Strategies for constructing seven-membered rings:Applications in natural product synthesis

The seven-membered ring motifs are found in bioactive pharmaceuticals and a wide range of natural products,including alkaloids and terpenoids,which hold significant importance in synthetic chemistry and has garnered considerable attention from both academia and industry.Despite the challenges faced in the past decade,the total synthesis of natural products incorporating the non-aromatic cycloheptane skeletons remains a compelling pursuit.Recently,numerous elegant strategies for constructing the sevenmembered ring system have been successfully developed.This review focuses on the recent advancements in this field from 2017 to April 2023,highlighting key transformations utilized to construct the non-aromatic cycloheptane core structures and serves as a valuable guide for synthetic chemists engaged in the total synthesis of natural products containing seven-membered ring motifs.

Single atom Cu-N-C catalysts for the electro-reduction of CO_(2) to CO assessed by rotating ring-disc electrode

The electrochemical CO_(2) reduction reaction(CO_(2)RR) to controllable chemicals is considered as a promising pathway to store intermittent renewable energy. Herein, a set of catalysts based on copper-nitrogendoped carbon xerogel(Cu-N-C) are successfully developed varying the copper amount and the nature of the copper precursor, for the efficient CO_(2)RR. The electrocatalytic performance of Cu-N-C materials is assessed by a rotating ring-disc electrode(RRDE), technique still rarely explored for CO_(2)RR. For comparison, products are also characterized by online gas chromatography in a H-cell. The as-synthesized Cu-NC catalysts are found to be active and highly CO selective at low overpotentials(from -0.6 to -0.8 V vs.RHE) in 0.1 M KHCO_(3), while H_(2) from the competitive water reduction appears at larger overpotentials(-0.9 V vs. RHE). The optimum copper acetate-derived catalyst containing Cu-N_(4) moieties exhibits a CO_(2)-to-CO turnover frequency of 997 h^(-1) at -0.9 V vs. RHE with a H_(2)/CO ratio of 1.8. These results demonstrate that RRDE configuration can be used as a feasible approach for identifying electrolysis products from CO_(2)RR.

Winter-spring minimum temperature variations inferred from tree-ringδ13C in southeastern China

Long-term temperature variations inferred from high-resolution proxies provide an important context to evaluate the intensity of current warming.However,tem-perature reconstructions in humid southeastern China are scarce and particularly lack long-term data,limiting us to obtain a complete picture of regional temperature evolution.In this study,we present a well-verified reconstruction of winter-spring(January–April)minimum temperatures over southeastern China based on stable carbon isotopic(δ^(13)C)records of tree rings from Taxus wallichiana var.mairei from 1860 to 2014.This reconstruction accounted for 56.4%of the total observed variance.Cold periods occurred during the 1860s–1910s and 1960s–1970s.Although temperatures have had an upward trend since the 1920s,most of the cold extremes were in recent decades.The El Niño-Southern Oscillation(ENSO)variance acted as a key modulator of regional winter-spring minimum temperature variability.However,teleconnections between them were a nonlinear process,i.e.,a reduced or enhanced ENSO variance may result in a weakened or intensified temperature-ENSO relationship.

Application and verification of simultaneous determination of cellulose δ^(13)C and δ^(18)O in Picea shrenkiana tree rings from northwestern China using the high-temperature pyrolysis method

Stable isotopes in tree-ring cellulose provide important data in ecological,archaeological,and paleoenvironmental researches,thereby,the demand for stable isotope analyses is increasing rapidly.Simultaneous measurement of cellulose δC and δO values from tree rings would reduce the cost of isotopic commodities and improve the analytical efficiency compared with conventional separate measurement.In this study,we compared the δC and δO values of tree-ringα-cellulose from Tianshan spruce(Picea schrenkiana)in an arid site in the drainage basin of the Urumqi River in Xinjiang of northwestern China based on separate and simultaneous measurements,using the combustion method(at1050°C)and the high-temperature pyrolysis method(at 1350°C and 1400°C).We verified the results of simultaneous measurement using the outputs from separate measurement and found that both methods(separate and simultaneous)produced similar δC values.The two-point calibrated method improved the results(range and variation)of δC and δO values.The mean values,standard deviations,and trends of the tree-ring δC obtained by the combustion method were similar to those by the pyrolysis method followed by two-point calibration.The simultaneously measured δO from the pyrolysis method at 1400°C had a nearly constant offset with that the pyrolysis method at 1350°C due to isotopic-dependence on the reaction temperature.However,they showed similar variations in the time series.The climate responses inferred from simultaneously and separately measured δC and δO did not differ between the two methods.The tree-ring δC and δO values were negatively correlated with standardized precipitation evapotranspiration index from May to August.In addition,the δO was significantly correlated with temperature(positive),precipitation(negative),and relative humidity(negative)from May to August.The tree-ring δC and δO values determined simultaneously through the high-temperature pyrolysis method could produce acceptable and reliable stable isotope series.The simultaneous isotopic measurement can greatly reduce the cost and time requirement compared with the separate isotopic measurement.These results are consistent with the previous studies at humid sites,suggesting that the simultaneous determination of δC and δO in tree-ringα-cellulose can be used in wide regions.

