聚丙烯腈热裂解产物的ESR和固体￣（13）CNMR研究

用电子自旋共振（ＥＳＲ）和固体￣（１３）ＣＮＭＲ研究了聚丙烯腈（ＰＡＮ）在不同裂解温度（Ｔ＿Ｐ）下的结构变化，当Ｔ＿Ｐ从２５０℃增加到６００℃，ＥＳＲ信号线形没有变化，ｇ值与Ｔ＿Ｐ无关，ΔＨ＿（ＰＰ）减小，自旋浓度（Ｎ＿Ｓ）开始增加，Ｔ＿Ｐ进一步升高，Ｎ＿Ｓ又减少．￣（１３）ＣＮＭＲ谱指出在不同Ｔ＿Ｐ下谱峰发生很大变化，与另文报道的红外及Ｘ－射经衍射结果一致，随Ｔ＿Ｐ升高，ＰＡＮ逐渐脱去小分子形成具有环化共轭结构的产物．     

菱钾沸石中铝在不等价四面体位上分布的^29SiMASNMR谱研究

根据菱钾沸石＾２９ＳｉＭＡＳＮＭＲ实验讨论了骨架Ｓｉ／Ａｌ比（Ｒ）和Ａｌ在两种不等价四面体位分配比率（ｒ）二者之间必须满足的关系，对于合成原粉，Ａｌ择优占据ＴＢ位；用（ＮＨ４）２ＳｉＦ６同晶取代脱铝，ＴＢ位上的Ａｌ择优解脱。     

双荧光剂荧光光度法研究与应用--四溴荧光素*丁基罗丹明B体系

向离子缔合物ＧａＣｌ４ＢＲＢ（ＢＲＢ是丁基罗丹明Ｂ）的甲苯萃取液中,加入ｐＨ＝８．７的ＮａＯＨ－ＫＨ２ＰＯ４缓冲溶液,离子缔合物解析后ＢＲＢ进入水相。向其中加入与ＢＲＢ颜色相近的四溴荧光素（ＴＢＦ）,形成的ＢＲＢ２ＴＢＦ再被甲苯萃取,萃取液中加入正丁醇（甲苯：正丁醇＝１１）。因萃取液中ＢＲＢ２ＴＢＦ［１］的双荧光剂协同作用,提高了测定镓的灵敏度。     

DEUTERIUM INFLUX PROFILE ALONG THE APEX OF THE UPPER X-POINT TILES IN JET

ＤＥＵＴＥＲＩＵＭＩＮＦＬＵＸＰＲＯＦＩＬＥＡＬＯＮＧＴＨＥＡＰＥＸＯＦＴＨＥＵＰＰＥＲＸ－ＰＯＩＮＴＴＩＬＥＳＩＮＪＥＴ￥Ｙ．Ｋ．Ｚｈｕ（ＳｏｕｔｈｗｅｓｔｅｒｎＩｎｓｔｉｔｕｔｅｏｆＰｈｙｓｉｃｓ，Ｐ．Ｏ．Ｂｏｘ４３２，Ｃｈｅｎｇｄｕ６１００４１...     

混煤氮的热解析出特性及燃料NO_x的形成规律

混煤氮的热解析出特性及燃料ＮＯ_ｘ的形成规律邱建荣，马毓义，曾汉才，吕焕尧，喻秋梅（华中理工大学煤燃烧国家重点实验室武汉４３００７４）关键词：混煤，ＮＯ_ｘ，混合比，燃烧。ＥＭＩＳＳＩＯＮＯＦＮＩＴＲＯＧＥＮＣＯＭＰＯＵＮＤＳＡＮＤＮＯ_ｘＦＯＲＭＡＴ?..     

THERMAL INSTABILITY OF D-T BURNING PLASMAS

ＴＨＥＲＭＡＬＩＮＳＴＡＢＩＬＩＴＹＯＦＤ－ＴＢＵＲＮＩＮＧＰＬＡＳＭＡＳ￥Ｂ．Ｒ．ＳＨＩＹ．Ｘ．ＬＯＮＧＨ．Ｇ．ＺＨＡＯ（ＳｏｕｔｈｗｅｓｔｅｒｎｉｎｓｔｉｔｕｔｅｏｆＰｈｙｓｉｃｓ，Ｐ．Ｏ．Ｂｏｘ４３２，Ｃｈｅｎｇｄｕ６１００４１，Ｓｉｃｈｕａｎ...     

GIANT MAGNETO-IMPEDANCE IN Fe-BASED SOFT FERROMAGNETIC RIBBONS

ＧＩＡＮＴＭＡＧＮＥＴＯ－ＩＭＰＥＤＡＮＣＥＩＮＦｅ－ＢＡＳＥＤＳＯＦＴＦＥＲＲＯＭＡＧＮＥＴＩＣＲＩＢＢＯＮＳＣｈｅｎＣｈｅｎＭｅｉＬｉａｎｇｍｏＤｅｐａｒｔｍｅｎｔｏｆＰｈｙｓｉｃｓ，ＳｈａｎｄｏｎｇＵｎｉｖｅｒｓｉｔｙ，Ｊｉｎａｎ２５０１００...     

