Antoioxidant Activity of Carboxymethyl Chitosan with Different Substituted Degrees

[Objective] In order to study the relations among different positions, degrees of substitution and antioxidant ability. [Method] N, O-carboxymethyl chitosan （NOA, NOB and NOC）with various degrees of substitution （DS）were obtained by etherizing chito-oligosacchaside. Their structure and substituted degree were characterized and their antioxldant activity to·OH was evaluated. [ Result] The IC50 s of NOA ,NOB and NOC were 0.15 ,0. 29 ,0. 23 mg/ml while their DSs of -NH2 position（DSN） were 0.51,0.29 and 0.38 and DSo were 0. 74 ,0. 84 ,0. 97respectively.[ Conclusion] With the increase of DSN ,antioxidant activity of N,O-carboxymethyl chitosan oligosaccharide to·OH was up.

Theoretical Study of the C-CI Bond Dissociation Enthalpy and Electronic Structure of Substituted Chlorobenzene Compounds

Quantum chemical calculations were used to estimate the bond dissociation energies （BDEs） for 13 substituted chlorobenzene compounds. These compounds were studied by the hybrid density functional theory （B3LYP, B3PW91, B3P86） methods together with 6-31G^＊＊ and 6-311G^＊＊ basis sets. The results show that B3P86/6-311G^＊＊ method is the best method to compute the reliable BDEs for substituted chlorobenzene compounds which contain the C-C1 bond. It is found that the C-C1 BDE depends strongly on the computational method and the basis sets used. Substituent effect on the C-C1 BDE of substituted chlorobenzene compounds is further discussed. It is noted that the effects of substitution on the C-C1 BDE of substituted chlorobenzene compounds are very insignificant. The energy gaps between the HOMO and LUMO of studied compounds estimate the relative thermal stability ordering are also investigated and from this data we of substituted chlorobenzene compounds.

减氮及有机肥替代对旱地冬小麦干物质积累、转运、分配和产量的影响

探究减氮及有机肥替代对旱地冬小麦产量形成和经济效益的影响,为实施化肥减量和有机肥替代提供理论和技术依据。2021-2023年度,基于2019年开始设置在黄土高原和黄淮海平原交汇处典型旱地冬小麦产区(河南洛宁和河南孟津)的定位试验,研究了冬小麦干物质积累转运分配特性、氮肥干物质生产效率、产量及其构成要素和经济效益。试验设置不施氮肥(NN)、农户施氮(FN)、基于FN减氮20%(RN)和RN基础上20%氮肥用有机肥替代(OSN)4个处理。结果表明:(1)与FN相比,RN处理降低了小麦拔节期、开花期和成熟期的干物质积累量、花前干物质转运量以及成熟期茎鞘、穂轴+颖壳和籽粒的干物质分配量,但对籽粒产量无显著影响。(2)与FN和RN相比, OSN处理提高了各生育阶段的氮肥干物质生产效率,从而增加了拔节期、开花期、成熟期的干物质积累量,而且提高了花前干物质转运量、花后干物质积累量、花后干物质积累量对籽粒的贡献率,进而使成熟期地上部各器官的干物质分配量均得到显著提高,最终使籽粒产量分别显著增加15.03%和17.12%,经济效益增加3.84%和4.23%。(3)小麦产量与花前干物质转运量、花后干物质积累量和花后干物质积累量对籽粒的贡献率呈极显著正相关,与花前干物质转运量对籽粒的贡献率呈极显著负相关。综上,在雨养条件下,小麦季施氮量为172kghm^(–2) (夏休闲-冬小麦)和192kg hm^(–2) (夏玉米-冬小麦)的基础上,OSN处理提高了氮肥干物质生产效率,增加各生育时期的干物质积累量,其花前干物质转运量和花后干物质积累量的协同增加使其获得了最高产量,实现增产增收,适宜在产量水平为5000kghm^(–2)的雨养旱地冬小麦高产栽培中应用。

