Two Tri-spin Complexes Based on Lanthanide (Ln~Ⅲ =Dy~Ⅲ and Tb~Ⅲ ) and Nitronyl Nitroxide Radicals: Syntheses, Structures and Properties

Two new tri-spin radical-Ln（III）-radical complexes, [Ln（hfac）3（NITPh-Ph）2] （Ln = Dy （1） and Tb （2）, NITPh-Ph = 4＇-biphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, and hfac = hexafluoroacetylacetonate） have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, Uv-visible and magnetic properties. X-ray analysis reveals that the two complexes are isomorphous and crystallize in the triclinic system, space group P1. For complex 1, a = 12.402（3）, b = 15.414（3）, c = 17.383（3） A, a = 68.61（3）, β = 81.97（3）, y = 79.40（3）°, V = 3031.7（11） A3, Z = 2, Mr = 1401.86, Dc = 1.536 g/cm^3, kt = 1.344 mm^-1, F（000） = 1398, the final GOF = 1.173, R = 0.0670 and wR = 0.1376 for 9035 observed reflections with 1 〉 2a（/）; while for complex 2, a = 12.397（3）, b = 15.391（3）, c = 17.395（4） A, a = 68.62（3）, fl = 81.97（3）, ）, = 79.60（3）°, V = 3030.0（11） A3, Z = 2, Mr = 1398.29, Dc = 1.537 g/cm^3,μ = 1.344 mm-1, F（000） = 1398, the final GOF = 1.130, R = 0.0644 and wR = 0.1382 for 8989 observed reflections with 1 〉 2a（/）. They all consist of the discrete adducts, in which the central Ln（lll） ions are coordinated by six oxygen atoms from three hfacs and two oxygen atoms from nitronyl radicals. The temperature dependency of magnetic susceptibilities for these two complexes is studied, showing that the magnetic interactions are governed by the depopulation of the Ln Stark levels.

Synthesis and electrochemical properties of polyradical cathode material for lithium second batteries

A stable polyradical, poly (2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA), was synthesized,and its structure was determined by infrared, ultraviolet-visible, and ESR spectroscopy. Cyclic voltammograms ofthe PTMA polyradical electrodes were obtained by using a three-electrode cell at a scan rate of 5 mV/s within a po-tential range of 3.2-4. 0 V. The results show that the shape of oxidation peak is very similar to that of reductionpeak, and oxidation peak current is equal to the corresponding reduction peak current, which suggest that PTMApossesses an excellent reversibility. The difference of the anodic peak potential (Ea,p =3.66 V, vs Li/Li+ ) and ca-thodic peak potential(Ec,p =3.58 V, vs Li/Li+ ) is estimated at 80 mV, which is extremely less than that of the oth-er organic positive materials in lithium second batteries such as organosulfide compounds, leading to a capability forhigh current capability in the charging and discharging process of the battery. The maximum discharge specific ca-pacity of PTMA is 78.4 mA @ h/g at the constant discharge current of 0.3 mA (0.2 C rate), the coulombic efficien-cy is about 95%, and the charging and discharging curves of the batteries have an obvious plateau at 3.65 V and3.56 V, respectively. The discharging specific capacity of the battery decreased is about 2% after 100 cycles. ThePTMA/Li button batteries exhibite an excellent stability.

Synthesis, Crystal Structure and Magnetic Properties of Cobalt(II) Complex Involving Imino Nitroxide Radicals

A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhombic, space group P212121 with a = 11.031(2), b = 13.492(3), c = 20.467(4) ?, V = 3046.0(11) ?3, C24H32CoN8O8, Mr = 619.51, Z = 4, Dc = 1.351 g/cm3, μ(MoKα) = 0.620 mm?1, F(000) = 1292, R = 0.0506 and wR = 0.0845 for 3752 observed reflections with I > 2σ(I). X-ray analysis reveals that the crystal structure consists of [Co(IM2- Py)2(NO3)]+ moiety and a NO3 anion. The cobalt(II) ion is six-coordinated with a distorted octahedral geometry. Tempera- ? ture dependence of susceptibility measurements show that there exist an antiferromagnetic inter- action in the compound.

Syntheses, Crystal Structures and Magnetic Properties of a New Nitronyl Nitroxide Radical and Its Cu(Ⅱ) Complex

A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798（9）, b = 11.2705（9）, c = 12.9559（10）A, β = 107.3770（10）°, V = 1488.3（2） A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g（MoKa） = 0.276 mm^-1, F（000） = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit （imidazoline ring） is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699（10）, b = 10.6286（11）, c = 15.1683（15）A, a = 77.5330（10）, ,β = 773080（10）, y = 87.3420（10）＊, V = 1592.5（3） A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ（MoKa） = 0.888 mm^-1, F（000） = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu（Ⅱ） ion is located at a center of symmetry, and each Cu（Ⅱ） is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu（Ⅱ） ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.