CALCULATION FOR STRETCHING VIBRATIONAL SPECTRUM OF CH_4

ＣＡＬＣＵＬＡＴＩＯＮＦＯＲＳＴＲＥＴＣＨＩＮＧＶＩＢＲＡＴＩＯＮＡＬＳＰＥＣＴＲＵＭＯＦＣＨ４ＣｈｅｎＸｉａｎｇｒｏｎｇＧｏｕＱｉｎｇｑｕａｎＰａｎｇＸｉａｏｆｅｎｇＩｎｓｔｉｔｕｔｅｏｆＡｔｏｍｉｃａｎｄＭｏｌｅｃｕｌａｒＳｃｉｅｎｃｅａｔＨｉｇ...     

［（μ－CF＿3CO＿2）＿2Ln（μ－CF＿3HCO＿2）Al（i－Bu）＿2·2THFl＿2（Ln＝Nd，Y）配合物的NMR和X－射线衍射研究

对［μ－ＣＦ＿３ＣＯ＿２）＿２Ｌｎ（μ－ＣＦ＿３ＨＣＯ＿２）Ａｌ（ｉ－Ｂｕ）＿２·ＴＨＦｌ＿２（Ｌｎ＝Ｎｄ，Ｙ）配合物单晶结构的Ｘ－射线分析指出，配合物具有中心对称性，配位中心由两个稀土和两个Ａｌ离子组成，稀土由两个ＴＨＦ和６个ＴＦＡ分子配位形成畸变的三盖三棱柱结构，Ａｌ由两个ＴＦＡＧ和两个ｉ－Ｂｕ配位形成四面体结构。桥连Ａｌ与两个稀土的ＴＦＡ分子的羧基发生歧化加氢，其碳原子由ＳＰ￣２型转变为ＳＰ￣３型．ＮＭＲ研究表明，在ＴＨＦ溶液中，该配合物保持了它在单晶中的配位结构，所不同的是两个ｉ－Ｂｕ在溶液中有两种异构形成，二者间为慢交换过程。     

TBP对部分皂化的DMHPA—正庚烷体系及萃取稀土有机相的影响

研究了部分皂化的二（１甲基庚基）磷酸（ＤＭＨＰＡ）磷酸三丁酯（ＴＢＰ）—正庚烷（Ｃ７Ｈ１６）体系及萃取稀土有机相的聚集状态。结果表明，ＴＢＰ可以扩大ＤＭＨＰＡＣ７Ｈ１６Ｈ２Ｏ微乳状液形成的区间，并且对萃取有机相的存在状态及水的行为有明显的影响，在一定的条件下有凝胶形成。ＦＴＩＲ光谱分析表明，该类凝胶中ＤＭＨＰＡ和ＴＢＰ与稀土离子以多种形式配位，ＴＢＰ与ＤＭＨＰＡ及水的氢键结合对凝胶网状结构的形成也起了一定的作用。     

萃金体系第三相的产生及其谱学研究

利用^198Au示踪法研究了十四烷基二甲基苄基氯化铵从碱性氰化液中萃取金第三相的产生过程，同时用傅里叶变换红外光谱（FTIR），核磁共振（NMR），激光光散射（DLS）等方法分析了第三相形成后上下两有机相的微观结构，结果表明，随着有机相中金浓度的增大，有机相中有纳米级的聚集体形成；当金浓度继续增大时，有机相分为上下两相，有机相中的金，磷酸三丁酯（TBP）和水主要集中在下层，下层有机相有明显的水特征吸收峰，TBP的P=O伸缩振动向低频移动，核磁共振（^31P-NMR)的化学位移明显移向高场；用激光光散射技术测定了两有机相中聚集体的大小。     

EXAFS研究硫酸硫脲反萃季铵氰化金的机理

季铵盐可以直接从氰化浸出液中萃取金 ,但反萃困难。酸性硫脲通空气反萃体系是目前从季铵盐中反萃氰化金最有效的体系 ,但对其机理的研究很少。文章采用扩展X射线吸收精细结构 (EXAFS)等方法研究了硫酸硫脲从负载氰化金季铵盐中反萃金的机理。研究结果表明 ,在反萃过程中 ,硫酸、硫脲和硫脲金都能以中性分子进入有机相 ,中性缔合在季铵盐反萃过程中不可忽视。反萃机理如下 :(1)硫酸和硫脲首先进入有机相被萃取 ;(2 )在有机相中 ,硫脲争夺金的氰根配位 ,使氰化金变成硫脲金 ,同时游离出来的氰根与硫酸中的氢离子作用变成氢氰酸 ,在鼓空气搅拌条件下氢氰酸被空气迅速带走排除 ;(3)硫脲金配合物在有机相和水相中分配 ,大部分硫脲金进入水相 ,从而达到反萃的目的。     

Ultrasonically induced phthalocyanine degradation: decolouration vs. metal release

The ultrasonically induced degradations of nickel(II) 2,9,16,23-tetraphenoxy-29H, 31H-phthalocyanine and vanadyl 2,9,16,23-tetraphenoxy-29H, 31H-phthalocyanine in a biphasic system consisting of chloroform and water are investigated. Decolourisation of the organic phase containing the metallo-phthalocyanines is found to occur rapidly (approximately minutes for 8 ml of ca. 5 microM solution). Analysis of the aqueous solute via ICP-OES, reveals significant amounts of the released nickel ultimately transfers into the aqueous phase but at a rate much slower than that of decolourisation, whereas the vanadium remains within the organic phase suggesting only partial degradation despite efficient decolourisation.     

