Asymmetric orbital hybridization in Zn-doped antiperovskite Cu_(1-x)Zn_(x)NMn_(3)enables highly efficient electrocatalytic hydrogen production

Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.

First Asymmetric Synthesis of (-)Methyl 2, 2-dimethyl-3-hydroxychromanyl-6-formate

Aim To synthesize naturally occurring (-) methyl2,2-dimethyl-3-hydroxychromanyl-6-formate. Methods Sharpless' asymmetric dihydroxylation wasemployed to construct the 3-hydroxychroman. Results First asymmetric synthesis of (-) methyl 2,2-dimethyl-3-hydroxychromanyl-6-formate (1) was accomplished starting from methyl 4-hydroxy-benzoate(2), and the absolute configuration was established. Conclusion A useful method for constructingchiral 3-hydroxychroman by employing Sharpless' asymmetric dihydroxylation is achieved.

Enantioselective synthesis of chiral phosphonylated 2,3-dihydrofurans by copper catalyzed asymmetric formal [3+2] cycloaddition of propargylic esters with β-keto phosphonates

Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.

有机催化3-氨基氧化吲哚与偶氮二羧酸酯的不对称加成反应

手性3,3-双取代氧化吲哚结构单元广泛存在于具有生物活性的天然产物和具有药物活性的化合物中,尤其存在于具有光学活性的3-氨基氧化吲哚中。此外,手性3,3-双取代氧化吲哚结构单元作为有效抗疟药(NITD609)、高效焦虑和抑郁抑制剂(SSR149415)以及HIV蛋白酶抑制剂而备受关注。因此,发展合成手性3-氨基氧化吲哚的新方法具有重要意义。为了实现反应的敏感性产物N,N′-缩靛红衍生物的不对称合成,使用金鸡纳碱衍生的方酰胺作催化剂,3-氨基氧化吲哚席夫碱与偶氮二羧酸酯作模板底物,最终以70%~85%的产率和45%~88%的对映选择性获得相应产物。该反应的实验条件温和,原子经济性高。

3-羟基色酮的不对称Michael加成反应

3-羟基色酮骨架存在于大量天然产物中,其衍生物多具有重要的生理活性和潜在的药用价值,但目前对3-羟基色酮的不对称手性催化反应研究较少。为丰富3-羟基色酮的研究多样性,通过控制变量法对手性金鸡纳碱类催化剂、溶剂、温度、投料比、底物浓度和催化剂用量进行筛选,确定了最佳的反应条件:以化合物1a和2a的反应为例,0.10 mmol的化合物1a与0.12 mmol的化合物2a在Cat*5(10%,物质的量分数)的催化下,在1.0 mL的甲基叔丁基醚(MTBE)中于0℃下反应24~48 h。对底物进行普适性研究,以中等至优异的收率(71%~99%)和较好的对映选择性(56%~89%)获得了2-芳基3-羟基色酮衍生物。将对映选择性最高的产物3al(89%)进行30倍放大反应,能够以99%的收率和76%的对映选择性获得目标产物。所有化合物的结构经1H NMR,13C NMR, HPLC以及HR-MS(ESI)确证。

3D Macro-Micro-Mesoporous FeC2O4/Graphene Hydrogel Electrode for High-Performance 2.5 V Aqueous Asymmetric Supercapacitors

Distinguished from commonly used Fe2O3 and Fe3O4,a three-dimensional multilevel macromicro-mesoporous structure of FeC2O4/graphene composite has been prepared as binderfree electrode for supercapacitors.The as-prepared materials are composed of macroporous graphene and microporous/mesoporous ferrous oxalate.Generally,the decomposition voltage of water is 1.23 V and the practical voltage window limit is about 2 V for asymmetric supercapacitors in aqueous electrolytes.When FeC2O4/rGO hydrogel was used as the negative electrode and a pure rGO hydrogel was used as the positive electrode,the asymmetrical supercapacitor voltage window raised to 1.7 V in KOH(1.0 mol/L)electrolyte and reached up to 2.5 V in a neutral aqueous Na2SO4(1.0 mol/L)electrolyte.Correspondingly it also exhibits a high performance with an energy density of 59.7 Wh/kg.By means of combining a metal oxide that owns micro-mesoporous structure with graphene,this work provides a new opportunity for preparing high-voltage aqueous asymmetric supercapacitors without addition of conductive agent and binder.

