Stereo-Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material.

The lone pair electrons in the electronic structure of molecules have been a prominent research focus in chemistry for more than a century. Stable s2 lone pair electrons significantly influence material properties, including thermoelectric properties, nonlinear optical properties, ferroelectricity, and electro(photo)catalysis. While major advances have been achieved in understanding the influence of lone pair electrons on material characteristics, research on this effect in organic-inorganic hybrid materials is in its initial stage. In this work, we successfully obtained a novel organic-inorganic hybrid multifunctional material incorporating Ge with 4s2 lone pair electrons, (MeHDabco)2[GeBr3]4-H2O (MeHDabco=N-methyl-1,4-diazabicyclo[2.2.2]octane) (1). Driven by the stereochemically active lone pair electrons on the Ge2+, 1 crystallizes in the noncentrosymmetric space group P21 at room temperature and exhibits good second harmonic generation (SHG) responses. Interestingly, 1 also shows electrocatalytic activity for the hydrogen evolution reaction (HER) due to the existence of lone pair electrons on Ge2+ cations. The electrochemical experiment combined with the density functional theory (DFT) calculations revealed that the lone pair electrons act as both an active site for proton adsorption and facilitate the ionization of water. This work not only emphasizes the important role of lone pair electrons in material properties and functions but also provides new insight for designing novel Ge-based multifunctional hybrid materials.

Homochiral Chemistry Strategy to Trigger Second-Harmonic Generation and Dual Dielectric Switches.

Switchable materials have attracted enormous interest due to their promising applications in important fields such as sensing, electronic components, and information storage. Nevertheless, obtaining multifunctional switching materials is still a problem worth investigating. Herein, by incorporating (Rac-, L-, D-2-amino-1-propanol) as the templating cation, we have obtained (Rac-, L-, D-HTMPA)CdCl3 (HTMPA = 1-hydroxy-N, N, N-trimethyl-2-propanaminium). We have adopted a chiral chemistry strategy that causes (Rac-HTMPA)CdCl3 in the central symmetric space to crystallize in the chiral space group. Based on the modulation of the homochiral strategy, (L-, D-HTMPA)CdCl3 shows a dual phasic transition at 269 and 326 K and a switchable second-harmonic generation response. In addition, (L-, D-HTMPA)CdCl3 is chiral switchable material to exhibit stable dual dielectric and second-harmonic generation (SHG) switches. This work provides an approach to exploring multifunctional chiral switchable materials.

[Relationship between the gross motor function classification system and hip and lumbar spine development in children with spastic cerebral palsy].

