Incorporating Catalytic Units into Nanomaterials: Rational Design of Multipurpose Catalysts for CO2 Valorization.

ConspectusCO2 conversion to valuable chemicals is effective at reducing CO2 emissions. We previously proposed valorization strategies and developed efficient catalysts to address thermodynamic stability and kinetic inertness issues related to CO2 conversion. Earlier, we developed molecular capture reagents and catalysts to integrate CO2 capture and conversion, i.e., in situ transformation. Based on the mechanistic understanding of CO2 capture, activation, and transformation at a molecular level, we set out to develop heterogeneous catalysts by incorporating catalytic units into nanomaterials via the immobilization of active molecular catalysts onto nanomaterials and designing nanomaterials with intrinsic catalytic sites.In thermocatalytic CO2 conversion, carbonaceous and metal-organic framework (MOF)-based catalysts were developed for nonreductive and reductive CO2 conversion. Novel Cu- and Zn-based MOFs and carbon-supported Cu catalysts were prepared and successfully applied to the cycloaddition, carboxylation, and carboxylative cyclization reactions with CO2, generating cyclic carbonates, carboxyl acids, and oxazolidinones as respective target products. Reductive conversion of CO2, especially reductive functionalization with CO2, is a promising transformation strategy to produce valuable chemicals, alleviating chemical production that relies on petrochemistry. We explored the hierarchical reductive functionalization of CO2 using organocatalysts and proposed strategies to regulate the CO2 reduction level, triggering heterogeneous catalyst investigation. Introducing multiple active sites into nanomaterials opens possibilities to develop novel CO2 transformation strategies. CO2 capture and in situ conversion were realized with an N-doped carbon-supported Zn complex and MOF materials as CO2 adsorbents and catalysts. These nanomaterial-based catalysts feature high stability and excellent efficiency and act as shape-selective catalysts in some cases due to their unique pore structure.Nanomaterial-based catalysts are also appealing candidates for photocatalytic CO2 reduction (PCO2RR) and electrocatalytic CO2 reduction (ECO2RR), so we developed a series of hybrid photo-/electrocatalysts by incorporating active metal complexes into different matrixes such as porous organic polymers (POPs), metal-organic layers (MOLs), micelles, and conducting polymers. By introducing Re-bipyridine and Fe-porphyrin complexes into POPs and regulating the structure of the polymer chain, catalyst stability and efficiency increased in PCO2RR. PCO2RR in aqueous solution was realized by designing the Re-bipyridine-containing amphiphilic polymer to form micelles in aqueous solution and act as nanoreactors. We prepared MOLs with two different metallic centers, i.e., the Ni-bipyridine site and Ni-O node, to improve the efficiency for PCO2RR due to the synergistic effect of these metal centers. Sulfylphenoxy-decorated cobalt phthalocyanine (CoPc) cross-linked polypyrrole was prepared and used as a cathode, achieving the electrocatalytic transformation of diluted CO2 benefiting from the CO2 adsorption capability of polypyrrole. We fabricated immobilized 4-(t-butyl)-phenoxy cobalt phthalocyanine and Bi-MOF as cathodes to promote the paired electrolysis of CO2 and 5-hydroxymethylfurfural (HMF) and obtained CO2 reductive products and 2,5-furandicarboxylic acid (FDCA) efficiently.

Advancements and Challenges in Reductive Conversion of Carbon Dioxide via Thermo-/Photocatalysis.

Carbon dioxide (CO2) is the major greenhouse gas and also an abundant and renewable carbon resource. Therefore, its chemical conversion and utilization are of great attraction for sustainable development. Especially, reductive conversion of CO2 with energy input has become a current hotspot due to its ability to access fuels and various important chemicals. Nowadays, the controllable CO2 hydrogenation to formic acid and alcohols using sustainable H2 resources has been regarded as an appealing solution to hydrogen storage and CO2 accumulation. In addition, photocatalytic CO2 reduction to CO also provides a potential way to utilize this greenhouse gas efficiently. Besides direct CO2 hydrogenation, CO2 reductive functionalization integrates CO2 reduction with subsequent C-X (X = N, S, C, O) bond formation and indirect transformation strategies, enlarging the diverse products derived from CO2 and promoting CO2 reductive conversion into a new stage. In this Perspective, the progress and challenges of CO2 reductive conversion, including hydrogenation, reductive functionalization, photocatalytic reduction, and photocatalytic reductive functionalization are summarized and discussed along with the key issues and future trends/directions in this field. We hope this Perspective can evoke intense interest and inspire much innovation in the promise of CO2 valorization.