替代率对某船用中速双燃料发动机性能的影响

为了改善某船用中速柴油机的燃油经济性和排放特性,对进气歧管加装天然气喷射装置的柴油/天然气双燃料发动机进行研究。基于仿真软件GT-Power,在螺旋桨推进特性的工况下,分析了某船用双燃料发动机纯柴油模式和双燃料模式下的缸内压力、燃油经济性和排放特性。结果表明:与纯柴油模式相比,双燃料模式的气缸峰值压力和NO_(x)排放量有所减少,NO_(x)排放量最多减少41.3%;随着天然气替代率的增加,发动机的燃油经济性最多提高了16.08%。综合来看,双燃料模式下发动机性能得到提升。

A 3D-QSAR Study on C-3 Substituted 4,6-Dichloroindole-2- Carboxylic Acids with Comparative Molecular Field Analysis

Aim and Method Comparative molecular field analysis (CoMFA), a threedimensional quantitative structure-activity relationship (3D-QSAR) method was applied to a novelseries of C-3 substituted 4, 6-dichloioindole-2-carboxylic acids to study the relationship betweentheir structure and the affinity for the glycine site of the NMDA receptor. Result Hie coefficientsof cross-validation q^2 and non cross-validation r^2 for the model established by the study are0.744 and 0.993, respectively, the value of variance ratio F is 261.343, and standard error estimate(SE) is 0.039. Conclusion These values indicate that the CoMFA model may have a good prediction forthe activity of C-3 substituted 4, 6-dichloroin-dole-2-carboxylic acids. As a consequence, thepredicted activity values of new designed compounds supports our conclusion from the model.

一种多重修饰血紫蛋白纳米氧载体的构建及体外性能检测

背景:血紫蛋白分子稳定性及生物相容性优于人和哺乳动物血红蛋白,经过修饰可能成为更加安全长效的红细胞代用品。目的:制备多重修饰血紫蛋白纳米微粒,进行理化性质表征及体外性能测试。方法:以切向流超滤法分离纯化方格星虫血紫蛋白,使用京尼平完成分子内交联,然后利用多巴胺完成纳米粒子封装,再用聚乙二醇完成钝化,获得多重修饰血紫蛋白纳米粒,表征该纳米粒的理化性质。将不同质量浓度(0,0.25,0.5,1.0,2.0 mg/mL)的血紫蛋白纳米粒、血紫蛋白、血红蛋白氧载体HBOC-201分别与巨噬细胞共同孵育6,24 h,与血管内皮细胞共同孵育24 h,采用CCK-8法检测细胞存活率,ELISA法检测血管内皮细胞培养液中一氧化氮及血管细胞黏附因子1水平。结果与结论:(1)血紫蛋白纳米粒电镜下呈现椭球形,有致密外膜,内部质地较为均匀,粒径为(150.12±1.67) nm,分散指数为0.21±0.03,Zeta电位为(-24.54±2.61) mV,半饱和氧分压为(0.97±0.15) kPa,Hill系数为1.49±0.16。(2)孵育6 h,在≤1.0 mg/mL质量浓度范围内,血紫蛋白纳米粒组、血紫蛋白组、HBOC-201组巨噬细胞存活率均在85%以上;在2.0 mg/mL质量浓度下,仅血紫蛋白纳米粒组巨噬细胞存活率在80%以上。孵育24 h,3组巨噬细胞存活率均低于80%,其中血紫蛋白纳米粒组巨噬细胞存活率高于血紫蛋白组、HBOC-201组(P <0.05)。(3)随着药物质量浓度的增加,3组血管内皮细胞存活率降低,在1.0 mg/mL或2.0 mg/mL质量浓度下,血紫蛋白纳米粒组细胞存活率高于血紫蛋白组、HBOC-201组(P <0.05);在相同质量浓度下,血紫蛋白纳米粒组一氧化氮水平高于血紫蛋白组、HBOC-201组(P <0.05);在0.25-2.0 mg/mL质量浓度范围内,血紫蛋白纳米粒组血管细胞黏附因子1水平低于血紫蛋白组、HBOC-201组(P <0.05)。(4)结果表明,经过分子内交联和聚多巴胺/聚乙二醇修饰的血紫蛋白纳米粒在体外具有良好的携氧活性,抗吞噬性能更优,细胞毒性更小。