Accurate theoretical evaluation of strain energy of all-carboatomic ring(cyclo[2n]carbon),boron nitride ring,and cyclic polyacetylene

Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbons of different sizes using regression analysis method based on electronic energies evaluated at the very accurate DLPNO-CCSD(T)/ccp VTZ theoretical level.In addition,ring strain of two systems closely related to cyclocarbon,boron nitride(BN)ring,and cyclic polyacetylene(c-PA),is also explored.Very ideal relationships between SE and number of repeat units(n)are built for cyclo[2n]carbon,B_(n)N_(n),and[2n]c-PA as SE=555.0·n^(-1),145.1·n^(-1),and 629.8·n^(-1)kcal·mol^(-1),respectively,and the underlying reasons of the difference and similarity in their SEs are discussed from electronic structure perspective.In addition,force constant of harmonic potential of C-C-C angles in cyclocarbon is derived based on SE values,the result is found to be 56.23 kcal·mol^(-1)·rad^(-2).The possibility of constructing homodesmotic reactions to calculate SEs of cyclocarbons is also explored in this work,although this method is far less rigorous than the regression analysis method,its result is qualitatively correct and has the advantage of much lower computational cost.In addition,comparisons show thatωB97XD/def2-TZVP is a good inexpensive alternative to the DLPNO-CCSD(T)/cc-p VTZ for evaluating energies used in deriving SE,while the popular and very cheap B3LYP/6-31G(d)level should be used with caution for systems with global electron conjugation such as c-PA.

Tree-Ring Carbon Isotopic Constraints on Carbon-Water Exchanges between Atmosphere and Biosphere in Drought Regions in Northwestern China

The comparison between the carbon isotope and the index of ring width of a pine disc from the Tuomuer Peak region in Xinjiang shows that the effects of climate changes on the tree-ring growth and carbon isotopic fractionation varies with time. The reason is probably relative to the characters of climate changes and adaptability of the tree-ring growth to climate changes. The relationships between the atmospheric CO2 level and the revised δ13Cair by the tree-ring carbon isotope indicate that the carbon cycle is not in a steady state, but under a stage-change condition in this area. It also can be concluded that the ratio of CO2 from the terrestrial eco-system has increased, and the flux of CO2 exchange between the atmosphere and the biosphere was gradually increasing over the past century. In addition, the results also confirm the validity and superiority of the carbon isotope to the research of the water-use efficiency.

RING-OPENING POLYMERIZATION OF TRIMETHYLENE CARBONATE CATALYZED BY NOVEL SINGLE COMPONENT RARE EARTH CALIXARENE COMPLEXES

In this paper,ring-opening polymerization of trimethylene carbonate(TMC)with rare earth(Nd,Y,La)ρ-tert- butylcalix[n]arene(n=4,6,and 8)complexes as catalysts has been studied.Poly(trimethylene carbonate)(PTMC)with M_v of 21,400 was produced by bulk polymerization under the conditions as follows:[TMC]_0/[Nd](molar ratio)=1000,80℃, 8 h.Mechanism study reveals that the polymerization proceeds via a coordination mechanism.

RING-OPENING POLYMERIZATION OF TRIMETHYLENE CARBONATE BY CALIX[8]ARENE-NEODYMIUM

Ring-opening polymerization of trimethylene carbonate (TMC) with a rare earth calixarene compound as catalyst has been studied for the first time. The effect of TMC/Nd (molar ratio) and polymerization conditions were investigated in detail. It was found that calix[8]arene-neodymium is a highly effective catalyst for the bulk polymerization of TMC and gives high molecular weight (M-v = 60,000) polymer. The optimum conditions of TMC polymerization were found to be as follows:TMC/Nd (molar ratio) = 2,000, 80 degrees C, 16 h. The polymers were characterized by NMR, GPC and DSC. Studying the mechanism by NMR showed that the polymerization of TMC catalyzed by calix[8]arene-neodymium proceeds via a cationic mechanism.