Suitable stocking density of fish in paddy field contributes positively to 2-acetyl-1-pyrroline synthesis in grain and improves rice quality.

BACKGROUND: Fragrant rice is increasingly popular with the public owing to its fresh aroma, and 2-acetyl-1-pyrroline (2-AP) is the main characteristic component of the aroma in fragrant rice. Rice-fish co-culture is an environmentally friendly practice in sustainable agriculture. However, the effect of rice-fish co-culture on 2-AP in grains has received little study. A conventional fragrant rice (Meixiangzhan 2) was used, and a related field experiment during three rice growing seasons was conducted to investigate the effects of rice-fish co-culture on 2-AP, as well as the rice quality, yield, plant nutrients, and precursors and enzyme activities of 2-AP biosynthesis in leaves. This study involved three fish stocking density treatments (i.e. 9000 (D1), 15 000 (D2), and 21 000 (D3) fish fries per hectare) and rice monocropping. RESULTS: Rice-fish co-culture increased the 2-AP content in grains by 2.5-49.4% over that of the monocropping, with significant increases in the early and late rice seasons of 2020. Rice-fish co-culture treatments significantly promoted seed-setting rates by 3.39-7.65%, and improved leaf nutrients and rice quality. Notably, the D2 treatment significantly increased leaf total nitrogen (TN), total phosphorus (TP), and total potassium (TK) contents and the head rice rate at maturity stage, while significantly decreased chalkiness degree. There was no significant difference in rice yield. CONCLUSION: Rice-fish co-culture had positive effects on 2-AP synthesis, rice quality, seed-setting rates, and plant nutrient contents. The better stocking density of field fish for rice-fish co-culture in this study was 15 000 fish ha-1 . © 2023 Society of Chemical Industry.

Oligomeric ricinoleic acid preparation promoted by an efficient and recoverable Brønsted acidic ionic liquid.

Raw material from biomass and green preparation processes are the two key features for the development of green products. As a bio-lubricant in metalworking fluids, estolides of ricinoleic acid are considered as the promising substitute to mineral oil with a favorable viscosity and viscosity index. Thus, an efficient and sustainable synthesis protocol is urgently needed to make the product really green. In this work, an environment-friendly Brønsted acidic ionic liquid (IL) 1-butanesulfonic acid diazabicyclo[5.4.0]undec-7-ene dihydrogen phosphate ([HSO3-BDBU]H2PO4) was developed as the efficient catalyst for the production of oligomeric ricinoleic acid from ricinoleic acid under solvent-free conditions. The reaction parameters containing reaction temperature, vacuum degree, amount of catalyst and reaction time were optimized and it was found that the reaction under the conditions of 190 °C and 50 kPa with 15 wt % of the [HSO3-BDBU]H2PO4 related to ricinoleic acid can afford a qualified product with an acid value of 51 mg KOH/g (which corresponds to the oligomerization degree of 4) after 6 h. Furthermore, the acid value of the product can be adjusted by regulating the reaction time, implying this protocol can serve as a versatile method to prepare the products with different oligomerization degree and different applications. The other merit of this protocol is the facile product separation by stratification and decantation ascribed to the immiscibility of the product and catalyst at room temperature. It is also worth mentioning that the IL catalyst can be used at least for five cycles with high catalytic activity. As a result, the protocol based on the IL catalyst, i.e. [HSO3-BDBU]H2PO4 shows great potential in industrial production of oligomeric ricinoleic acid from ricinoleic acid.

Intramuscular Injection of Adenoassociated Virus Encoding Human Neurotrophic Factor 3 and Exercise Intervention Contribute to Reduce Spasms after Spinal Cord Injury.