钢纤维增强碱矿渣再生骨料混凝土的力学性能

碱矿渣再生混凝土是以碱激发胶凝材料替代水泥、再生骨料取代天然石子制备而成的新型混凝土,能有效降低波特兰水泥用量,提高废弃混凝土利用率,但尚未见对其力学性能的相关研究。为研究碱矿渣再生混凝土的基本力学性能,以钢纤维取代率和再生骨料取代率为主要试验参数,进行抗压试验、劈裂抗拉试验和抗折试验。研究结果表明:随着再生粗骨料取代率的增加,碱矿渣再生混凝土的抗压强度f_(cu)、劈裂抗拉强度f_(t)和抗折强度f_(w)均降低,再生粗骨料取代率为100%时的降低幅度分别为30%、10%、15%;碱矿渣再生混凝土抗压强度和劈裂抗拉强度随钢纤维体积取代率增加先提高后降低,钢纤维体积取代率为0.6%时,抗压强度和抗折强度达到最大值;碱矿渣再生混凝土抗折强度随钢纤维体积取代率增加而增加。

Magnetic properties of La-Zn substituted Sr-hexaferrites by self-propagation high-temperature synthesis

The La-Zn substituted SrM-type ferrites with the composition of Sr1-xLaxFe12-xZnxO19 （x=0-0.4） were prepared by self-propagating high-temperature synthesis （SHS）. The single SrM phase was detected by XRD in the as-received samples by controlling the Fe contents in the reagents. The substitution of La^3＋and Zn^2＋ obviously increased the magnetic properties of the as-prepared samples. The maximum improvements of Br, Hcb and （BH）m were 14.4%, 15.3% and 30.7%, respectively compared with that of the samples without La-Zn substitution. Microstructure observation by SEM showed that the SHS method benefited forming the better particle features and achieving the higher Hcj in comparison with the traditional firing method.

Structural Characterization and Acute Toxicity Prediction of Substituted Aromatic Compounds by Using Molecular Vertexes Correlative Index

A molecular structural characterization （MSC） method called molecular vertexes correlative index （MVCI） was used to describe the structures of 30 substituted aromatic compounds. Through multiple linear regression （MLR） and stepwise multiple regression （SMR）, a quantitative structure-toxicity relationship （QSTR） model with 4 variables was obtained. The correlation coefficient （R） of the model was 0.9467. Through partial least-squares regression （PLS）, another QSTR model with 5 principal components was obtained. The correlation coefficient （R） of the model was 0.9518. Both models were evaluated by performing the cross-validation with the leave-one-out （LOO） procedure and the Cross-Validation （CV） correlation coefficients （Rcv） were 0.9208 and 0.9214, respectively. The results suggested good stability and predictability of the models, and the molecular vertexes correlative index could successfully describe the structures of the substituted aromatic compounds.

Synthesis,Characterization and Antibacterial Property of Strontium Half and Totally Substituted Hydroxyapatite Nanoparticles

Nanoparticles of hydroxyapatite（HAP）, strontium half substituted hydroxyapatite （SrCaHAP） and strontium totally substituted hydroxyapatite （SrHAP） were prepared by sol-gel-supercritical fluid drying （SCFD） method. The nanoparticles were characterized by element content analysis, FT-IR, XRD and TEM, and the effects of strontium substitution on crystal structure, crystallinity, particle shape and antibacterial properties of the nanoparticles on Escherichia coli, Staphylococcus aureus, Lactobacillus were researched. Results show that strontium can half and totally substitute for calcium and enter the structure of apatite according to the initial atomic ratios of Sr/[Sr＋Ca] as 0.5, 1. The substitution decreases the IR wavenumbers of SrCaHAP and SrHAP, and changes the morphology of the nanoparticles from short rod shaped HAP to needle shaped SrCaHAP, and back to short rod shaped SrHAP. The crystallinity of HAP is higher than that of SrCaHAP, but is lower than that of SrHAP. Moreover, the antibacterial property of SrCaHAP and SrHAP are improved after the calcium is half and totally substituted by strontium.