Progress in organocatalytic asymmetric (4+3) cycloadditions for the enantioselective construction of seven-membered rings

Chiral seven-membered ring systems such as seven-membered carbocycles and heterocycles are widely found in natural products and pharmaceuticals.Therefore,the catalytic enantioselective construction of such frameworks has evoked considerable interest in the field of chemistry.Among the various approaches,organocatalytic asymmetric(4+3)cycloadditions are highly effective for the enantioselective construction of seven-membered rings.Over the past two decades,substantial efforts have been devoted to this field and chemists have developed various organocatalytic asymmetric(4+3)cycloadditions.This review summarizes the progress in organocatalytic asymmetric(4+3)cycloadditions from 2003 to early 2022 and provides insights into challenging issues faced in this research field,enabling the future development of this field.

Ring chromosome aberrations in human lymphocytes induced by 5-20 Gy carbon ion irradiation

In this paper,we study the biological response induced by heavy ions irradiation of high dose,human peripheral blood lymphocytes are irradiated in vitro by the carbon ions of LET=35 keV/μm,and the chromosome aberrations at absorbed doses of 0-20 Gy are analyzed by the calyculin A-induced premature chromosome condensation(PCC).The frequencies of PCC-rings at the stage of G2/M-phase increase steeply with radiation doses up to 20 Gy at a rate of 0.017 Gy^(-1).The G2-PCC index remains more than 5%up to 15 Gy,and 3%after 20 Gy,this is high enough to score a substantial number of chromosome spreads without dose-rate effect.The results show that the calyculin A-induced PCC technique is suitable for analyzing the chromosome damage induced by carbon ions irradiation of high dose.

Synthesis and Characterization of Novel Aliphatic Polycarbonates Bearing Pendant Allyl Ether Groups

A new six-membered cyclic carbonate monomer, 5-allyloxytrimethylene carbonate （ATMC）, was synthesized starting from glycerol, and the corresponding polycarbonates, poly（5-allyloxytrimethylene carbonate）（PATMC） were further synthesized by ring-opening polymerization in bulk at 150℃ using stannous octanoate as an initiator. The structures of the monomer and the polymers were confirmed by IR, IH-NMR, 13C-NMR, and GPC analysis.

Rare Earth Complex Initiated Ring-Opening Polymerization of 2,2-Dimethyltrimethylene Carbonate

The ring opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC) initiated by single component of tris(2,6-di-tert-butyl-4-methylphenoxo) lanthanide (Ln(OAr)(3)) is reported. The initiators are highly active to the polymerization and give high molecular weight polymers. (HNMR)-H-1 spectra and DSC measurement suggest the polymerization is free of decarboxylation. Mechanism study shows that the monomer insertion is via the break of acyl-oxygen bond of DTC.

基于多个热成像探头传感器的滑环装置碳刷温度监测与分析

文章设计了一款基于多个热成像探头传感器的滑环装置碳刷温度监测系统,该系统利用热成像探头传感器来获取碳刷的温度数据,并通过数据处理和分析,实现对碳刷温度的监测和报警。系统采用热成像视频监测,增加现地显示装置,通过对系统进行设计,实现了历史数据查询、故障预警等多种功能,可更好地保障水利发电的安全运行。

用于铝压延厂房油雾控制的环吸式排风罩设计方法

环吸式排风罩是针对铝压延加工工艺油雾散发特征而提出的一种高效捕集设备,可以大幅降低系统风量,从而减少能耗和降低碳排放量,但目前仍缺乏此类排风罩的通用设计方法。本文选取10个铝压延车间铝冷轧机及排风罩为研究对象,探究了不同轧机尺寸组合下排风罩罩口处污染物扩散断面尺寸和排风罩捕集性能,通过回归分析得到了排风罩罩口设计尺寸和设计风量的计算方法,可供工程设计人员参考。

Differential response of radial growth and δ^(13)C in Qinghai spruce(Picea crassifolia) to climate change on the southern and northern slopes of the Qilian Mountains in Northwest China