A rational preparation strategy of phase tuned MoO_(3) nanostructures for high-performance all-solid asymmetric supercapacitor

In this work,phase and morphology-tuned MoO_(3) nanostructures are synthesized through a novel modified co-precipitation method,and their electrochemical properties are investigated.For the first time,such a simple surfactant-assisted synthesis process aided by minor temperature variations is reported which results in phase transition of the nanoparticles from h-MoO_(3) nano-rods to a-MoO_(3) nano-flakes.The nanostructures thus developed are highly porous and crystalline with significantly large specific surface area as compared to previous literature.The theoretical bandgap energy of the optimized sample calculated using Perdew-Zunger local density approximation(LDA) is in good agreement with the experimental findings.An overall structural,morphological,and surface-behavioural analysis predicts the electrochemical superiority in 2D a-MoO_(3).The cyclic voltammetry and galvano-potentiometry measurements of 2D a-MoO_(3) in the potential window of-0.6 V to +0.2 V present the highest pseudosupercapacitive response with a maximum specific capacitance of 829 F g^(-1)at 2 A g^(-1)as compared to h-MoO_(3) (452 F g^(-1)) and h@a-MoO_(3) (783 F g^(-1)).Thus,the MoO_(3) 2D nanostructures synthesized through our novel synthesis technique display excellent specific capacitance as compared to previous reported data.Additionally,a-MoO_(3) exhibits a galvanostatic charging-discharging cyclic stability of about 91%after 2000 cycles,indicating that it can serve as an excellent electrode material for supercapacitors.A solid-state asymmetric supercapacitor device is successfully constructed using a-MoO_(3) which can light up 4 red LEDs for 10 s.The specific energy density of the device reaches a maximum value of 36.3 W h kg^(-1)at the power density of 50 W kg^(-1).

一种基于LTCC技术的3 dB电桥设计与制作

针对当前通信系统对3 dB电桥等多种无源器件多频带和小型化等要求,利用低温共烧陶瓷(LTCC)工艺设计了一款具有新型结构的3 dB 90°电桥,采用蛇形和螺旋宽边耦合带状线的方式,实现了电桥的小型化和超宽带。通过软件ANSYS HFSS对电桥进行三维建模,并在LTCC工艺线加工制作,实际制作的电桥的测量结果与仿真结果几乎一致。研制的3 dB电桥的工作频率为1~2.7 GHz,尺寸为3.2 mm×1.6 mm×0.95 mm,相位不平衡度小于±5°,幅度不平衡度小于2 dB,带内插损小于2 dB,隔离度大于15 dB,输入电压驻波比小于1.5。

Asymmetric synthesis of 3-butylphthalide using isomannide and isosorbide as chiral auxiliaries

A new approach for asymmetric syntheses of （S） and （R）-3-n-butylphthalide （NBP） is presented. The diastereoselective addition of dibutylzinic to aromatic aldehyde 10 or 11 generated from isomannide- or isosorbide-derived chiral auxiliary afforded S-NBP or R-NBP in high optical yields.

Modeling and Simulation of Pipeline Security Monitoring System Based on Line-Structure Sagnac Interferometer with 3×3Coupler

The third damage action,human disruption behavior,is one of the major threats to pipeline operation.It is necessary to monitor and locate the perturbation behavior that may threat pipeline safety in real-time.Therefore,a new pipeline security monitoring system is designed by using line-structure Sagnac optic fiber interferemeter with the characteristic of 3×3coupler that can modulate the phase of optic signal,with no need for phase modulation and demodulation.The optic structure of the new system is simplified,the signal processing accuracy is improved,and the polarization effect is reduced.The working principle of the monitoring in ideal condition is described,the phase demodulation is analyzed and the location of the possible damage action point is formulated.By using simulink,the optic signal propagation and interference is simulated and interference signals in different frequencies are obtained.The results validate the feasibility of the monitoring system and indicate that the low frequency signal less than 1kHz resulting from the human damage action can be detected.The disturbance set at 10 km can be located by calculating the demodulation signal accurately over a long monitoring distance.