OBJECTIVE: To investigate the relationship among the gross motor function classification system (GMFCS)and the development of hip joint and lumbar spine in children with spastic cerebral palsy. METHODS: The clinical data of 125 children with spastic cerebral palsy admitted from January 2018 to July 2021 were retrospectively analyzed. There were 85 males and 40 females, aged from 4 to 12 years old with an average of (8.4±2.9) years. According to GMFCS, the patients were divided into gradeⅠ, Ⅱ, Ⅲ and Ⅳ groups. There were 27 cases in gradeⅠgroup, 40 cases in gradeⅡgroup, 35 cases in grade Ⅲ group and 23 cases in grade Ⅳ group. The migration percentage(MP), central edge angle(CE), neck-shaft angle(NSA), acetabular index(AI) were measured by the radiograph of pelvis, abnormal parameters were selected to evaluate the relationship between different GMFCS grades and hip joint development. Lumbar sagittal Cobb angle, lumbar sacral angle, lumbar lordosis index and apical distance were measured by lateral lumbar radiographs to evaluate the relationship between different GMFCS grades and lumbar spine development. RESULTS: ①Among the 125 spastic cerebral palsy children, there were 119 cases of pelvic radiographs that met the measurement standards. In the four groups with gradeⅠ, Ⅱ, Ⅲ, Ⅳ, MP was (22.72±3.88), (26.53±4.36), (33.84±4.99), and (49.54±7.87)%, CE was(30.10±6.99) °, ( 22.92±4.19) °, ( 17.91±5.50) °, and (-0.70±17.33)°, AI was (16.41±2.77) °, (20.46±4.63) °, (23.76±5.10) °, and ( 29.15±7.35)°, respectively, there were significant differences between the two comparisons (P<0.05). And the higher GMFCS grade, the greater MP and AI, and the smaller CE.The NSA was(142.74±10.03) °, (148.66±9.09) °, (151.66±10.52) °, and (153.70±8.05)° in four groups with gradeⅠ, Ⅱ, Ⅲ, Ⅳ, respectively. The differences between the two comparisons of the GMFCS gradeⅠgroup and the other three groups were statistically significant (P<0.05). NSA of GMFCSⅠgroup was significantly lower than that of the others, there was no significant difference among other groups(P>0.05). ② Among the 125 spastic cerebral palsy children, there were 88 cases of lumbar spine radiographs that met the measurement standards. ③The lumbar sagittal Cobb angle was(32.62±11.10) °, (29.86±9.90) °, (31.70±11.84) °, and (39.69±6.80)° in the four groups with gradeⅠ, Ⅱ, Ⅲ, Ⅳ, respectively;GMFSS of grade Ⅳ group was significantly higher than that of other three groups, there was significant difference between the two comparisons (P<0.05);there were no significant differences between other groups (P>0.05). In the four groups with gradeⅠ, Ⅱ, Ⅲ, Ⅳ, the lumbosacral angle was (31.02±9.91) °, ( 26.57±9.41) °, (28.08±8.56) °, and ( 27.31±11.50)°, the lumbar lordosis index was (4.14±12.89), (8.83±13.53), (13.00±11.78), and (10.76±9.97) mm, the arch apex distance was (9.50±6.80), (6.68±3.20), (7.16±4.94), and (6.62±4.13) mm, respectively, there were no significant differences between the two comparisons(P>0.05). CONCLUSION: ①In children with GMFCS gradeⅠ-Ⅳ, the higher the GMFCS grade, the worse the hip develops. ② Children with GMFCS grade Ⅲ-Ⅳ may be at greater risk for lumbar kyphosis.

A hierarchically combined reduced graphene oxide/Nickel oxide hybrid supercapacitor device demonstrating compliable flexibility and high energy density.

This work demonstrates a hierarchical structure design with mixed holey graphene oxide (HGO) and Ni(OH)2 active material layer made by one-pot hydrothermal reaction clinging to Nickel foam as backbone and ice-template oriented graphene oxide (GO) aerogel as filling, aiming to create an asymmetric solid supercapacitor (ASC) device with compliable flexibility and high electrochemical performance. The effects of hydrothermal treatment and ice-template freezing parameters on electrochemical stability under repeated exterior deformation are discussed, the optimal parameters result in a high areal capacitance of 479.8 mF/cm2 in asymmetric supercapacitor device setup. The use of porous HGO and oriented GO aerogel synergistically contribute to the high energy and power density up to 1.69 Wh/m2 and 9 W/m2 as well as excellent electrochemical performance retention under repeated curving deformation which reaches 102% thanks to a novel activation process. The electrode assembly including metal foam and the buffering GO aerogel should be instructive for future supercapacitor design.

Fabrication of a NiO@NF supported free-standing porous carbon supercapacitor electrode using temperature-controlled phase separation method.

To address the problem that capacitor electrode being low in capacitance and reliant on binder to retain shape, a binder-free, self-supporting supercapacitor electrode is made via pyrolysis of porous polyacrylonitrile (PAN) formed by phase separation, supported by hydrothermally treated nickel foam backbone. The role of hydrothermal reaction time and PAN solution concentration on electrochemical properties was thoroughly studied, and the results indicate a generally peaked capacitance at 4 h of hydrothermal reaction time, but after a certain threshold, a supposed micro-domain buffering mechanism would take over and enhance the pseudocapacitance from NiO to reach a specific capacitance as high as 152 F/g at a high active material mass load of 14.98 mg/cm2, providing the area specific capacitance up to 1.98 F/cm2. The use of temperature-controlled phase separation and incorporation of nickel oxide together guarantees the electrode sufficient ion and electron transportation pathway while improving its capacitance by redox electrochemical reactions.

[Role of JAK2/STAT3 signaling pathway in microglia activation after hypoxic-ischemic brain damage].