Limb spasms are phenomena of hyperreflexia that occur after spinal cord injury. Currently, the clinical treatment is less than ideal. Our goal is to develop a combination therapy based on individualized medicine to reduce spasticity after spinal cord injury. In this study, rats received a severe contusive injury at the T9 segment of the spinal cord, followed by gene therapy with adenoassociated virus encoding human neurotrophic factor 3 (AAV-NT3) and a 2-week exercise program starting at 4 weeks after injury. We quantified the frequency of spasms during a swimming test at 4 and 6 weeks after injury and confirmed the results of the swimming test by measuring the H-reflex of the plantar muscle. We obtained weekly hind limb exercise scores to assess the effect of the interventions in hind limb motor function improvement. Then, we used immunofluorescence to observe the immunoreactivity of spinal motor neurons, synaptophysin, cholinergic interneurons, and GABAergic interneurons. We also measured the expression of KCC2 in the spinal cord by western blot. We found that AAV-NT3 gene therapy, exercise, and combination therapy all attenuated the frequency of spasms in the swimming test conducted at 6 weeks after spinal cord injury and increased rate-dependent depression of H-reflex. Combination therapy was significantly superior to AAV-NT3 alone in protecting motor neurons. Recovery of KCC2 expression was significantly greater in rats treated with combination therapy than in the exercise group. Combination therapy was also significantly superior to individual therapies in remodeling spinal cord neurons. Our study shows that the combination of AAV-NT3 gene therapy and exercise can alleviate muscle spasm after spinal cord injury by altering the excitability of spinal interneurons and motor neurons. However, combination therapy did not show a significant additive effect, which needs to be improved by adjusting the combined strategy.

[Value of sperm acrosin activity detection in selecting the method of assisted reproduction for patients with unexplained infertility].

OBJECTIVE: To investigate the clinical significance of sperm acrosin activity detection in selecting the method of assisted reproduction for patients with unexplained infertility (UI). METHODS: This retrospective study included 49 UI couples treated by IVFET (49 cycles) after three failures in intrauterine insemination (IUI) and another 95 couples with uterine tube obstruction (UTO) treated by IVF (131 cycles). We analyzed the laboratory data, clinical outcomes and sperm acrosin activity in the two groups of patients. According to the level of sperm acrosin activity of the males, we further divided the UI patients into two subgroups, a < 36 IU/106 sperm group (20 cycles) and a ≥36 IU/106 sperm group (29 cycles), and compared the fertilization rates between the two groups. RESULTS: Compared with UI couples treated by IVFET, the UTO couples treated by IVF had a significantly lower rate of fertilization (67.0% vs 76.4%, P < 0.05) and a higher rate of remedial intracytoplasmic sperm injection (ICSI) (20.4% vs 6.1%, P < 0.05), but showed no statistically significant differences in the rates of MII oocytes, available embryos, highquality embryos, implantation, and clinical pregnancy from the latter group (P >0.05). The sperm acrosin activity was remarkably lower in the UI than in the UTO patients (36.03 vs 61.98 IU/106, P < 0.01), and so was the fertilization rate in the < 36 IU/106 than in the ≥36 IU/106 sperm subgroup (47.7% vs 80.3%, P < 0.01). CONCLUSIONS: The low fertilization rate caused by decreased sperm acrosin activity may be the main cause of infertility and the potential factor of UI. When sperm acrosin activity is < 36 IU/106 sperm, IVF plus shortterm fertilization by remedial ICSI should be preferred to IUI.

The combination of TRPM8 and TRPA1 expression causes an invasive phenotype in lung cancer.

Our recent studies have shown that hypothermic microenvironment promotes tumor progression and that the molecular sensors for cold are the transient receptor potential (TRP) channels TRPM8 and TRPA1. To evaluate the contribution of TRPM8 and TRPA1 to cancer malignancy, we screened cell subpopulations from Lewis lung cancer (LLC) using limiting dilutions and Western blotting. We identified that LLC-1 cells express 3-fold more TRPM8 than TRPA1, LLC-2 cells express TRPM8 at levels similar to TRPA1, and LLC-3 cells express TRPM8 at one-third the level of TRPA1. LLC-2 cells showed greater adhesion, migration, invasiveness and resistance to hypothermia than LLC-1 and LLC-3 cells, although LLC-2 cells had a longer doubling time. TRPM8 or TRPA1 knockdown using siRNA promoted cell proliferation and decreased adhesion and invasiveness in LLC-2 cells. When assessed for UCP2 staining, LLC-1 cells showed increased staining compared to LLC-2 cells, both of which had more UCP2-positive cells than the LLC-3 subpopulation. In an autophagy assay, hypothermia induced substantially less autophagy in LLC-1 cells than in LLC-2 cells, which displayed decreased autophagy compared to LLC-3 cells. Moreover, mice injected with LLC-2 cells had significantly more spontaneous and experimental lung metastases and a shorter overall survival time than mice injected with LLC-1 or LLC-3 cells. Importantly, LLC-2 cells were also more resistant to activated spleen CTL and the chemotherapeutic drug doxorubicin than LLC-1 and LLC-3 cells in vitro. Collectively, our data suggest that TRPM8 induces UCP2 to trigger metabolic transformation, whereas TRPA1 induces autophagy during adverse conditions, and the combination of both genes contributes directly to an invasive phenotype in lung cancer.