Tree radial growth can have significantly differ-ent responses to climate change depending on the environ-ment.To elucidate the effects of climate on radial growth and stable carbon isotope(δ^(13)C)fractionation of Qing-hai spruce(Picea crassifolia),a widely distributed native conifer in northwestern China in different environments,we developed chronologies for tree-ring widths and δ^(13)C in trees on the southern and northern slopes of the Qilian Mountains,and analysed the relationship between these tree-ring variables and major climatic factors.Tree-ring widths were strongly influenced by climatic factors early in the growing season,and the radial growth in trees on the northern slopes was more sensitive to climate than in trees on the southern.Tree-ring δ^(13)C was more sensitive to climate than radial growth.δ^(13)C fractionation was mainly influenced by summer temperature and precipitation early in the growing season.Stomatal conductance more strongly limited stable carbon isotope fractionation in tree rings than photosynthetic rate did.The response between tree rings and climate in mountains gradually weakened as climate warmed.Changes in radial growth and stable carbon isotope fractionation of P.crassifolia in response to climate in the Qilian Mountains may be further complicated by continued climate change.

力载荷下分瓣式碳环密封结构变形研究

为探究力载荷下分瓣式碳环密封结构参数对密封面径向变形的影响规律,采用数值计算求解压力控制雷诺方程,获得气膜压力,再结合有限元分析软件进行流固热耦合仿真模拟,探究特定工况下不同结构参数对碳环变形的影响,分析主密封面径向变形特性。研究表明:力变形中,防转销的安装位置对碳环径向变形量影响最大,选取恰当的安装位置可减小径向变形量;外部凸结构不均匀且圆心角比例较大时,径向变形量较小;两侧搭接口比例越大时径向变形量越小;拉紧弹簧和压紧弹簧的选取对碳环径向变形量影响较小;弹簧压力越大时径向变形量越小,但弹簧压力过大时,容易导致碳环磨损加剧、断裂甚至密封失效,应参考实际工况选择适当弹簧压力。研究结果为分瓣式碳环密封的结构优化设计提供参考。

水轮发电机组碳刷/集电环摩擦副接触电阻计算及仿真验证

碳刷/集电环组件作为水轮发电机组励磁系统的重要组成部分,常因界面接触状态变化而出现碳刷过热、打火、电弧侵蚀等问题.其界面间的接触状态目前无法直接监测,间接监测则成为解决该问题的关键.载流摩擦副间的接触状态常用接触电阻进行表征,因此,本文中基于电接触和传热学的相关理论,建立了接触电阻的数学模型,该模型旨在根据碳刷温度估算接触电阻值.通过碳刷/集电环载流摩擦试验确定模型中的相关参数,计算并分析不同额定电流、转速、弹簧压力条件下,接触电阻的动态变化及关键影响因素.将计算结果代入COMSOL Multiphysics有限元分析软件中,基于其内置的物理场控制方程,仿真模拟碳刷的温度并与试验得到的碳刷的温度作比较,以验证该模型的有效性.计算结果表明:当界面接触压力一定时,接触电阻值随着额定电流的增大而减小;当额定电流一定时,界面接触压力大的碳刷接触电阻值小;当集电环转速增大时,弹簧压力对接触电阻的影响进一步增大.

改性淀粉基碳氮硫硅环钢结构防火涂料的研究

本试验对淀粉进行改性,制备了改性淀粉基碳氮硫硅环保钢结构防火涂料,探究了改性淀粉加入量对涂料性能的影响,并对其进行阻燃机理分析。结果表明,改性淀粉的加入能显著增强涂层黏结性能,对其余基本性能无影响,符合GB 14907—2018的规定;改性淀粉能显著提高涂层发泡性能和耐火性能,改性淀粉加入量为2%~6%时,涂层发泡厚度大于3.0 cm,涂层背面温度小于183.6℃;改性淀粉在受热时形成熔融状态钠醚盐,具有较好传质传热作用,有利于气源物质同步气化,与碳源炭化协调一致,改性淀粉在289.1℃左右时开始分解,相变结束后残碳量约为36.5%,在涂层中主要起碳源和小部分气源作用,且能改善涂层的成膜性能,降低成本,具有较好应用前景。

磷矿配炭球团高温固结工艺研究

为解决窑法磷酸工艺中回转窑结圈问题,提出一种球团高温固结工艺,考察了黏结剂种类、固结温度、固结时间对磷矿球团强度及其还原性的影响。结果表明,固结温度800℃以上,采用膨润土为黏结剂,球团抗压强度和落下强度明显高于腐殖酸钠为黏结剂的球团。在配碳量为理论用量的1.4倍、CaO与SiO_(2)物质的量比0.35、膨润土添加量为总物料量的1.5%、固结温度1000℃、固结时间30 min条件下,球团抗压强度和落下强度分别为345.36 N和33.50次。