Synthesis and Characterization of a Homochrial Manganese(Ⅱ)Complex Constructed from (1R,2R)-(-)-Diaminocyclohexane-N,N biscarboxyl-salicylidene)

A homochrial manganese（Ⅱ） complex derived from chiral salen ligand （1R,2R）-（-）diaminocyclohexane-N,N-biscarboxyl-salicylidene） （1） has been synthesized through solvothermal procedure and characterized by IR,elemental analysis,TGA,circular dichroism （CD）,powder and single-crystal X-ray crystallography.It crystallizes in monoclinic,space group C2 with a=32.987（7）,b=7.4662（15）,c=17.931（4）,β=97.82（3）°,V=4375.0（15） 3,Z=8,D c=1.544 g/cm 3,F（000）=2096,M r=508.36,μ=0.658 mm-1,the final GOOF=0.975,R=0.0676 and wR=0.2068 for 6357 observed reflections with I 2σ（Ⅰ）.The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by the dicarboxyl-functionalized metallosalen ligand （MnSalen）,and the polymeric chains are further assembled into a 2D supramolecular network structure via strong intermolecular hydrogen bonding interactions between the adjacent zigzag chains.

Synthesis and Crystal Structure of a Manganese(Ⅱ) Complex with 2-(4′-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Mn2（cbba）4（phen）2 （Hcbba = 2-（4＇-chlorine-benzoyl）- benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrotherrnally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound crystallizes in orthorhombic, space group Pbcn with α = 12.154（5）, b = 18.166（7）, c = 31.197（13） A, V = 6887（5） A^3, C80H48Cl4Mn2N4O12, Mr= 1508.90, Dc = 1.455 g/cm^3, μ（MoKα） = 0.591 mm^-1, F（000） = 3080, Z = 4, the final R = 0.0408 and wR = 0.0873 for 4033 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from phen ligands, showing a distorted octahedral geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions.

Syntheses and Characterizations of Two Manganese(Ⅱ)Coordination Polymers Containing Three-dimensional Interpenetrating Networks Constructed by Mixed Ligands

Two new three-dimensional coordination polymers, namely [Mn（L）（bpdc）]n（1）, [Mn（L）0.5（ndc）]n（2）（L = 1,4-bis（2-methylbenzimidazole）butane, H2 bpdc = 4,4＇-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthalenedicarboxylic acid） have been successfully synthesized under hydrothermal conditions. Two complexes were characterized by physico-chemical, spectroscopic methods and single-crystal X-ray diffraction. Complex 1 shows a 3D → 3D 5-fold interpenetrated network with a 4-connected uninodal dia topology. Complex 2 possesses a 3D → 3D 3-fold interpenetrating architecture with a binodal（4,5）-connected xah topology. The fluorescence and thermal properties of the title complexes were discussed.

搭接长度等对Ⅱ型APC接头拉伸性能的影响

为研究搭接长度和钢筋直径对Ⅱ型APC接头力学性能的影响,对63个该接头进行单向拉伸试验,分析了接头破坏模式、极限承载力、延性和黏结应力等。结果表明:钢筋直径相同时,随搭接长度增加,平均黏结应力降低,试件强度、延性、最大力总伸长率明显提高,残余变形整体呈下降趋势;钢筋拉断破坏试件强度、延性、最大力总伸长率和残余变形满足规范要求;加载过程中,套筒中部截面短边纵向和长边环向始终受拉;极限荷载下,随搭接长度增加,套筒中部截面短边侧环向压应变先转变为拉应变再向压应变发展,长边侧纵向压应变转变为拉应变;相对搭接长度相同时,极限承载力随钢筋直径增加而提高;提出的极限黏结强度及临界搭接长度计算公式与试验值吻合较好,可为实际工程应用提供参考。单拉工况下,钢筋直径不大于18 mm时,建议接头搭接长度大于12 d。

Heterointerface Engineering-Induced Oxygen Defects for the Manganese Dissolution Inhibition in Aqueous Zinc Ion Batteries

Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.