A Equivalent Definition of Radical Property

This paper study the radical propertys in the sence of Amitsut and Kurosh from reference[1].

Theoretical Study on the Spectroscopic Parameters and Transition Properties of MgH Radical Including Spin-orbit Coupling

An accurate theoretical study on the MgH radical is reported by adopting the high-level relativistic MRCI＋Q method with a quintuple-zeta quality basis set. The reliable potential energy curves of the five A-S states of MgH are derived. Then the associated spectroscopic parameters are determined and found to be in good accordance with the available experimental results. The permanent dipole moments （PDMs） and the spin-orbit （SO） matrix elements of A-S states are computed. The results show that the abrupt changes of PDMs and SO matrix elements are attributed to the variations of electronic configurations at the avoided crossing point. The SOC effect leads to the five A-S states split into ten Ω states and results in the double potential well of （2）1//2 state. Finally, the transition properties from the （2）1//2, （1）3//2 and （3）1//2 states to the ground state X2∑＋1//2 transitions are obtained, including the transition dipole moments, Franck-Condon factors and radiative lifetimes.

Syntheses,Crystal Structures and Magnetic Properties of Two Nitrophenyl Substituted Nitronyl Nitroxide Radical-lanthanide Complexes

Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes [Ln（hfac）3（NITmNO2）2] （Ln = Sm（Ⅲ） （1）, Tb（Ⅲ） （2）, hfac = hexafluoroacetylacetonate, NITmNO2 = 2-（3-nitrophenyl）-4,4,5,5-tetramethyl-imidazo- line-1-oxyl-3-oxide） have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln（Ⅲ）-radical structures, in which the central Ln（Ⅲ） ions are all eight coordinated in D2d dodecahedral （DD） geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm（Ⅲ） ion and NITmNO2 in complex 1, while weak ferromagnetic interaction between Tb（Ⅲ） ion and NITmNO2 in complex 2.

Relations of complete creep processes and triaxial stress-strain curves of rock

Based on the results of triaxial compressive creep tests for five kinds of rock under the different stress loading,unloading and cycle-loading-unloading conditions,the creep deformation is not only a function of stress and time,but also it has the corresponding relations to the triaxial stress-strain curves of rock.The deformation properties of soften-strain,harden-strain and ideal plasticity presented by conventional triaxial compressive test curves under the different stress states were utilized,and the creep characteristics,the creep starting stress and the different entire creep process curves of rock were studied systematically according to creep experiment results,and the relations of the triaxial stress-strain curves to the creeping starting stress,the terminating curve,the different creep processes,and the different creep fracture properties were established.The relations presented in this paper were verified partially by the creep experiment results of five types of rock.

Bis-radicals (nitronyl nitroxide and imino nitroxide) Substituted Benzene with Long Alkyl Chain: Synthesis, Magnetic Study and Formation of LB film

The titled compound 1 as well as compounds 2 and 3 with similar chemical structures were prepared and characterized. The magnetic properties of 1 were investigated with SQUID (MPMS, quantum design) magnetometer. Studies with Langmuir-Blodgett (LB) technique indicated that stable condensed film of 1 could be formed at air-water interface and could be transferred onto various solid substrate under suitable conditions.

Synthesis of End Functional Polymers via Atom Transfer Radical Polymerization in Immobilized Catalytic System

Cross-linked polystyrene with azo-crown ether functional side chain (PSt-1, 10-dicarbonyl-3,6,9-trizaoeylcode-cane) was prepared under microwave irradiation and the structure was characterized through FT-IR and element analysis. The functionalized cross-linked polystyrene (cross-link degree, 3.5%) combining with immobilized catalyst system (CuBr and ethylα-bromo-isobutyrate) can catalyze atom transfer radical polymerization of Styrene. Neat polymer products can be obtained then. Complex of La and the polymer end group (EBiB) was synthesized. The third order nonlinear optical property of the polymer-La complex was investigated and the structure was also characterized by FT-IR and XPS.