Reconfigurable 3/6 dB Novel Branch Line Coupler

In this paper, a new idea of reconfigurable 3/6 dB branch line coupler is proposed. The proposed coupler is tuned through a simple open and short circuit at the coupler’s branches’ edges. At the short edges case, a 3 dB branch line coupler is obtained. In this case, the coupler’s branches are considered as microstrip transmission lines with 0.3 mm slot width which is etched in each coupler’s branch. At the open edges case, the coupler’s branches are considered as asymmetric coupled microstrip lines. In this case, a 6 dB branch line coupler is obtained. Both CST and IE3D simulators are used to optimize the reconfigurable 3/6 dB branch line coupler dimensions. As a prototypes, two BLCs are designed, analyzed and tested at the “on” and “off” states at 2.5 GHz. The measured S-parameters confirm the proposed concept of the reconfigurable 3/6 dB branch line coupler.

Representation of the ENSO Combination Mode and its Asymmetric SST Response in Different Resolutions of HadGEM3

Previous studies have revealed a combination mode （C-mode） occurring in the Indo-Pacific region, arising from nonlinear interactions between ENSO and the western Pacific warm pool annual cycle. This paper evaluates the simulation of this C-mode and its asymmetric SST response in HadGEM3 and its resolution sensitivity using three sets of simulations at horizontal resolutions of N96, N216 and N512. The results show that HadGEM3 can capture well the spatial pattern of the C-mode associated surface wind anomalies, as well as the asymmetric response of SST in the tropical Pacific, but it strongly overestimates the explained variability of the C-mode compared to the ENSO mode. The model with the three resolutions is able to reproduce the distinct spectral peaks of the C-mode at the near annual combination frequencies, but the performance in simulating the longer periods is not satisfactory, presumably due to the unrealistic simulation of the ENSO mode. Increasing the horizontal resolution can improve the consistency between atmospheric and oceanic representations of the C-mode, but not necessarily enhance the accuracy of C-mode simulation compared with observation.

Nucleon ~3pF_2 Superfluid Pairing Gap in Asymmetry Nuclear Matter

The 3 P F2 superfluidity of neutron and proton is investigated in isospin-asymmetric nuclear matter within the Brueckner-Hartree-Fock approach and the BCS theory by adopting the Argonne V14 and the Argonne V18 nucleonnucleon interactions. We find that pairing gaps in the 3PF2 channel predicted by adopting the AV14 interaction are much larger than those by the AV18 interaction. As the isospin-asymmetry increases, the neutron 3 pF2 superfluidity is found to increase rapidly, whereas the proton one turns out to decrease and may even vanish at high enough asymmetries. As a consequence, the neutron 3pF2 superfluidity is much stronger than the proton one at high asymmetries and it predominates over the proton one in dense neutron-rich matter.

SYNTHESIS AND STRUCTURE OF AN ASYMMETRIC TRICOBALT COMPOUND Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3

Compound Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3 was obtained by reaction of CoCl_2, o-HOC_6H_4SH(H_2mD)and PEt_3 in ethanol in the presence of NaOCH_3.The three Co atoms are triangularly arranged and asymmetrically bridged by four S and one O atoms from the four H_2mp ligands and terminally ligated by one O and three P atoms.Two free hydroxyl groups form two internal hydrogen bonds with adjacent oxo donor atoms.

NATURAL PRODUCTS SYNTHESIS BY RETRO-DIELS-ALDER REACTION Ⅱ~1 ASYMMETRIC SYNTHESIS OF (+) AND (-) 5-OXO-ENDO-TRICYCLO [5.2.1.0.^(2, 6)] DECA-3, 8-DIENE 1 BY ENZYME-CATALYZED REACTION

Asymmetric syntheses of both enantiomerically pure (+) and (-) 5-oxo-endo-tricyclo [5.2.1.0.^(2,6)] deca-3, 8-diene 1 was described. The key step is the use of enzyme-catalyzed hydrolysis of meso-diacetate 5.