Synthesis of Dimethyl Carbonate via Transesterification of Ethylene Carbonate and Methanol over Mesoporous KF-loaded Mg-Fe Oxides.

A series of KF/Mg-Fe oxides were fabricated via the solid-state reaction between KF and Mg-Fe oxides. Especially, when 20 wt % KF was supported on the Mg-Fe bi-metal oxides and calcined at 400-600 °C, the solid material with more basic sites than the support itself was obtained. When applied as catalyst to dimethyl carbonate (DMC) synthesis through transesterification of ethylene carbonate (EC) and methanol, this material can afforded up to 88 % yield and 97 % selectivity toward DMC in 2 h under reflux conditions with the molar ratio of methanol to ethylene carbonate set at 8. It is worth noting that the catalyst was easily separated and reused, retaining at least 89 % catalytic activity during the first four recycles. Although an attenuated activity was still observed due to the inevitable filtration loss and dissolution, this solid base can still provide clues to the development recyclable catalyst in green synthesis of DMC.

Electrochemical E-Selective Semireductive Dicarboxylation of Aryl Alkynes with CO2.

Herein, we report an electrochemical protocol for the dicarboxylation of aryl alkynes using CO2. With a graphite rod as the cathode and Al as the sacrificial anode, a series of valuable butenedioic acids are obtained in moderate to excellent yields with an E/Z ratio up to 50:1. This method features high E-selectivity, high step and atom economy, easy scalability, and a nice substrate scope, which renders it appealing for promising applications in organic synthesis and materials chemistry.

Hydroformylation of Olefins with CO2/H2 and Hydrosilane by Copper/Cobalt Tandem Catalysis.

A Cu/Co tandem catalysis protocol was developed to conduct the hydroformylation of olefins using CO2/H2 and PMHS (polymethylhydrosiloxane) as a readily available and environmentally friendly hydride source. This methodology was performed via a two-step approach consisting of the copper-catalyzed reduction of CO2 by hydrosilane and subsequent cobalt-promoted hydroformylation with H2 and the in situ formed CO. The optimized triphos oxide ligand, which presumably facilitates the migratory insertion of CO gives moderate to excellent yields for both terminal and internal alkenes. This earth-abundant metal catalysis provides a reliable and efficient way to afford useful aldehydes in industry using silicon by-product PMHS as hydrogen source and renewable CO2 as carbonyl source.

Mononuclear Iron Pyridinethiolate Complex Promoted CO2 Photoreduction via Rapid Intramolecular Electron Transfer.

Designing earth-abundant metal complexes as efficient molecular photocatalysts for visible light-driven CO2 reduction is a key challenge in artificial photosynthesis. Here, we demonstrated the first example of a mononuclear iron pyridine-thiolate complex that functions both as a photosensitizer and catalyst for CO2 reduction. This single-component bifunctional molecular photocatalyst efficiently reduced CO2 to formate and CO with a total turnover number (TON) of 46 and turnover frequency (TOF) of 11.5 h-1 in 4 h under visible light irradiation. Notably, the quantum yield was determined to be 8.4 % for the generation of formate and CO at 400 nm. Quenching experiments indicate that high photocatalytic activity is mainly attributed to the rapid intramolecular quenching protocol. The mechanism investigation by DFT calculation and electrochemical studies revealed that the protonation of Febpy(pyS)2 is indispensable step for photocatalytic CO2 reduction.

[Diagnostic investigation of the detection of granulocyte-macrophage colony stimulating factor antibody in serum for pulmonary alveolar proteinosis].