Protective effects of protocatechualdehyde - thiosemicarbazone-copper (Ⅱ)complex, a mimic of SOD, on O_2^- radical-mediated oxiditive damage

Objective: To explore the biological role of ptotocatechualdehyde-thiosemicarbazone-copper(Ⅱ)complex (PTC), its scavenging O2- free radical mechanism and to develop a new drug with high effective and low-toxicity. One of the essential components of this metal complex is an extract from a traditional Chinese medicinal herb. Methods:①Xathine- Xathine oxidase-luminol chemiluminescence (CL)was applied to detect SOD-like activity of PTC. ②Effects of SOD and its mimic (PTC) on the free radical-mediated change of blood viscosity and zymosan-activated leukocytic chemiluminescence, as well as the prptectove effects of PTC on oxiditive damage after burn were observed. Results: ①PTC has a significantly high SOD-like activity with an [ID]50 of 150 μg/L (SOD-300 μg/L). ②PTC can significantly inhibit zymosan-activated leukocytic chemiluminescence.③PTC can lower phagocyte-dependent increase in blood viscosity and inhibit the lipid peroxidation in blood. ④PTC can alleviate secondary oxygen free radical injury after burn. Conclusion:PTC is a significantly effective O2- free radical scanvenger. It can be applied to treat diseases resulting from abnormality of active oxygen free radical reaction in the body.

Water Repellent Finishing on Cotton Fabric via Atom Transfer Radical Polymerization

In order to enhance the water repellence property of cotton fabric, cotton fabric was grafted using hexafluorobutyl methacrylate( HFMT) monomer via atom transfer radical polymerization( ATRP) method. Water repellent cotton fabric was successfully prepared, and characterized by scanning electron microscopy( SEM),Fourier transform infrared spectroscopy( FTIR), and X-ray photoelectron spectroscopy( XPS). The SEM images of the HFMT-treated cotton displayed significant difference from the untreated one. FT-IR characterization of the HFMTtreated cotton indicated that HFMT was successfully grafted onto the surface of the cotton fabric. XPS analysis indicated that the fluorine element of the HFMT-treated cotton existing on the surface of the cotton fabric. The surface contact angle test as well as the water repellence rating test showed that the water repellence of the HFMTtreated cotton fabric was much better than that of the untreated cotton fabric. The surface contact angle of the HFMT-treated cotton fabric could reach( 132. 4 ± 2. 2) °,and the water repellence rating could achieve grade 3. The washing durability of the HFMT-treated fabric was also investigated. The surface contact angle of the HFMTtreated cotton fabric could reach( 121. 1 ± 2. 1) ° after 20 washing times. Furthermore, the whiteness, air permeability, breaking strength,and breaking elongation of the HFMT-treated cotton fabric decreased slightly compared with the untreated cotton fabric.Finally,cotton fabric with good water repellence property and excellent washing durability could be obtained with little effect on the intrinsic properties of cotton fabric.

腹腔镜下D2根治术联合CME对局部进展期胃癌术后腹腔游离癌细胞检出率及预后的影响

目的:探讨腹腔镜下D2根治术联合完整系膜切除术(complete mesocolic excision,CME)对局部进展期胃癌腹腔游离癌细胞及预后的影响。方法:回顾性分析2021年06月至2022年06月于医院住院治疗的128例局部进展期胃癌患者临床资料,将64例实施腹腔镜下D2根治术的患者纳入对照组,64例实施腹腔镜下D2根治术联合CME的患者纳入研究组。记录两组手术、住院及并发症情况,采用生活质量综合评定问卷-74(GQOLI-74)评定生活质量。分别于腹腔镜探查后和肿瘤切除后收集腹腔冲洗液,应用细胞学检查检测腹腔游离癌细胞。术后随访1年,记录总生存期(OS)及无进展生存期(PFS)情况。结果:研究组淋巴结清扫总数及阳性淋巴结数量显著大于对照组(P<0.05)。与术前比较,研究组术后腹腔游离癌细胞阳性率显著降低(P<0.05)。与术前比较,两组术后GQOLI-74评分均显著增加,且研究组高于对照组(P<0.05)。两组腹腔感染/积液、胃排空障碍、肠梗阻、吻合口瘘、胰瘘、淋巴漏发生率及不良反应总发生率比较,差异均无统计学意义(P>0.05)。研究组术后1年PFS率和OS率均显著高于对照组(P<0.05)。结论:腹腔镜下D2根治术联合CME有利于彻底清除局部进展期胃癌淋巴结,减少术后复发,促进术后康复,且不增加腹腔游离癌细胞脱落和手术并发症风险,具有临床推广价值。

