), formation of interfacial film, interfacial activity, dynamic interfacial tension (IFT), coalescence time of droplets and zeta potential were adopted to probe the demulsification mechanism.

Statins for neuroprotection in spontaneous intracerebral haemorrhage (STATIC): protocol for a multicentre, prospective and randomised controlled trial.

INTRODUCTION: Intracerebral haemorrhage (ICH) is a neurological emergency with high morbidity and mortality, and current treatment is limited. Emerging evidence has reported that statins can exert neuroprotective effects in cerebrovascular diseases. However, most of the published clinical studies are retrospective. Therefore, it is important to conduct a prospective randomised controlled trial to further validate the efficacy and safety of statins in patients with ICH. METHODS AND ANALYSIS: The present study is performed at Xuan Wu Hospital Capital Medical University, Beijing Fengtai You'anmen Hospital and Shunping County Hospital, Hebei Province. The target number of patients is 98. Eligible patients are randomly assigned in a 1:1 ratio to the statins group or the control group. The primary outcome is the perihaemorrhagic oedema to haematoma ratio at 7 days. Secondary outcomes include mortality at 30 days, haematoma resolution rate at 7 days, National Institute of Health stroke scale (NIHSS) score at 7 days or discharge, ordinal distribution of modified Rankin scale (mRS) score at 90 days, the proportion of patients with an mRS score of 0-2 on day 90, the proportion of patients with an mRS score of 0-3 on day 90, absolute haematoma volume changes between initial and 7-day follow-up CT scan, absolute perihaematomal oedema changes between initial and 7-day follow-up CT scan. ETHICS AND DISSEMINATION: The trial has been approved by the ethics committees of Xuan Wu Hospital Capital Medical University, Beijing Fengtai You'anmen Hospital and Shunping County Hospital, Hebei Province. The results will be disseminated in a peer-reviewed journal and in conference reports. TRIAL REGISTRATION NUMBER: NCT04857632.

Large-scale expression, purification, and glucose uptake activity of recombinant human FGF21 in Escherichia coli.

As a novel important regulator of glucose and lipid metabolism homeostasis, human fibroblast growth factor 21 (hFGF21) has become a potential drug candidate for the treatment of metabolic diseases including obesity, and type 2 diabetes, as well as non-alcoholic fatty liver disease. To improve the production of recombinant hFGF21 to meet the increasing demand in clinical applications, an artificial gene encoding its mature peptide sequence was constructed, cloned into vector pET-3c and then expressed in Escherichia coli Origami B (DE3). Under optimal conditions in a 50-L fermentor, the average bacterial yield and the soluble expression level of recombinant hFGF21 of six batches attained 1750 ± 185 g and 32 ± 1.5%, respectively. The target protein was purified by the combination of nickel-nitrilotriacetic acid affinity chromatography and Sephadex S-100 resin. 5% (w/v) trehalose solution was able to prevent rhFGF21 from degradation effectively. The purity of rhFGF21 was higher than 97%, and the yield was 213 ± 17 mg/L. The preliminary biochemical characterization of rhFGF21 was confirmed using Western blot and peptide map finger analysis. Based on the glucose oxidase-peroxidase assay, the EC50 of glucose uptake activity of the purified rhFGF21 was 22.1 nM.

Diagnosis of an Acinetobacter pittii from a patient in China with a multiplex PCR-based targeted gene sequencing platform of the cerebrospinal fluid: A case report with literature review.

BACKGROUND: The traditional diagnosis model has great challenges for the etiological diagnosis of the central nervous system (CNS) diseases with similar clinical manifestations, especially for the diagnosis of rare pathogens. It is very important to make rapid and accurate identification of pathogens for guiding clinical choices in administering countermeasures. CASE SUMMARY: On August 22, 2020, a 49 years old Chinese male patient had a headache for two days, and then the computed tomography (CT) scan of the brain showed subarachnoid hemorrhage. Subsequently, he underwent twice craniotomy and about 3 weeks of hospitalization. Since September 20, the patient was in the local rehabilitation hospital for hyperbaric oxygen therapy for about three weeks. Then the patient developed acute purulent meningoencephalitis. In the absence of diagnosis of specific pathogenic bacteria, vancomycin (1 g every 12 hours), ceftazidime (2 g every 8 hours), mannitol dehydration (125 mL, every 8 hours), and sodium valproate (0.4 g tid) was used timely according to cerebrospinal fluid (CSF) examination and clinical manifestations. CSF smear and routine culture test were negative during hospitalization. We used the metagenomic next-generation sequencing (mNGS) analysis of CSF for quick and accurate diagnosis, which identified human herpesvirus type 4 (EBV), Corynebacterium corynebacterium, Achromobacter xylose oxidation, and Acinetobacter baumannii, But the mapping degree was not high. Then, we used the modified method-multiplex PCR-based targeted gene sequencing platform (ptNGS) to detect CSF samples and found that the sequences detected were Acinetobacter pittii (A. pittii) and Staphylococcus epidermidis. S. epidermidis might come from skin colonization during lumbar puncture, so it was excluded from the etiological diagnosis. Therefore, we highly suspected that A. pittii was the pathogen in this case. After about three weeks of hospitalization treatment, the patient's symptoms were relieved. CONCLUSION: In conclusion, empirical medication before the identification of pathogens is very important. The ptNGS may be an effective method for the diagnosis of pathogens.