Facile synthesis of Cu-doped manganese oxide octahedral molecular sieve for the efficient degradation of sulfamethoxazole via peroxymonosulfate activation

Advanced processes for peroxymonosulfate(PMS)-based oxidation are efficient in eliminating toxic and refractory organic pol-lutants from sewage.The activation of electron-withdrawing HSO_(5)^(-)releases reactive species,including sulfate radical(·SO_(4)^(-)),hydroxyl radical(·OH),superoxide radical(·O_(2)^(-)),and singlet oxygen(1O_(2)),which can induce the degradation of organic contaminants.In this work,we synthesized a variety of M-OMS-2 nanorods(M=Co,Ni,Cu,Fe)by doping Co^(2+),Ni^(2+),Cu^(2+),or Fe^(3+)into manganese oxide oc-tahedral molecular sieve(OMS-2)to efficiently remove sulfamethoxazole(SMX)via PMS activation.The catalytic performance of M-OMS-2 in SMX elimination via PMS activation was assessed.The nanorods obtained in decreasing order of SMX removal rate were Cu-OMS-2(96.40%),Co-OMS-2(88.00%),Ni-OMS-2(87.20%),Fe-OMS-2(35.00%),and OMS-2(33.50%).Then,the kinetics and struc-ture-activity relationship of the M-OMS-2 nanorods during the elimination of SMX were investigated.The feasible mechanism underly-ing SMX degradation by the Cu-OMS-2/PMS system was further investigated with a quenching experiment,high-resolution mass spec-troscopy,and electron paramagnetic resonance.Results showed that SMX degradation efficiency was enhanced in seawater and tap water,demonstrating the potential application of Cu-OMS-2/PMS system in sewage treatment.

Covalency competition induced selective bond breakage and surface reconstruction in manganese cobaltite towards enhanced electrochemical charge storage

Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.

Mechanism of Capacity Fading Caused by Mn(Ⅱ)Deposition on Anodes for Spinel Lithium Manganese Oxide Cell

The capacity fade of spinel lithium manganese oxide in lithium-ion batteries is a bottleneck challenge for the large-scale application.The traditional opinion is that Mn（Ⅱ） ions in the anode are reduced to the metallic manganese that helps for catalyzing electrolyte decomposition.This could poison and damage the solid electrolyte interface（SEI） film,leading to the the capacity fade in Li-ion batteries.We propose a new mechanism that Mn（Ⅱ） deposites at the anode hinders and/or blocks the intercalation/de-intercalation of lithium ions,which leads to the capacity fade in Li-ion batteries.Based on the new mechanism assumption,a kind of new structure with core-shell characteristic is designed to inhabit manganese ion dissolution,thus improving electrochemical cycle performance of the cell.By the way,this mechanism hypothesis is also supported by the results of these experiments.The LiMn2-xTixO4 shell layer enhances cathode resistance to corrosion attack and effectively suppresses dissolution of Mn,then improves battery cycle performance with LiMn_2O_4 cathode,even at high rate and elevated temperature.

Synthesis, Crystal Structure and Theoretical Calculation of a Novel 2D Network of Manganese(Ⅱ) Complex

A novel complex, [Mn（2-NCP）（H2BTC）（H2O）]n（1, 1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid, 2-HNCP = 2-（2-carboxyphenyl）-1 H-imidazo（4,5-f）-（1,10）phenanthroline）, was hydrothermally synthesized and structurally characterized by elemental analysis, IR, XRD and single-crystal X-ray diffraction. Structural analyses reveal that complex 1 exhibits a（6, 6）-connected topology network with a Schl?fli symbol of（63）. The adjacent 2 D layers are further stacked via strong hydrogen-bonding interactions, giving a 3 D supramolecular framework. In addition, the structure of complex 1 was calculated by the B3LYP/LANL2 DZ method by Gaussian program. The results from natural bond orbital（NBO） analysis shows obvious covalent interaction between the coordinated atoms and Mn（Ⅱ） ion.