铝/聚四氟乙烯复合材料的研究进展

系统综述了铝/聚四氟乙烯(Al/PTFE)复合材料的研究进展。就复合材料的动态力学性能而言,应变率越大,强度越高;复合材料中Al含量增加,弹性模量和屈服强度随之增加;温度升高,复合材料韧性增加,但动态压缩强度降低;铁粉、镍粉、钨粉、氧化铜、氢化钛、氢化锆等可以提高Al/PTFE复合材料的抗压强度。就复合材料的热性能而言,Al/n-PTFE的放热量远高于其他铝热剂,且纳米级铝粉与PTFE的反应性优于微米级铝粉。就复合材料的点火和燃烧性能而言,复合材料中PTFE的质量含量约35%时,燃烧压力最高,燃烧时间最短,中心火焰温度也最高;限域空心结构的复合材料样品燃烧优于实心、空心、核壳结构的样品;氢化钛、高氯酸铵、碳纳米管具有一定的助燃作用。就复合材料的冲击反应性能而言,加载应变率越高,材料反应延迟时间越小,反应越剧烈,且纳米级铝粉反应性和反应程度优于微米级铝粉;添加氧化物(三氧化铋、氧化铜、三氧化钼和三氧化铁)可以调节材料的能量释放特性。就复合材料的反应完全性而言,其作为弹丸发射速率越高,反应越完全;铝粉含量对反应完全性有非常显著的影响;氧化铜可以提高反应的完全性。就复合材料的应用场景而言,其对靶板的毁伤效果、纵火能力、提高推进剂力学性能和燃烧效率、作为防护材料的防护效果,比传统材料都有显著提高。此研究结果预计会对火炸药行业和战斗部行业从业者有重要的参考价值。

不同乳突根治术联合鼓室成形术治疗慢性化脓性中耳炎的临床效果对比

目的探讨不同乳突根治术联合鼓室成形术治疗慢性化脓性中耳炎的临床效果。方法86例慢性化脓性中耳炎患者根据手术方法的不同分为两组。完壁组采用完壁式乳突根治术联合鼓室成形术治疗,开放组采用开放式乳突改良根治术联合鼓室成形术治疗。比较两组的术后恢复情况、复发率及听力阈值。结果术后,两组的鼓膜愈合情况比较,差异无统计学意义(P>0.05);完壁组的干耳时间短于开放组,复发率高于开放组(P<0.05)。术后6个月,两组的500、1000、2000 Hz听力阈值比较,差异无统计学意义(P>0.05);完壁组的4000 Hz听力阈值低于开放组(P<0.05)。结论与开放式乳突改良根治术联合鼓室成形术相比,完壁式乳突根治术联合鼓室成形术对慢性化脓性中耳炎患者高频听力的重建效果更佳,术后干耳更快,但复发率较高。

基于有效性完整表达的白芍质量标志物研究

目的:基于中药质量标志物(Q-marker)有效性原则,采用“性-效-物”三元论研究思路,从药性(味)和药效角度揭示白芍Q-marker。方法:采用液相色谱-质谱联用法(LC-MS),解析白芍、炒白芍、赤芍化学物质组;在此基础上,通过分子对接方法,选择白芍中各结构类型代表化合物为配体小分子,通过与苦、酸味受体进行分子对接实验,预测白芍潜在药性(味)物质基础;采用网络药理学方法,通过SwissTargetPrediction、中药系统药理学数据库与分析平台(TCMSP)等数据库预测化合物潜在作用靶点,并进行生物信息学分析,构建化合物-靶点-信号通路-药理作用-功效网络,进一步以体外抗炎药效筛选模型,验证白芍及关键化合物的抗炎药效作用,明晰基于药效的白芍物质基础,进而基于有效性完整表达结果确定白芍Q-marker。结果:共解析出白芍中42个成分、炒白芍中41个成分、赤芍中34个成分。其中单萜及其苷类化合物可能为白芍最主要的苦味物质基础,带有没食子酰基的鞣质类化合物可能为白芍最主要的酸味物质基础。网络药理学结果发现,白芍中17个成分通过作用于191个潜在靶点干预了165条相关通路,可发挥促进骨髓造血功能、抑制子宫收缩、抗炎、镇痛、保肝、抗高血压和抑制汗腺分泌等作用;验证实验表明,白芍中8个主要成分可通过下调白细胞介素-6、肿瘤坏死因子-α和一氧化氮等炎症因子的表达发挥抗炎作用。结论:初步确定芍药苷、芍药内酯苷、氧化芍药苷、没食子酰芍药苷、苯甲酰芍药苷、儿茶素、五没食子酰葡萄糖及没食子酸为基于有效性完整表达的白芍Q-marker。