ASYMMETRIC SYNTHESIS Ⅻ:HIGHLY ENANTIOSELECTIVE SYNTHESIS OF α-AMINO ACIDS BY ALKYLATION OF THE KETIMINE FROM 2-HYDROXY-PINAN-3-ONE AND MENTHYL GLYCIN-ATE A DOUBLE ASYMMETRIC INDUCTION SYSTEM

A series of α-amino acids are obtained in 72-96% optical yields by alkylation of the ketimine derived from(+)-2-hydroxy-pinan-3-one and(-)-menthyl glycinate fol- lowed by hydrolysis of the alkylated intermediates with mineral acid.The double asymmetric induction are explained by the transition model of lithium enolate.

Asymmetric 1,3-Dipolar Cycloaddition of the Chiral Nitronic Esters with Acrylate

Asymmetric 1,3-dipolar cycloaddihon of the chiral nitronic esters with acrylate giving the enantiomerically pure novel chiral bisheterocyclic compounds is describcd

Asymmetric Diels-Alder Reaction of 1-(S_R)-p-Tolylsulfinyl-3-penten-2-one with Cyclopentadiene Catalzed by a Chiral Titanium Reagent

Double asymmetric Diels-Alder reaction of 1(SR)-p-Tolylsulfinyl-3-penten-2-one with cyclopentadiene using a chiral titanium reagent was performed. The diastereoselectivity dependent on the size of aryl substituent involved in the chiral ligands was discussed Absolute configuration of the cycloadducts was conformed. Dramatic reversal of selectivity is observed.

Asymmetric synthesis of 3β-acetoxy-17,17-ethylendioxy-15β,16β-methylene-5-androsten-7β-ol

acetoxy-17,17-ethylendioxy-15β,16β-methylene-5-androsten-7β-ol（Ⅰ） was prepared by 3 steps from 3β-acetoxy-15β,16β-methylene-5-androsten-17-one （Ⅱ） with overall yield of 52.7%. Thus, interaction of ethylene glycol and material （Ⅱ） gave 3β-acetoxy- 17,17-ethylendioxy-15β,16β-methylene-5-androsten （Ⅲ） which was subsequently oxidated and stereoselectively reduced to produce compound（Ⅰ）. The normal influencing factors, such as the types of oxidants and reductives, the mole ratio of reactants, the reaction temperature, and the addition ways of reactants, in oxidation and reduction were discussed. The results show that the oxidation rate order is CrO3-C5H5N （1∶1, mole fraction）>CrO3-C5H5N（1∶2）>（C5H5NH）2Cr2O7 in terms of the oxidant, the yield of the oxidation becomes higher with increasing the oxidant stoichiometry and raising the reaction temperature. And the optimum condition is that the reaction temperature is at 30 ℃, and n （Ⅲ）/ n （CrO3-C5H5N（1∶2））=1∶20. The yield of the -7β alcohol order with Li[Al（OC（CH3）3）3H] （e.g.78.6%） is more than that with NaBH4 （e.g.14.5%） in terms of the reductive （agent） and the reduction rate decreases in the course of reaction. The compound （Ⅰ） is characterized by IR and MS.

基于3×3耦合器的双马赫-曾德尔干涉仪数字化相位解调

由于马赫-曾德尔(Mach-Zehnder)光纤干涉传感系统的定位精度在实际应用中受到初始相位偏移的影响,本文针对系统的光路结构,提出了一种基于3×3耦合器的被动数字化解调方法。利用3×3耦合器的2路输出信号构成椭圆曲线,在约束条件下对信号系数进行最小二乘拟合,然后采用微分交叉相乘法解调出相位信号。与传统的解调方法相比,提出的方法降低了对耦合器高对称性的要求,不需限制其它参数;约束条件下椭圆拟合的鲁棒性好,尤其是对于椭圆度较差的数据点具有很强的适应能力,适用于微弱振动信号的解调。仿真结果和现场实验数据证明该方法切实有效,运算量小,利用现场数据解调出的相位信号相关性达到0.992 0;互相关计算显示其在总长43km的管道上的定位误差为81.2m,有效提高了系统性能。