OBJECTIVE: To evaluate the diagnostic value of granulocyte-macrophage colony stimulating factor (GM-CSF) antibody in serum for pulmonary alveolar proteinosis (PAP). METHODS: Twelve PAP patients visiting Peking University People's Hospital or Fujian Provincial Hospital from January 1, 2002 to December 31, 2012, 25 patients with other pulmonary diseases (disease control), and 25 healthy volunteers (healthy control) were recruited in the study. The titer level of GM-CSF antibody in serum was determined with enzyme-linked immunosorbent assay (ELISA), and the clinical characteristics were collected in the PAP patients. RESULTS: The geometric mean titers of GM-CSF antibody in the PAP patients, the disease controls and the healthy controls were 1: 25 349, 1: 311 and 1: 256, respectively. The differences between the disease controls and the healthy controls were of no statistic significance (t = -1.14, P = 0.261) . With 3 times standard error (3s) above the mean value as the higher limit of X value(X = lgT, T standing for the reciprocal of the titer), the upper limit for T was 1698. With the T value ≥ 1698 as the diagnostic threshold for PAP, both the sensitivity and the specificity were 100%. The diagnostic value of GM-CSF antibody was similar to that of surgical lung biopsy and higher than that of transbronchial lung biopsy. CONCLUSION: The detection of serum GM-CSF is non-invasive, convenient and efficient for the diagnosis of PAP with high sensitivity and specificity.

Meta analysis of ovulation induction effect and pregnancy outcome of acupuncture & moxibustion combined with clomiphene in patients with polycystic ovary syndrome.

Objective: Using Mesh Meta Analysis to evaluate the efficacy of Acupuncture & Moxibustion, Clomiphene, Acupuncture & Moxibustion combined with Clomiphene for treating Polycystic Ovary Syndrome (PCOS), in order to provide evidence-based medical evidence for whether to recommend Acupuncture & Moxibustion or Combine western medicine to treat PCOS. Methods: Eight databases including The Cochrane Library, Pubmed, Embase, Web of Science, CNKI, Wanfang Date, VIP and CBM were searched by computer. The included research period is from the establishment of the database to May 2023, which concerned with randomized controlled trials involving Acupuncture & Moxibustion, Clomiphene, Acupuncture & Moxibustion combined with Clomiphene on ovulation induction and pregnancy outcome in patients with PCOS. The duration of the research paper is from 2016 to 2023.The inclusion criteria refer to the Rotterdam standards issued by the European Center for Human Reproduction and Embryology and the American Society of Reproductive Medicine in January 2003, or the Expert Consensus on the Diagnosis and Treatment of Polycystic Ovarian Syndrome by the Endocrinology Group of the Obstetrics and Gynecology Branch of the Chinese Medical Association. Simultaneously exclude related diseases, repetitive literature, as well as literature with incomplete abstract information and no original data provided. Two researchers independently screened the literature, extracted data, and evaluated the risk of bias included in the study, using Stata17.0 software for a mesh meta-analysis. Results: Six randomized controlled trials were included, covering 1410 PCOS patients. Three interventions included Acupuncture & Moxibustion, Clomiphene, Acupuncture & Moxibustion combined with Clomiphene. Mesh Meta Analysis showed that in terms of improving ovulation rate, there was no statistical difference between Acupuncture & Moxibustion (A), Clomiphene (B), Clomiphene combined with Acupuncture & Moxibustion (C) (P>0.05).Acupuncture & Moxibustion (A) versus Clomiphene (B) [MD=0.15,95% CI (-0.51,0.80)], Acupuncture & Moxibustion (A) versus Clomiphene combined with Acupuncture & Moxibustion (C) [MD=1.60,95% CI (0.97,2.23)], Clomiphene (B) versus Clomiphene combined with Acupuncture & Moxibustion (C) [MD=1.45,95% CI (0.91,1.99)]. In terms of pregnancy outcome, the difference between the three intervention methods was statistically significant (P<0.05). Acupuncture & Moxibustion (A) versus Clomiphene (B) [MD=-0.80,95% CI (-1.84,0.23)], Acupuncture & Moxibustion (A) versus Clomiphene combined with Acupuncture & Moxibustion (C) [MD=0.29,95% CI (-0.73,1.30)], and Clomiphene (B) versus Clomiphene combined with Acupuncture & Moxibustion (C) [MD=1.09,95% CI (0.39,1.79)], The order of pregnancy rate from high to low is Acupuncture & Moxibustion combined with Clomiphene (C), Acupuncture & Moxibustion (A), Clomiphene (C).In terms of influencing endometrial thickness, the difference between the three intervention methods was statistically significant (P<0.05). Acupuncture & Moxibustion (A) versus Clomiphene (B) [MD=-0.84,95% CI (-1.87,0.19)], Acupuncture & Moxibustion (A) versus Acupuncture & Moxibustion combined with Clomiphene (C) [MD=0.26,95% CI (-1.01,1.53)], Clomiphene (B) versus Acupuncture & Moxibustion combined with Clomiphene (C) [MD=1.10,95% CI (0.36,1.84)], Acupuncture & Moxibustion combined with Clomiphene (C) has the best effect on improving endometrial thickness. In subgroup analysis, the effect of Acupuncture & Moxibustion treatment frequency on ovulation rate and pregnancy rate was not statistically significant. The combination of Acupuncture & Moxibustion, Electroacupuncture and warm Acupuncture & Moxibustion has no effect on the pregnancy rate, but the combination of Electroacupuncture and Clomiphene has the best effect on improving the ovulation rate. In the observation of adverse reactions, compared with clomiphene alone, Acupuncture & Moxibustion combined with Clomiphene can reduce the occurrence of Luteinized Unruptured Follicle Syndrome (LUFS) and Ovarian Hyperstimulation Syndrome (OHSS), and reduce the occurrence of physical adverse reactions such as nausea, vomiting, headache and dermatitis. Conclusion: Acupuncture & Moxibustion is effective in improving the ovulation promoting effect and pregnancy outcome of PCOS patients. The ovulation promoting effect of Acupuncture & Moxibustion or combined with Clomiphene is similar to that of Clomiphene alone, but Acupuncture & Moxibustion combined with Clomiphene has more advantages in improving the pregnancy rate of PCOS, and it also can reduce the adverse reactions of Clomiphene alone. Acupuncture & Moxibustion can be used as a recommended treatment for PCOS. More cases should also be included in the subgroup analysis to study the impact of Acupuncture & Moxibustion programs on clinical efficacy and further optimize the Acupuncture & Moxibustion treatment program. Systematic review registration: https://www.crd.york.ac.uk/PROSPERO/#myprospero, identifier (CRD42023433057).