射孔完井近井地带等效剪切控制体物理模型

为研究地层对含聚液体的剪切降解作用,应用ANSYS软件求解了射孔完井近井地带的压力场和速度场分布,并用MATLAB对压力场和速度场数据进行后处理,划分出10段射孔孔眼控制体,计算各控制体内等压面上的平均流速和各等压面沿流线轨迹到射孔孔壁距离,得出各段孔眼控制体内渗流速度随流线轨迹上渗流距离的变化关系。通过变直径、等直径岩心组合物模实验,测试了各段孔眼控制体内沿流线轨迹不同渗流距离处聚合物溶液的流变性,用流量加权法计算出了整个射孔孔眼控制区域聚合物溶液黏度保留率,按照等效剪切原理确定了射孔孔眼等效剪切控制体的位置及参数,研制了射孔孔眼等效剪切控制体物理模型,该模型在定排量条件下即可准确模拟射孔完井近井地带的变速渗流场对含聚液体的剪切降解作用。

超高性能海水海砂混凝土单轴受压应力-应变关系

为研究超高性能海水海砂混凝土(Ultra-High Performance Seawater Sea-sand Concrete,UHPSSC)轴压应力-应变关系,探究钢纤维体积掺量对UHPSSC轴压力学性能和轴压应力-应变全曲线的影响,使用Instron 1346万能材料试验机测得UHPSSC应力-应变全曲线,借助Pycharm曲线拟合程序与已有混凝土应力-应变全曲线模型进行拟合与修正.结果表明:钢纤维掺量越高,轴压作用下UHPSSC的破坏程度越小,抗压强度和峰值应变也随之增加;已有模型拟合的UHPSSC应力-应变全曲线上升段与试验曲线比较相近,下降段后期差距较大;通过修正下降段形状参数,得到了更适用于描述UHPSSC应力-应变全曲线的修正模型,并验证该修正模型的适用范围.

完整结肠系膜切除术在老年结肠癌手术治疗中的应用

目的探究完整结肠系膜切除术(complete mesocolic excision,CME)用于老年结肠癌的手术治疗效果。方法选取2017年9月—2022年9月湖北省潜江市中心医院收治的120例老年结肠癌患者为研究对象,根据接受的不同手术方式分为两组,对照组(n=58)行常规腹腔镜结肠癌根治术,观察组(n=62)行腹腔镜CME。比较两组手术指标(手术切口长度、术中出血量、手术时间、术后排气时间、术后下床时间及术后住院时间)、淋巴结(右半结肠淋巴结、左半结肠淋巴结、阳性转移淋巴结)清除数目、应激反应、并发症发生率及术后6个月与术后12个月总复发率。结果比较两组手术时间、术中出血量、手术切口长度、术后排气时间、术后下床时间、术后住院时间,差异无统计学意义(P均>0.05)。观察组右半结肠淋巴结、左半结肠淋巴结、阳性转移淋巴结的清除数目均多于对照组,差异有统计学意义(P均<0.05)。术后2 h两组的肾上腺素、皮质醇及促肾上腺皮质激素均高于术前,差异有统计学意义(P均<0.05);但两组间应激反应(肾上腺素、皮质醇及促肾上腺皮质激素)指标比较,差异无统计学意义(P均>0.05)。观察组并发症发生率低于对照组,差异无统计学意义(P>0.05)。观察组术后6个月和12个月的总复发率为3.23%(2/62),低于对照组的15.52%(9/58),差异有统计学意义(χ^(2)=5.437,P<0.05)。结论与常规腹腔镜结肠癌根治术比较,腹腔镜CME能提高淋巴结清扫数量,降低肿瘤复发风险,不影响手术进程与术后恢复,且不会加大患者机体应激反应。

国产图迈■内窥镜手术机器人辅助右半结肠癌根治术的应用分析

目的:初步探讨图迈■内窥镜手术机器人辅助右半结肠癌根治术的安全性及可行性。方法:收集甘肃省人民医院普外科一病区于2022年04月至06月收治的6例右半结肠癌患者的临床病例资料,其中男性4例,女性2例,中位年龄57岁,范围37~68岁;患者均行图迈■内窥镜手术机器人辅助右半结肠癌根治术,即右半结肠D3+全结肠系膜切除术。结果:6例患者均顺利完成手术;平均手术时间204.16 min,术中出血量108.31 mL,术后下床活动时间为3.16 d,术后胃肠功能恢复时间为4.16 d,术后进食流质食物时间为5 d,腹腔引流管引流时间8 d,淋巴结清扫数目为23.33枚,术后住院时间9.5 d;术中、术后均无器械相关的不良事件发生;6例患者均行全身静脉化疗,方案为FOLFOX,疗程为6~8个周期;1年总体生存率为100%。结论:图迈■内窥镜手术机器人辅助右半结肠癌根治术安全、可行,临床疗效良好;该机器人系统有望成为国内辅助根治结肠癌的主要手段。