固定式下颌前移矫治器治疗青少年骨性Ⅱ类下颌后缩的临床效果

目的:观察固定式下颌前移矫治器治疗青少年骨性Ⅱ类下颌后缩的临床效果。方法:选取2023年3月—2024年8月在南昌大学附属口腔医院诊治的80例青少年骨性Ⅱ类下颌后缩患者,而后分组,指导原则为随机抽签法,具体组别为对照组、试验组,各组40例;其中,固定式下颌前移矫治器治疗方案用于试验组,对照组采用双颌垫矫正器,就青少年骨性Ⅱ类下颌后缩问题治疗效果展开比较。结果:两组治疗后SNA、ANB、U1-SN、L1-MP和Y轴角指标差异均无统计学意义(P>0.05),试验组SNB、MP-SN指标均比对照组大,差异均有统计学意义(P<0.05);治疗后,试验组L6-Ptm、L6-MP、CO-GO、GO-GN和ANS-Me指标均比对照组大,试验组U6-Ptm和U6-PP指标均比对照组小,差异均有统计学意义(P<0.05)。结论:在对青少年骨性Ⅱ类下颌后缩进行治疗时,将固定式下颌前移矫治器与双颌垫矫正器做比较,在部分角度及线性距离相关指标上,二者呈现出了不同的治疗效果,固定式下颌前移矫治器治疗效果优于双颌垫矫正器,这为临床治疗此类疾病提供了更多的参考依据,方便医生依据患者的具体情况选用更适宜的矫治器。

氨基酸功能化丝瓜络的辐射制备及其对Pb(Ⅱ)的吸附性能研究

以农林废弃物丝瓜络(LC)为基材,采用电子束辐射接枝法将聚甲基丙烯酸缩水甘油酯(PGMA)接枝到丝瓜络纤维表面,再通过开环反应引入赖氨酸(Lys)和精氨酸(Arg)功能性基团,制备得到2种氨基酸功能化丝瓜络LC-PGMA-Lys、LC-PGMA-Arg,通过FTIR、元素分析、XRD和SEM等方法对其进行了表征,系统研究了初始pH值、吸附时间、吸附温度、Pb(Ⅱ)初始浓度等因素对Pb(Ⅱ)吸附量的影响,并探究了其对Pb(Ⅱ)的吸附行为。结果表明,LC-PGMA-Lys、LC-PGMA-Arg吸附Pb(Ⅱ)的最佳初始pH值均为6;在初始pH值为6、吸附时间为200 min、吸附温度为35℃的最佳条件下,LC-PGMA-Lys对Pb(Ⅱ)的最大吸附量为71.18 mg·g^(-1);LC-PGMA-Lys对Pb(Ⅱ)的吸附过程符合准二级动力学方程和Freundlich等温吸附模型,表明吸附过程以多分子层吸附、化学吸附为主。

Hydrothermal Synthesis and Crystal Structure of a One-dimensional Manganese(Ⅱ) Compound Bridged by 2,6-Dichlorobenzoic Acid and Water

A novel manganese（Ⅱ） coordination polymer [Mn（L^1）2（H2O）]·2H2O （HL^1 = 2,6- dichlorobenzoic acid） 1 has been synthesized and structurally characterized. X-ray diffraction analyses reveal that 1 is a one-dimensional chain structure bridged by water molecules and 2,6- dichlorobenzoic acid. The crystal is of monoclinic, space group P21/c with α = 12.9701（19）, b = 20.592（3）, c = 7.3759（10） A, β = 102.660（2）°, V = 1.9221（5）. nm^3, Z = 4, C14H12Cl4MnO7, Mr= 488.98, Dc= 1.690 g/cm^3, p = 1.275 mm^-1, F（000） = 980, Rint = 0.0348, R = 0.0350, and wR = 0.0755. In the crystal the manganese atom is six-coordinated by two oxygen atoms from water and four oxygen atoms from four 2,6-dichlorobenzolate molecules, completing an octahedral geometry.

Crystal Structure of cis-Dichlorobis-(1,10-phenanthroline) Manganese(Ⅱ)

MnCl2 (C12,H8N2)2, Mr= 486. 26, monoclinic, P21,/c, a= 9. 461 (5),b= 15. 20(1), c= 14. 514(2) A, β=98. 82(3)°, V=2062(2) A3, Z=4, Dc= 1. 57g/cm3. λ(MoKα) = 0. 71073 A, μ(MoKα) = 0. 895 mm-l, F (000) = 988, T= 296K. Final R= 0. 043, Rw= 0. 053 for 2569 observed reflections. The Mn atom is co-ordinated by two Cl anions and four N of two phenanthroline (phen) molecules, forming a distorted octahedron. Two Mn--Cl bond lengths are 2. 437(2) and 2. 449(2) A,respectively. The Mn--N bond lengths vary from 2. 290(3) to 2. 367 (4) A。 The dihedral angle between two phen best planes is 90. 4°.