Oxygen permeation and phase structure properties of partially A-site substituted BaCo_(0.7)Fe_(0.225)Ta_(0.075)O_(3-δ) perovskites

Ba0.9R0.1Co0.TFe0.225Ta0.07503-δ （BRCFT, R = Ca, La or Sr） membranes were synthesized by a solid-state reaction. Metal cation Ca2＋, La3＋ or Sr2＋ doping on A-site partially substituted Ba2＋ in BaCoo.TFe0.225Ta0.07503-δ oxides, and its subsequent effects on phase structure stability, oxygen permeability and oxygen desorption were systematically investigated by XRD, TG-DSC, Hz-TPR, O2-TPD techniques and oxygen permeation experiments. The partial substitution with Ca2＋, La3＋ or Sr2＋, whose ionic radii are smaller than that of Ba2＋, succeeded in stabilizing the cubic perovskite structure without formation of impurity phases, as revealed by XRD analysis. Oxygen-involving experi- ments showed that BRCFT with A-site fully occupied by Ba2＋ exhibited good oxygen permeation flux under He flow, reaching about 2.3 mL.min-l .cm-2 at 900 with I mm thickness. Of all the membranes, BLCFT membrane showed better chemical stability in CO2, owing to the reduction in alkalinity of the mixed conductor oxide by La doping. In addition, we also found the stability of the perovskite structure under reducing atmospheres was strengthened by increasing the size of A-site cation （Ba2＋〉La3＋〉SrZ＋〉Ca2＋）.

A Novel Nucleophilic Substitution of 3-Halo-6-phenoxypyridazines

A novel nucleophilic substitution of pyridazines is found, in which phenoxy group is dislodged rather than the halogen atom, on treating 3-halo-6-phenoxypyridazines with alkoxy anion. The reactivity of substituents on benzene ring and the halogen atom of pyridazines are studied. Reasonable explanation based on the quantum chemical calculations are given.

A Novel Green Preparation of a, a'-Bis (substituted benzylidene)-cycloalkanones Promoted by FeCl_3 6H-2O in Ionic Liquid

a, a'-Bis(substituted benzylidene)cycloalkanones were efficiently prepared from cycloalkanones and benzaldehydes in [bmim][BF4] by using iron(III) chloride hexahydrate as a catalyst. It is shown that [bmim][BF4] and iron(III) chloride hexahydrate can be quantitatively recovered and be reused effectively for many times. Compared with the known methods, this novel process has the advantage of being an envkonmentally benign process together with good yields and mild reaction conditions.

Synthesis of Bis-substituted Calix[4]arenes and Mechanism of Substituents Effect on K^+ and Hg^(2+) Ions Transports through Liquid Membrane

New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was examined.For K+ ion transfer,preserving phenolic hydroxyl in the lower rim of calix[4]arene could enhance its transport ability.When benzoyl replaced phenolic hydroxyl,the transport would fall off,because benzoyl caused steric hindrance on the K+ transfer.The study also revealed that the group having the electron-withdrawing conjugative effect on phenolic hydroxyl,-NO2 in the upper rim of calix[4]arene,made transport ability of calix[4]arene fall off.On the contrary,-NH2 that had electron-repulsive conjugative effect enhanced the transport ability of the compound.For Hg2+ ion,only -NH2 in the upper rim of calix[4]arenes had high affinity for it and contributed to Hg2+ transfer.Transport amount of Hg2+ ion increased with increasing calix[4]arene5 concentration and ΔpH in BLM.

Experimental and QSPR Studies on n-Octanol/water Partition Coefficient (lgK_(ow)) of Substituted Aniline

The n-octanol/water partition coefficients （lgKow） of 18 substituted anilines were determined at 25 ℃ by shake-flask method. The geometrical optimization of substituted anilines has been performed at B3LYP/6-311G^＊＊ level with Gaussian98 program, and the molecular surface areas of substituted anilines were calculated using ChemOffice 2004 program. The calculated structural parameters of substituted anilines were used as theoretical descriptors and the two-parameter （molecular surface area （MA） and the energy of the highest occupied molecular orbital （EaoMo）） quantitative structure-property relationship （QSPR） model of lgKow for substituted aniline with molecular structural parameters was developed by multi-linear regression method. The regression coefficient square （r^2） is 0.990 and the standard deviation SE 0.109. The model was validated by variance inflation factors （VIF） and t-test, and the results show that there exists small self-correlation between variables of the model with perfect stability. The model gives results in good qualitative agreement with experimental data. At last, the model was applied to predict lgKow values of five substituted anilines whose lgKow values have not been determined experimentally.

