混合稀土储氢合金中氧和氮的测定

研究了混合稀土储氢合金中氧和氮的测定方法。针对稀土金属高温易挥发、分解的特点，选择适宜的加热温度，使用镍浴，选择高温座坩埚进行试验：选择出了合适的助熔剂的预处理方法。方法已用于实际样品。对含氧0．43％、含氮0.018％的试样，分析精密度为氧4．3％，氮5.9％，加标回收率氧为93％～104％，氮为92％～110％。     

碳素钢氧氮气体标准样品的研制

依据《标准样品工作导则》(GB/T 15000.1~15000.5-1994)和《冶金产品分析用标准样品技术规范》(YB/T 082-1996)研制了3个水平含量的碳素钢氧氮气体标准样品,对其均匀性、稳定性检验后进行定值,定值结果分别为氧:0.002 2%、0.008 8%、0.011 5%;氮:0.007 00%、0.003 20%、0.002 5%。定值水平与国内外同类样品相当。     

不同前处理制样方法对钢中氧、氮测定结果的影响

讨论了不同物理和化学制样方法对钢中氧、氮测定结果的影响。试验结果表明,物理制样采用锉刀打磨样品表面后剪切,再用乙醚清洗除去油污;化学制样先用20%盐酸溶液溶解样品表面氧化层,再用滴加了4滴30%过氧化氢的10%草酸溶液浸泡,取出后依次用水、无水乙醇浸洗,风干。用以上两种方法制样,钢标准样品中氧、氮含量测定值与标示值一致。在测定钢中氮含量时,可用乙醚清洗后直接测定,以缩短检测周期和减轻劳动强度。该研究结果可用于指导钢样品中氧、氮含量测定时样品的处理。     

自动元素分析仪测定碳纤维中氮、碳、氢

利用Vario ELⅢ型元素分析仪测定了碳纤维中氮、碳和氢的含量。优化的试验条件为:称样量2.1～2.4 mg,加氧时间120 s,燃烧管温度980℃。选用乙酰苯胺计算当天校正因子,方法用于碳纤维和石墨样品分析,含碳量在88.05%～99.46%之间,而在绝大多数样品中氮和氢的质量分数都小于0.30%。     

基于氦离子化气相色谱法测定微量氧、氮的影响因素

探讨氦离子化气相色谱法测定样品中微量氧、氮含量的影响因素。采用控制变量法,对色谱柱温度、进样流量、进样管道环境及极化电压等因素对微量氧、氮测定结果的影响进行讨论和分析。结果表明,当色谱柱温度为25~45℃时,色谱柱对氧、氮吸附量最小;当进样流量不小于70 mL/min时,微量氧、氮测定结果受外界干扰最小;当极化电压为80~160 V时,氧、氮具有最佳的响应值;初次测定样品中微量氧、氮含量时,需使进样管道表面吸附的氧、氮处于饱和状态,以便获得理想的测定结果。讨论的结果可为氦离子化气相色谱法测定相关样品中微量氧、氮含量时提供技术参考。     

烯丙基钯催化区域选择性氧化制备甲基酮的研究

报道了以氯化钯作催化剂，区域选择性氧化９－烯丙基－１－氧代－４－氮杂双环（４．３．０）壬烷及１０－烯丙基－１－氧代－４－氮杂双环（５．３．０）癸烷，制备了９－丙酮基－１－氧化－４－氮杂双环（４．３．０）壬烷及１０－丙酮基－１－氧代－４－氮杂双环（５．３．０）癸烷。比较了不同催化条件和溶剂系统的反应收率，发现以ＰｄＣｌ２／对－苯醌为催化系统和以含水的ＤＭＦ溶剂系统氧化收率最高。     

螯合树脂研究 ⅩⅩⅤ．环硫（氧）氯丙烷与三（二）乙醇胺钠盐反应合成硫氮杂冠醚型树脂

环硫（氧）氯丙烷，不经过预先聚合，直接与三（二）乙醇胶的钠盐进行反应，制得交联的硫、氮杂冠醚型螫合树脂．提出了可能的反应机理．还研究了这类树脂对一些贵金属和非贵金属离子的吸附性能．比较了相应的含硫、氮和氧氮树脂吸附性能的差别．总的说来合硫氮的树脂对贵金属的吸附性能优于含氧、氮树脂．     

脉冲加热-红外吸收、热导法测定粉末高温合金中氧、氮

利用脉冲加热-红外吸收、热导法测定粉末态粉末高温合金中氧、氮含量.通过助熔剂试验,确定了用镍盒包裹试样来分析样品的方法.结果表明粉末高温合金试样中总氧量的测定相对标准偏差RSD为4.2%,总氮量的测定相对标准偏差RSD为20%.分析标钢中氧的回收率为91.7%～110.8%.氮的回收率为95.9%～108.2%.     

脉冲加热-热导法测定氮化锰粉末中的氮含量

介绍采用TC-600氧氮分析仪测定氮化锰粉末中氮的方法。对氮化锰粉末样品,采用手动模式进样。对加热功率、称样量、空白值等测定条件进行试验,确定了最佳测定条件。氮的加标回收率为98.18%~101.10%,测定结果的相对标准偏差小于1%(n=9)。该方法测定结果与化学法测定结果一致。     

稀土金属钕和镝中氧氮的测定方法研究

研究了稀土金属钕和镝中杂质氧和氮的测定方法。针对稀土金属高温易挥发的特点,选择适宜的加热温度,使用镍浴选择高温座坩埚进行试验,获得了满意的测定效果。对于降低助熔剂和浴料的空白值进行了研究,确定了合适的助熔剂的预处理方法。对于氧质量分数0．12％、0．013％氮的试样,相对标准偏差为氧9．6％、氮8、9％;加标回收率为氧90％～106％、氮94％～110％。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.