Synthesis and Crystal Structure of a Mixed-ligand Manganese(Ⅱ) Complex Containing Abundant Hydrogen-bonding Interactions

A new mixed-ligand Mn（II）complex,namely [Mn（bipy）2（Huca）]·5H2O（1,bipy = 2,2＇-bipyridine,and H3uca = uracil-5-carboxylic acid）has been prepared and characterized by single-crystal X-ray diffraction,FT-IR spectroscopy and thermogravimetric analysis.It crystallizes in monoclinic,space group C2/c with a = 23.597（8）,b = 16.434（5）,c = 15.531（6）,β = 112.785（6）o,C25H28MnN6O9,Mr = 611.47,V = 5553（3）3,Z = 8,μ = 0.538,Dc = 1.463 g/cm3,F（000）= 2536,R = 0.0441 and wR = 0.1230 for all 5227 observed reflections（I 2σ（I））.The manganese（II）center is surrounded by three bidentate chelating ligands,and it displays a severely distorted octahedral geometry,with cis angles ranging from 72.14（6）to 109.78（6）o.Extensive intermolecular hydrogen bonds link the [Mn（bipy）2（Huca）] monomers and lattice water molecules to yield a three-dimensional supramolecular framework.TGA shows complete removal of all lattice water molecules above 270 ℃.

Synthesis and Crystal Structure of a Novel Three-dimensional Manganese(Ⅱ) Coordination Polymer:[Mn(pdc)]_n (pdc=Pyridine-2,4-dicarboxylate)

A novel manganese（H） coordination polymer [Mn（pdc）]n （pdc = pyridine-2,4- dicarboxylate） has been synthesized under hydrothermal conditions. The crystal is of monoclinic, space group P211n with a = 6.506（4）, b = 9.392（6）, c = 11.217（7） A, β = 105.650（12）°, V= 660.0（7）A3, Z = 4, Mr = 220.04, Dc = 2.215 g/cm3,μ = 1.971 mm-1, F（000） = 436, Rint = 0.0345, R = 0.0360 and wR = 0.0778 for 1259 observed reflections with I 〉 2σ（I）. In the structure, the Mn（Ⅱ） atom is coordinated in a distorted octahedral arrangement by one pyridine N and five carboxylate O atoms from five pdc ligands, each of which coordinates to five Mn atoms to propagate a three-dimensional layered framework.

Synthesis,Crystal Structure and Magnetic Behavior of a New Manganese(Ⅱ) Coordination Polymer [Mn(DPPZ)(PZDC)(H_2O)] (DPPZ=Dipyrido[3,2-a:2',3'-c]-phenazine and H_2PZDC=Pyrazine-2,3-dicarboxylic Acid)

The title complex, [Mn（DPPZ）（PZDC）（H2O）] 1 （DPPZ = dipyrido[3,2 -a：2＇,3＇- c]phenazine and H2PZDC = pyrazine-2,3-dicarboxylic acid）, has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analyses, IR, TG- DTA and magnetic susceptibility measurement. It crystallizes in triclinic, space group P1^- with a = 6.6842（5）, b = 7.5741（6）, c = 20.5755（15）A, α = 90.1160（10）, β = 97.0560（10）, γ = 97.3350（10）°, V= 1025.16（13）A^3, Z = 2, MnC24H14N6O5, Mr= 521.35, Dc= 1.689 g/cm^3, F（000） = 530, μ（MoKa） = 0.699 mm^-1, R = 0.0366 and wR = 0.0810. Compound 1 contains one- dimensional chains which are further stacked through π-π interactions to form a 3D supramolecular architecture. The water molecule O（1W） is involved in hydrogen bonding interactions with symmetric carboxylate oxygen atom 0（4） at （x＋ 1, y＋1, z） and symmetric PZDC nitrogen atom N（6） at （1-x, 1-y, 1-z）, which completes the structure of 1. Magnetic susceptibility measurement indicates that the compound behaves a weak antiferromagnetic exchange interaction.