Hypoxic-ischemic encephalopathy (HIE) is the leading cause of neonatal death and neurodevelopmental disorders in infants. Part of patients have different degrees of neurological sequelae, such as cerebral palsy, cognitive and motor function development disorders. Hypoxia-ischemia may activate JAK2/STAT3 signaling pathway, which leads to the microglia activation and neuroinflammation. Down-Regulating JAK2/STAT3 signaling pathway can inhibit microglia activation and regulate the inflammatory injury of nervous system. At present, the treatment of hypoxic ischemic encephalopathy is limited, so the study of regulatory mechanism about microglia activation has important value for the treatment of hypoxic-ischemic encephalopathy. This paper summarizes the role of JAK2/STAT3 signaling pathway in microglia activation and analyzes the relationship between them, in order to provide new ideas and strategies for treatment on hypoxic-ischemic encephalopathy.

[Clinical observation of selective posterior rhizotomy for improving spasticity and gross movement in patients with cerebral palsy].

OBJECTIVE: To explore the effect of selective lumbosacral posterior rhizotomy(SPR) on lower limb spasticity and gross motor function in patients with cerebral palsy. METHODS: From January 2018 to October 2018, 47 patients with cerebral palsy were treated with rehabilitation alone and SPR combined with rehabilitation. According to whether SPR was performed, the patients were divided into group A and group B. Group A was treated with rehabilitation combined with SPR at lumbosacral level, and group B was treated with rehabilitation alone. There were 23 cases in group A, including 15 males and 8 females, with an average age of (7.30±3.25) years old; 24 cases in group B, 13 males and 11 females, with an average age of (7.00±3.09) years old. Forty-seven patients were assessed with modified Ashworth(MAS) and Gross Motor Function Scale(GMFM-88 items) before and after treatment. The changes of MAS and GMFM-88 scores before and after treatment were compared to evaluate the degree of spasm and the improvement of gross motor function in the two groups. RESULTS: All 47 patients were followed up. At 6 months after treatment, the MAS classification of the two groups was significantly improved(P<0.05), and the improvement of group A was more obvious than that of group B(P<0.05). Six months after treatment, the D, E and total scores of GMFM-88 between two groups were significantly improved compared with those before operation(P<0.05). The improvement of D and total scores in group A was more obvious than that in group B. There was no significant difference in the improvement of area E between two groups. CONCLUSIONS: Selective posterior rhizotomy combined with rehabilitation can significantly improve the spastic state and gross motor function of lower limbs in children with cerebral palsy, and can effectively promote the reconstruction and recovery of motor function of lower limbs in children with cerebral palsy.

[A Meta-analysis of the Effectiveness of Acupuncture in the Treatment of Epilepsy].

OBJECTIVE: To evaluate the efficacy and safety of acupuncture in the treatment of epilepsy. METHODS: We first collected research data about randomized control trials (RCTs) of acupuncture treatment of epilepsy from databases CNKI, CBM, VIP and Wanfang using key words "(acupuncture)", "(epilepsy)"or "(epilepsy)"or "(epilepsy)", and from PubMed, Google Scholar, and Cochrane Library using key words "acupuncture" "needling" "prod" "epilepsy" "epilepsies" or "seizure disorder" or "simple seizure" from the date of database construction to May 5, 2017. Then, two researchers extracted the study outcomes and evaluated the evidence qualification of the research data independently using GRADE profile 3.6 software and analyzed the primary outcome indexes using RevMan 5.3 and STATA 14.0. RESULTS: Eleven articles containing 827 cases were included in the Meta-analysis. We found that acupuncture or acupuncture in combination with other conventional drugs had a significantly better efficacy than conventional drugs in the treatment of epilepsy [OR=3.94, 95%CI (2.49, 6.24), Z=5.85, P<0.000 01]. There was a statistical heterogeneity (P=0.04, l2=60%), and the Meta-analysis was not feasible for the studies of acupuncture vs medication. Combination of acupuncture and Chinese traditional drugs was significantly better than simple Chinese traditional drugs [OR = 4.61, 95%CI (2.18, 9.74), Z=4.01, P<0.000 1], and combination of acupuncture and wes-tern medicines was obviously better than simple western medicines [OR=3.07, 95%CI(1.24, 7.65), Z=2.41, P=0.02] in the treatment of epilepsy. CONCLUSION: Acupuncture therapy may have a positive effect in the treatment of epilepsy but the conclusion needs further verification due to very fewer high-quality and well-designed RCTs found at the present.

[A Meta-analysis of Effectiveness of Acupoint Catgut Embedding Therapy for Insomnia].