Demulsification of oily wastewater using a nano carbon black modified with polyethyleneimine.

In this work, nano carbon black was modified with polyethyleneimine (CB-PEI) under an ultrasonic field. The obtained product was used as a demulsifier to break oily wastewater. Morphology, structure, and chemical composition of CB-PEI were systematically analyzed. Bottle test was carried out to evaluate the influence of dosage, pH value and salinity on the demulsification efficiency of the emulsion. The results showed that the light transmittance of water phase (TSW) after the demulsification was 79.1% and corresponding oil removal rate (ORR) could reach up to 99.4% with 60 mg/L of CB-PEI at ambient temperature for 30 min. In addition, the possible demulsification mechanism was explored by dynamic interface tension (IFT), elasticity modulus, wettability, self-assemble of interfacial membrane, zeta potential and micrograph analysis. It indicated that CB-PEI had an appropriate amphiphilicity and good interfacial activity, which could improve it quickly transfer to the oil-water interface and result in the oil-water separation. The current work provides a simple method to prepare a demulsifier with excellent performance, so it has a good application prospect for the treatment of oil-water emulsions.

Applying the pathogen-targeted next-generation sequencing method to pathogen identification in cerebrospinal fluid.

BACKGROUND: The cerebrospinal fluid (CSF) culture is a widely used method for the diagnosis of meningitis, but its detection sensitivity is low. Several new methods have been developed for pathogen detection, including metagenomic next-generation sequencing (mNGS) and pathogen-targeted NGS (ptNGS). In this study, we aimed to evaluate the performance of ptNGS in pathogen detection in CSF. METHODS: CSF specimens were acquired from 38 patients with meningitis who were diagnosed at Xuanwu Hospital, Capital Medical University between October 2020 and February 2021. DNA was extracted from the CSF samples, and pathogens were identified using both ptNGS and mNGS. SPSS 22.0 software was used to compare the pathogen detection performance of ptNGS and mNGS in CSF. RESULTS: Among the 38 patients with meningitis, 14 had a non-infectious disease (NID) and 24 had an infectious disease (ID). Of the 38 samples, both ptNGS and mNGS detected 9 (23.7%) positive samples, and 12 (31.6%) negative samples. Thirteen (34.2%) samples were detected to be positive by ptNGS only, and 4 (10.5%) were detected to be positive by mNGS only. The positivity rate detected by ptNGS for the ID group was higher than that detected by mNGS (P=0.080), and the positivity rates detected by ptNGS and mNGS for the NID group were comparable. The positive predictive value (PPV) and negative predictive value (NPV) of diagnosing an ID by ptNGS were 77.3% and 56.3%, respectively. While, the PPV and NPV of diagnosing an ID by mNGS were 76.9% and 44.0%, respectively. ptNGS increased the sensitivity rate by approximately 70%. The sensitivity rate of ptNGS was higher than that of mNGS (70.8% vs. 41.7%), while the specificity rate of mNGS was higher than that of ptNGS (78.6% vs. 64.3%). Additionally, ptNGS required a shorter time for pathogen diagnosis (15 vs. 24 hrs) and had lower costs than mNGS. CONCLUSIONS: ptNGS has a number of advantages over mNGS, including its sensitivity, timeliness, and economy, all factors that are important considerations in clinical use.

The Effect of Dexmedetomidine on Emergence Agitation or Delirium in Children After Anesthesia-A Systematic Review and Meta-Analysis of Clinical Studies.

Background: We conducted this systematic review and meta-analysis to investigate the clinical effect of dexmedetomidine in preventing pediatric emergence agitation (EA) or delirium (ED) following anesthesia compared with placebo or other sedatives. Methods: The databases of Pubmed, Embase, and Cochrane Library were searched until 8th January 2020. Inclusion criteria were participants with age<18 years and studies of comparison between dexmedetomidine and placebo or other sedatives. Exclusion criteria included adult studies; duplicate publications; management with dexmedetomidine alone; review or meta-analysis; basic research; article published as abstract, letter, case report, editorial, note, method, or protocol; and article presented in non-English language. Results: Fifty-eight randomized controlled trials (RCTs) and five case-control trials (CCTs) including 7,714 patients were included. The results showed that dexmedetomidine significantly decreased the incidence of post-anesthesia EA or ED compared with placebo [OR = 0.22, 95% CI: (0.16, 0.32), I 2 = 75, P < 0.00001], midazolam [OR = 0.36, 95% CI: (0.21, 0.63), I 2 = 57, P = 0.0003], and opioids [OR = 0.55, 95% CI: (0.33, 0.91), I 2 = 0, P = 0.02], whereas the significant difference was not exhibited compared with propofol (or pentobarbital) [OR = 0.56, 95% CI: (0.15, 2.14), I 2 = 58, P = 0.39], ketamine [OR = 0.43, 95% CI: (0.19, 1.00), I 2 = 0, P = 0.05], clonidine [OR = 0.54, 95% CI: (0.20, 1.45), P = 0.22], chloral hydrate [OR = 0.98, 95% CI: (0.26, 3.78), P = 0.98], melatonin [OR = 1.0, 95% CI: (0.13, 7.72), P = 1.00], and ketofol [OR = 0.55, 95% CI: (0.16, 1.93), P = 0.35]. Conclusion: Compared with placebo, midazolam, and opioids, dexmedetomidine significantly decreased the incidence of post-anesthesia EA or ED in pediatric patients. However, dexmedetomidine did not exhibit this superiority compared with propofol and ketamine. With regard to clonidine, chloral hydrate, melatonin, and ketofol, the results needed to be further tested due to the fact that only one trial was included for each control drug.