Synthesis and Crystal Structure of a Three-dimensional Manganese(Ⅱ)Complex Constructed via Covalent and Hydrogen Bonds

The assembly of 1,4-benzenedicarboxylic acid (H2bdc), 4,4?bipyridine (4,4?bipy), trimethyltin chloride and MnBr24H2O in hydrothermal conditions gave rise to a hydrogen-bonded three-dimensional complex {[Mn(4,4?bipy)4H2O](bdc)}n which has been characterized by single- crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P2/n with a = 7.0001(2), b = 11.5540(3), c = 11.4192(1) ? = 101.754(2)? V = 904.21(4) 3, Z = 2, C18H20MnN2O8, Mr = 447.30, Dc = 1.643 g/cm3, F(000) = 462 and m(MoK? = 0.783 mm-1. The final R and wR are 0.0499 and 0.1301, respectively for 1335 observed reflections with I ≥ 2(I). The Mn (Ⅱ) is six-coordinated in a distorted octahedral geometry. 4,4?Bipyridine in a m-bridge mode links [Mn(H2O)4]2+ into a linear cation chain. bdc acts as a counter anion and links the linear chains into a three-dimensional structure through hydrogen bonds.

Hydrothermal Synthesis, Crystal Structure and Luminescence Property of a 2D Manganese(Ⅱ) Coordination Polymer

Solvothermal reactions of MnCl_2·4H_2O with(pyridin-2-yl)methyl 4-(2-(4-((pyridin-2-yl)methoxy)phenyl)diazenyl)benzoate(L1) via an in situ ligand transformation reaction produced a new coordination polymer, {[Mn_(2.5)Cl_3L_2(H_2O)]·H_2O}_n(1, where HL = 4-(2-(4-((pyridin-2-yl)methoxy)phenyl)diazenyl)benzoic acid). The L1 ligand was decomposed in situ to L^- which was coordinated with Mn(Ⅱ) to form compound 1 in the solvothermal synthesis process. Complex 1 was characterized by IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction.Compound 1 possesses a 2D network. In addition, stability and photoluminescent property of 1 were also investigated.

Inhibiting manganese(Ⅱ)from catalyzing electrolyte decomposition in lithium-ion batteries

A once overlooked source of electrolyte degradation incurred by dissolved manganese(Ⅱ)species in lithium-ion batteries has been identified recently.In order to deactivate the catalytic activity of such manganese(II)ion,1-aza-12-crown-4-ether(A12C4)with cavity size well matched manganese(Ⅱ)ion is used in this work as electrolyte additive.Theoretical and experimental results show that stable complex forms between A12C4 and manganese(II)ions in the electrolyte,which does not affect the solvation of Li ions.The strong binding effect of A12C4 additive reduces the charge density of manganese(II)ion and inhibits its destruction of the PF_(6)^(-)structure in the electrolyte,leading to greatly improved thermal stability of manganese(II)ions-containing electrolyte.In addition to bulk electrolyte,A12C4 additive also shows capability in preventing Mn^(2+) from degrading SEI on graphite surface.Such bulk and interphasial stability introduced by A12C4 leads to significantly improved cycling performance of LIBs.

A New Manganese(Ⅱ) Coordination Compound Constructed by 1,10-Phenanthroline Derivative and Chlorine Anions: Synthesis, Crystal Structure and Theoretical Calculation

The new manganese（Ⅱ） coordination compound, [Mn（Cl）2（L）2]（1, L = 11-fluorodipyrido[3,2-a:2?,3?-c]phenazine）, has been achieved under hydrothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction. 1 crystallizes in monoclinic system, space group C2/c with a = 8.419（2）, b = 12.286（2）, c = 28.451（6） ?, β = 95.889（3）°, V =2927.5（10） ?3, Z = 4, C36 H16 MnF2 Cl2 N8, Mr = 724.41, Dc = 1.644 g/cm3, F（000） = 1460, μ（Mo Ka）= 0.691 mm-1, R = 0.0445 and wR = 0.0982. Adjacent compounds are stacked by one type of π-πinteraction among L ligands to generate a 1D supramolecular chain. Further, the 1D supramolecular chains are stacked by another type of π-π interaction among L ligands to give a 2D supramolecular layer. Moreover, the C-F···π interactions between the carbon atom of the L ligand and the pyrazine ring of the adjacent L ligand further stabilize the supramolecular layer of 1. In addition, natural bond orbital（NBO） analysis has been calculated by the B3LYP/LANL2DZ method, which shows obvious covalent interaction between the coordinated atoms and Mn（Ⅱ） ion.