The conscious processing of emotion in depression disorder: a meta-analysis of neuroimaging studies.

Background: Depression is generally accompanied by a disturbed conscious processing of emotion, which manifests as a negative bias to facial/voice emotion information and a decreased accuracy in emotion recognition tasks. Several studies have proved that abnormal brain activation was responsible for the deficit function of conscious emotion recognition in depression. However, the altered brain activation related to the conscious processing of emotion in depression was incongruent among studies. Therefore, we conducted an activation likelihood estimation (ALE) analysis to better understand the underlying neurophysiological mechanism of conscious processing of emotion in depression. Method: Electronic databases were searched using the search terms "depression," "emotion recognition," and "neuroimaging" from inceptions to April 10th, 2023. We retrieved trials which explored the neuro-responses of depressive patients to explicit emotion recognition tasks. Two investigators independently performed literature selection, data extraction, and risk of bias assessment. The spatial consistency of brain activation in conscious facial expressions recognition was calculated using ALE. The robustness of the results was examined by Jackknife sensitivity analysis. Results: We retrieved 11,365 articles in total, 28 of which were included. In the overall analysis, we found increased activity in the middle temporal gyrus, superior temporal gyrus, parahippocampal gyrus, and cuneus, and decreased activity in the superior temporal gyrus, inferior parietal lobule, insula, and superior frontal gyrus. In response to positive stimuli, depressive patients showed hyperactivity in the medial frontal gyrus, middle temporal gyrus, and insula (uncorrected p < 0.001). When receiving negative stimuli, a higher activation was found in the precentral gyrus, middle frontal gyrus, precuneus, and superior temporal gyrus (uncorrected p < 0.001). Conclusion: Among depressive patients, a broad spectrum of brain areas was involved in a deficit of conscious emotion processing. The activation of brain regions was different in response to positive or negative stimuli. Due to potential clinical heterogeneity, the findings should be treated with caution. Systematic review registration: https://inplasy.com/inplasy-2022-11-0057/, identifier: 2022110057.

[Association between polymorphisms of insulin-like growth factor receptor gene and susceptibility to non-small-cell lung cancer in Fujian Chinese].