[Optimal dose of local anesthetic mixture in ultrasound-guided infraclavicular brachial plexus block via coracoid approach: analysis of 160 cases].

OBJECTIVE: To investigate the optimal dose of local anesthetic mixture in ultrasound-guided infraclavicular brachial plexus block via coracoid approach. METHODS: 160 patients scheduled for surgery of the hand or forearm were randomly divided into 4 equal groups (Groups A, B, C, and D). To receive 8, 7, 6, or 5 ml of anesthetic mixture of 0.75% ropivacaine and 2% lidocaine for radial nerve, axillary nerve, median nerve, ulnar nerve, median cutaneous nerve of arm, median antebrachial cutaneous nerve, and lateral antebrachial cutaneous nerve respectively ultrasound-guided infraclavicular brachial plexus block via coracoid approach. The time for anesthesia taking effect, anesthesia maintenance time, and quality of sensory block were observed. RESULTS: Anesthesia took effect about 4 minutes after injection in these 4 groups without significant differences among then (all P > 0.05). The good analgesic effect rates of Groups A, B, and C were all 100%, all significantly higher than that of Group D (87.5%, P = 0.027). The block maintenance times of Groups A, B, and C were (377 +/- 111) min, (369 +/- 135) min, and (351 +/- 112) min respectively, all significantly longer than that of Group D [(296 +/- 101) min, P = 0.024]. No anesthesia-related complication was found in these 4 groups. CONCLUSION: Ultrasound-guided infraclavicular brachial plexus block via coracoid approach can reduce the volume of local anesthetic mixture. The dose of 6 ml local anesthetic mixture for each nerve fascicle, totally 18 ml, provides good analgesic effect and does not seem to affect the time for anesthesia taking effect.

Dorsal Penile Nerve Block via Perineal Approach, an Alternative to a Caudal Block for Pediatric Circumcision: A Randomized Controlled Trial.

BACKGROUND: General anesthesia combining with a caudal block (CB) has been commonly performed in pediatric patients undergoing circumcision surgeries. However, some severe complications have been suspected of a caudal block in the combined use. To avoid these issues of a caudal block, this study introduces a novel dorsal penile nerve block (DPNB) via perineum guided by ultrasound as an alternative to a caudal block in pediatric circumcision surgeries. METHODS: A total of 104 pediatric patients scheduled for circumcision surgeries were involved and randomly divided into 2 groups: the CB group (n=52) and the DPNB group (n=52). A laryngeal mask was inserted followed by induction and maintenance anesthesia of inhaled sevoflurane. In the DPNB group, a dorsal penile nerve block (DPNB) guided by a real-time ultrasonography was performed by a single injection via perineum of 0.25% ropivacaine plus 0.8% lidocaine with total injection volume of 3-5ml. In the CB group, a dose of 0.5 ml/kg was given via the caudal canal following the same general anesthesia with that of Group DPNB. The time to the first analgesic demand after surgery is the key data collected for comparing between the two study groups. Heart rates and respiratory rates changes before and during the surgical procedure, pain score when leaving the PACU, and the time taken for the first micturition after a surgery were also recorded to analyze the differences in analgesic effects between the CB and DPNB groups. RESULTS: No significant difference in heart rates and respiratory rates was found between the two groups before and during the surgery. Pain scores were similar before pediatric patients leave the PACU. However, the time taken for the first micturition after a surgery in Group DPNB is shorter than Group CB. The patients in Group DPNB asked for analgesics later than those in Group CB. Additionally, no significant differences in adverse effects were noted between two groups except the numbness of the lower limbs occurring less in Group DPNB. CONCLUSIONS: The ultrasound-guided dorsal penile nerve block via perineal approach can basically act as a safe and effective alternative to the caudal block in pediatric patients undergoing circumcision surgeries. Clinical Trials identifier is ChiCTR-IPR-15006670. Protocol is available at http://www.chictr.org.cn/showproj.aspx?proj=11319.