OBJECTIVE: To evaluate the effectiveness and superiority of acupoint catgut-embedding in the treatment of insomnia. METHODS: Randomized controlled trials (RCTs) for insomnia treated by acupoint implantation of catgut were included in the present study. We searched the related articles from 6 databases (PubMed, Google Scholar, CBM, CNKI, VIP and Wanfang) from the date of inception to March 19, 2017 by using keywords "catgut implantation at acupuncture point" or "catgut implantation at acupoint" and "insomnia" or "agrypnia" and "randomised (or randomized) clinical trial". Quality assessments were performed by two researchers independently using GRADE profile 3.6, followed by crosscheck. Data were analyzed using software Revman 5.3 and STATA 14.0. RESULTS: Twenty-two trials met the inclusion criteria were included. They recruited 1 714 cases of insomnia. GRADE grading suggests a low quality of these articles. Heterogeneous test (numerical test) showed χ2＝31.11, P＝0.07, I2＝32%. Gabriz chart and sensitivity analysis ultimately determined that these trials have smaller or no heterogenity. The effective rate of acupoint catgut embedding for insomnia was higher than that of the control group (OR＝ 3.77; 95% CI: 2.63－5.41; P<0.00001). CONCLUSION: Acupoint catgut embedding therapy has a positive role in clinical treatment of insomnia. But due to lower quality of current literature, more high-quality randomized controlled clinical trials are required.

[Using Machine Learning to Investigate Factors Influencing the Efficacy of "Shoulder Tri-needles Therapy" in Treatment of Shoulder-hand Syndrome in 586 Stroke Patients].

OBJECTIVE: To analyze the factors influencing the therapeutic effect of "Shoulder Tri-needles therapy" in the treatment of shoulder-hand syndrome of stroke patients by using machine learning approach, so as to provide a feasibility for improving clinical efficacy. METHODS: A total of 586 stroke patients with shoulder-hand syndrome eligible for this study were involved in our machine learning experiments for classification of the influential factors. Their data including the age, gender, pulse condition, complexion, tongue quality, tongue coating, disease stage, body mass index (BMI), blood pressure, blood glucose, blood triglyceride, blood total cholesterol, smoking history, drinking history, and final outcomes were extracted from the medical record system (from Oct. of 2014 to Jan. of 2017 in the First Affiliated Hospital and Shenzhen Futian Hospital of Guangzhou University of Chinese Medicine). The single rule algorithm (1 R) was adopted to learn, followed by optimization with Repeated Incremental Pruning to Produce Error Reduction (RIPPER) algorithm, and C 5.0 decision tree algorithm. RESULTS: The accurate classification rates of 1 R, RIPPER and decision tree model were 87.37%(512/586), 95.90% (562/586), and 97.10% (569/586), respectively. The final outcomes of machine learning of this study showed that the disease stage (acute or recovery stage), complexion difference, tongue coating difference, blood pressure level, consumption of alcohol, BMI, and smoking habit were the most important factors influencing the therapeutic effect of "Shoulder Tri-needles" in the treatment of shoulder-hand syndrome of stroke patients. CONCLUSION: The disease stage, complexion and tongue identification, blood pressure level, alcohol drinking and smoking habits, and BMI are the principal factors affecting the therapeutic effect of "Shoulder Tri-needles therapy" in the treatment of shoulder-hand syndrome of stroke patients.

New phenanthrene and 9, 10-dihydrophenanthrene derivatives from the stems of Dendrobium officinale with their cytotoxic activities.

Two new phenanthrene and 9, 10-dihydrophenanthrene derivatives (1-2) with six known congeners (3-8) were isolated from the extraction of stems of Dendrobium officinale. Compounds 1 and 2 were based on carbon skeleton in which phenanthrene and 9, 10-dihydrophenanthrene moiety were linked with a phenylpropane unit through a dioxane bridge, respectively. Their structures were determined by comprehensive NMR spectroscopic data, the absolute configuration of new compounds were determined by comparing their experimental and calculated ECD for the first time. All the compounds were investigated contains two cancer cell lines (HI-60, THP-1). All the isolates showed cytotoxicity, especially compound 4 showed markedly cytotoxic activities against HI-60 and THP-1 cell lines with IC50 values of 11.96 and 8.92 µM.