OBJECTIVE: To assess the association between polymorphisms of insulin-like growth factor receptor (IGF-1R and IGF-2R) and genetic susceptibility and non-small-cell lung cancer (NSCLC). METHODS: A case-control study of 260 patients with NSCLC and 258 cancer-free subjects from Fujian was carried out. Genotypes of polymorphisms of IGF-1R +1013 and IGF-2R +1619 were determined by DNA sequencing and polymerase chain reaction-restrictive fragment length polymorphism. RESULTS: (1) Significant differences in allele frequency and genotypes distribution of IGF-1R +1013 (G/A) were found between the two groups (P<0.05). On multivariate analysis after controlling age and gender, compared with GG genotype of the IGF-1R +1013 (G/A), the risk of lung cancer for individuals with GA genotype was increased by 0.80 times (95%CI: 1.24-2.59, P = 0.002), those with AA genotype was increased by 2.56 times (95%CI: 1.78-7.26, P = 0.000), and those with the polymorphic A variant (GA or AA) was increased by 0.98 times (95%CI: 1.39-2.83, P = 0.000). No significant differences in genotypic or allelic frequencies of IGF-2R +1619 (G/A) were found between the two groups (P> 0.05). (2) After stratification of the clinical status, the IGF-1R +1013 A allele increased the risk of lung squamous cell carcinoma (OR = 3.20, 95%CI: 1.75-5.84, P = 0.000), lung adenocarcinoma (OR = 1.55, 95%CI: 1.00-2.41, P = 0.049) and other types of lung cancer (OR = 1.96, 95% CI: 1.10-3.49, P = 0.023), but no association was found between the two SNPs and other clinical features. (3) IGF-1R +1013 (G/A) and IGF-2R +1619(G/A) polymorphisms showed a synergic effect (P = 0.003). CONCLUSION: The common IGF-1R gene polymorphism G1013A may influence the risk of lung cancer. The polymorphisms of IGF-1R +1013 (G/A) and IGF-2R +1619 (G/A) have synergistic influence on the risk of lung cancer.

Palladium-catalyzed carboxylative cyclization of propargylic amines with aryl iodides, CO2 and CO under ambient pressure.

A palladium-catalyzed four-component carboxylative cyclization comprising propargylic amines, aryl iodides, CO2 and CO was developed. By selecting Et3N and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the base, respectively, both terminal and internal propargylic amines proceeded well facilitated by Pd(PPh3)2Cl2, affording the functionalized 2-oxazolones in moderate yields. This protocol enlarges the product diversity based on CO2 conversion and simultaneously provides a cooperative transformation route for both CO2 and CO.

Visible light-driven carbamoyloxylation of the α-C(sp3)-H bond of arylacetones via radical-initiated hydrogen atom transfer.

Photocatalytic synthesis has emerged as an efficient route to transform CO2 into functionalized organic carbamates by photocatalysis. Herein, a catalyst-free carbamoyloxylation of arylacetones with CO2 and amines under visible light was developed for the synthesis of O-ß-oxoalkyl carbamates in yields up to 93%. This protocol proceeded smoothly with the assistance of inexpensive carbon tetrabromide at room temperature under atmospheric CO2 pressure, leading to simultaneous construction of C-O and C-N bonds. Mechanism studies suggested the photoinduced hydrogen atom transfer (HAT) pathway followed by radical addition or single electron transfer (SET).

Biomass-Based N-Rich Porous Carbon Materials for CO2 Capture and in-situ Conversion.

Capturing CO2 and subsequently converting into valuable chemicals has attracted extensive attention. Herein, a series of biomass-based N-rich porous carbon materials with high specific surface area and pore volume were prepared using biomass waste soybean dregs as precursors. The nitrogen content was up to 4 % with different forms in the carbon skeleton such as pyridine-N, pyrrole-N. The synergistic effect of ultra-micropore (pore size <0.7 nm) and N-containing groups endowed the materials with a high CO2 adsorption capacity, reaching 6.3 and 3.6 mmol g-1 at 0 and 25 °C under atmospheric pressure, respectively. In addition, the sufficient interaction between N-containing groups and CO2 was demonstrated by solid-state nuclear magnetic resonance spectroscopy, and the captured CO2 was possibly activated in the form of carbamate, which is conducive to subsequent conversion. Therefore, the supported catalyst with the as-synthetic porous carbon material as the carrier and ZnII as catalytic sites was prepared and successfully applied for carboxylative cyclization of propargylic amine with CO2 to afford the 3-benzyl-5-methyleneoxazolidin-2-one. The results showed that CO2 capture and in-situ conversion work effectively to produce highly value-added chemicals. In this process, the captured CO2 could be activated and fixed into chemicals in mild conditions. More importantly, the energy consumption in CO2 desorption and adsorbent regeneration could be avoided. The valorization of both solid waste and CO2 to valuable chemicals provides an elegant strategy of killing three birds with one stone.

The effects of acupuncture therapy in migraine: An activation likelihood estimation meta-analysis.