Determination and QSAR Study on the Toxicity of Substituted Phenol against Qinghaiensis sp (Q67)

Toxicities （-1gEC50） of 16 phenolic compounds against Q67 were determined, and structural parameters as well as thermodynamic parameters of these compounds were obtained through fully optimized calculations by using B3LYP method of density functional theory （DFT） at the 6-311G^＊＊ level. Moreover, a 3-parameter （molecular average polarizability （α）, heat energy corrected value （Eth） and the most positive hydrogen atomic charge （qH^＋）） correlation model with R^2 = 0.981 and q^2 = 0.967 to predict -1gEC50 was obtained from experimental data based on the above-mentioned parameters as theoretical descriptors. Therein a was the most significant on -1gEC50. Variance Inflation Factors （VIF）, t-value and cross-validation were applied to verify the model, confirming that the resultant model has fairly better stability and predictive ability to predict -1gEC50 of similar compounds.

The magnetic and dielectric properties of multiferroic Sr-substituted Zn_2-Y hexagonal ferrites

The magnetic and dielectric properties of Sr-substituted Zn2-Y hexagonal ferrites （Ba2-x SrxZn2Fe12O22, 1.0 〈 x ≤ 1.5） are studied in this paper. Sr substitution will lead to the variation of cation occupation, which influences both the magnetic and electric properties. As Sr content x rises from 1.0 to 1.5, magnetic hysteresis loop gets wider gradually and the permeability drops rapidly due to the transformation from ferrimagnetic to antiferromagnetic phase. Moreover, permittivity rises with increasing Sr content. Under a certain external magnetic field, the phase transition of helical spin structure of Ba0.5Srl.5Zn2Fe12O22 at about 295 K seems to open a possibility for the room-temperature ferroelectricity induced by magnetic field. But its low resistivity prevents the observation of ferroelectric and magnetoelectric properties at room-temperature.

A Study of the Driving Force for Inclusion Complexation of α- and β- Cyclodextrin with Substituted Benzene

The driving force for inclusion complexation of α and β CD with substituted benzene(PhX) was studied by means of step wise regression analysis. A set of multiple regression equations was established with correlation coefficients 0 96 and 0 94 for the individual complexation of α CD and β CD with PhX. The ln K a(calc.) values calculated with the aid of the regression equations were close to those determined experimentally. The inclusion complexation is dominantly driven by van der Waals force and hydrophobic interactions.

Correlation Study of Toxicity of Substituted Phenols to River Bacteria and Their Biodegradability in River Water

To study the correlation of toxicity with biodegradability （BODT） in order to promote QSBR development and understand the degradation mechanism. Methods Toxicity of substituted phenols to river bacteria was determined by the turbidities that were measured using a spectrophotometer （UV-190） at 530 nm against a blank control. The biodegradability of substituted phenols was expressed as BODT and the DO concentrations were determined by the iodometric titration method. Results The BODT and toxicity（log 1/IC50） of 12 substituted phenols to bacteria from the Songhua River were determined respectively. The correlation of biodegradability with toxicity was developed： BODT=8.21 （±2.22） pKa -32.44 （±8.28） log 1/IC50 ＋89.04 （±38.20）, n=12, R^2=0.791, R^2（adj）=0.745, SE=9.134, F=17.066, P=0.001. Conclusion The BODT of substituted phenols was influenced by their toxicity and the ionization constant pKa. The stronger the toxicity, the less readily the compound was degraded by river bacteria.

Fe-substituted cobalt-phosphate polyoxometalates as enhanced oxygen evolution catalysts in acidic media

All-inorganic and earth-abundant bi-/trimetallic hydr(oxy)oxides are widely used as oxygen evolution electrocatalysts owing to their remarkable performance.However,their atomically precise structures remain undefined,complicating their optimization and limiting the understanding of their enhanced performance.Here,the underlying structure-property correlation is explored by using a well-defined cobalt-phosphate polyoxometalate cluster [{(Co4)(OH)3(PO4)}4(SiW9 O34)4]^32-(1),which may serve as a molecular model of multimetal hydr(oxy)oxides.The catalytic activity is enhanced upon replacing Co by Fe in 1,resulting in a reduced overpotential(385 mV) for oxygen evolution(by 66 mV) compared to that of the parent 1 at 10 mA cm^-2 in an acidic medium;this overpotential is comparable to that for the IrO2 catalyst These abundant-metal-based polyoxometalates exhibit high stability,with no evidence of degradation even after 24 h of operation.