Background: Previous functional magnetic resonance imaging studies indicated that acupuncture could activate the brain regions in patients with migraine. However, these studies showed inconsistent results. This activation likelihood estimation (ALE) meta-analysis aimed to investigate the consistent activated change of brain regions between pre- and post-acupuncture treatment in migraineurs. Methods: We conducted a literature search in PubMed, Embase, Web of Science, the Cochrane Library, the China National Knowledge Infrastructure, the Chinese Science and Technology Periodical Database, the Wanfang Database, and the Chinese Biomedical Literature Database from their inception to 18 August, 2022, to obtain articles assessing the functional magnetic resonance imaging changes of acupuncture for migraine. Two investigators independently performed literature selection, data extraction, and quality assessment. The methodological quality was assessed with a modified version of the checklist. The reporting quality of interventions among included studies was evaluated by the Revised Standards for Reporting Interventions in Clinical Trials of Acupuncture (STRICTA). Our meta-analysis was conducted according to the GingerALE software. The Jackknife sensitivity analysis was used to assess the robustness of the results. Results: 14 articles were finally included according to the eligible criteria. Regarding the immediate effect of acupuncture on migraine, the ALE meta-analysis demonstrated that the deactivation regions were mainly located in the superior frontal gyrus, and middle frontal gyrus (uncorrected P < 0.001). The ALE meta-analysis of the cumulative effect showed that the activation regions were the thalamus, superior frontal gyrus, posterior lobe of the cerebellum, insula, middle frontal gyrus, precentral gyrus, anterior cingulate, and the deactivation brain regions were located in the transverse temporal gyrus, postcentral gyrus, superior temporal gyrus, anterior cingulate, parahippocampal gyrus, inferior parietal lobule, and inferior occipital gyrus (uncorrected P < 0.001). Conclusion: Acupuncture could activate multiple brain areas related with the regulation of pain conduction, processing, emotion, cognition, and other brain regions in patients with migraine. In the future, the combination of multiple imaging technologies could be a new approach to deeply investigate the central mechanism of acupuncture for migraine.

[Effects of human Livin gene down-regulation by RNA interference on xenograft of transplantation tumor induced by SPC-A1 in nude mice].

OBJECTIVE: To explore the in vivo inhibitory effect of Livin gene silencing by RNA interference on xenograft of lung adenocarcinoma SPC-A-1 cells in BALB/C nude mice. METHODS: Three different BALB/C nude mice models were established by subcutaneously inoculating differently treated SPC-A-1 cells into 3 nude mice groups: the blank control group was inoculated with blank SPC-A-1 cells, while the negative group was inoculated with cells transfected with lentivirus-delivered negative shRNA, the experimental group was inoculated with cells with lentivirus-delivered Livin shRNA. Then the growth of tumors was observed, and the volume and weight of the tumors were measured at different time points. The curve of tumor growth was then described, and the inhibition rate was calculated. Livin gene expression in the tumor tissues was determined by RT-PCR and Immunohistochemistry. Cell apoptosis of tumor tissues was detected by TUNEL. RESULTS: Slower tumor growth, smaller tumor volume and lighter tumor weight were observed in the experimental group as compared to the blank and negative groups (F = 70.509, P < 0.01; F = 12.821, P < 0.01). The inhibition rate of tumor volume was (59.5 ± 3.4)%, and the inhibition rate of tumor weight was (71.1 ± 5.6)%. Livinα mRNA and Livinß mRNA expressions in the experimental group were significantly lower than the 2 control groups [(37.2 ± 1.6)% versus (63.3 ± 3.8)%, (66.1 ± 2.6)%; (29.4 ± 1.1)% versus (53.2 ± 3.4)%, (52.3 ± 3.1)% (F(α) = 45.309, P < 0.01; F(ß) = 30.076, P < 0.01)]. Livin protein expression level was also significantly lower than the blank and the negative groups [(15.3 ± 2.8)% versus (51.3 ± 2.1)%, (52.5 ± 2.5)%, F = 78.92, P < 0.01]. The apoptosis rate in the experimental group was significantly higher than that in the 2 control groups [(35.4 ± 3.2)% versus (5.4 ± 1.3)%, (8.6 ± 1.5)%, F = 14.509, P < 0.01]. CONCLUSION: The lentivirus-delivered Livin shRNA was shown to inhibit the proliferation of transplantation tumor of lung carcinoma effectively, and Livin may be a target for gene therapy in lung cancer.