Matrix effects on the surface plasmon resonance of dry supported gold nanocrystals

We present a method to characterize surface-chemical properties of gold nanocrystals. Spherical, 60 nm gold nanocrystals were immobilized on quartz substrates by a coupling agent and cleaned in a hydrogen plasma. The nanocrystals were then functionalized with alkanethiol self-assembled monolayers (SAM) of varying chain lengths by adsorption from the gas phase, and localized surface plasmon resonance (LSPR) spectroscopy was performed on the samples. Depending on the alkanethiol chain length, the adsorption of the SAM redshifted the LSPR to different extents, in accordance with Mie theory. SAM thickness differences below 1 nm could be easily resolved. Our results demonstrate that LSPR spectroscopy can be applied to characterize thin organic layers on dry supported gold particles with high sensitivity.     

我国几种地带性土壤中磷素形态的研究

探明土壤磷素的存在形态,有助于揭示其在环境中的累积、迁移和转化过程及生物有效性。目前,在大尺度样带上开展土壤磷素形态空间变异规律的研究较少。本研究中,沿纬度方向采集了我国东部不同气候带分布的7种地带性林地土壤（包括寒温带的棕色针叶林土、中温带的暗棕壤、暖温带的棕壤、北亚热带的黄棕壤、中亚热带的黄壤、南亚热带的赤红壤和热带的砖红壤）,将化学浸提法与溶液磷-31核磁共振（31P NMR）波谱法相结合,分析了土壤中磷素形态以及与其他土壤性质之间的关系,以期为阐明土壤磷素形态的空间变异性及其驱动因素提供基础资料。结果表明：供试土壤中,全磷、有效磷、无机磷和有机磷的含量范围分别为179.8～825.2,2.41～15.3,92.6～351.2和14.7～474.4 mg·kg-1,其中活性、中等活性、中等稳定性和高稳定性有机磷组分的含量范围分别为1.38～30.9,8.63～213.7,3.01～32.2和1.73～199.2 mg·kg-1。根据溶液31P NMR波谱,鉴定出供试土壤中含有无机形态的磷素即正磷酸盐和焦磷酸盐,同时也鉴定出了磷酸单酯、磷酸二酯和膦酸盐等有机形态磷素的存在,其中磷酸单酯中又鉴定出了新-肌醇六磷酸、D-手性-肌醇六磷酸、RNA单核苷酸、α-磷酸甘油、肌-肌醇六磷酸、β-磷酸甘油和鲨-肌醇六磷酸,磷酸二酯中又鉴定出了DNA的存在;所有土壤中均未检测出多聚磷酸盐的存在,除棕色针叶林土和暗棕壤外的其他土壤中未检测出膦酸盐的存在,而赤红壤中未检测出DNA的存在;无机形态的磷素以正磷酸盐为主,而有机形态的磷素则以磷酸单酯为主。总体来看,无论化学浸提法还是溶液31P NMR波谱法,从寒温带的棕色针叶林土到热带的砖红壤,全磷、有效磷、无机磷、有机磷及其组分的含量均呈现下降趋势。溶液31P NMR波谱与化学浸提法鉴定的磷素形态之间存在相关关系,其中正磷酸盐与活性有机磷的关系最为密切,磷酸单酯和膦酸盐与中等活性有机磷的关系最为密切,而焦磷酸盐和磷酸二酯与中等稳定性有机磷的关系最为密切。与化学浸提法相比,溶液31P NMR波谱法能从详细的分子水平上揭示土壤磷素形态的空间变异规律。     

Temperature-induced particle self-assembly

Agglomeration of monodisperse thiol-stabilized gold particles with diameters of 6 nm, suspended in organic solvents, was induced by the cooling of the suspension. A sharp transition between the stable suspension and agglomeration resulted. The temperature of the transition depends on the concentration and the compatibility of the solvent. The morphology of the formed particle structures upon agglomeration implies that the used metal colloid can be described as a van der Waals-gas. The particles undergo phase transitions from a stable fluid phase to a metastable phase, in which nucleation and growth occur, or to an instable phase, in which spinodal decomposition occurs. The results will direct research on routes to nanostructured materials using nanoparticles as building blocks.     

三烷基氧化膦及其萃合物的红外光谱研究

三烷基氧化膦是一种新型的镧系元素和锕系元素萃取剂，本文研究了其红外光谱特征及其与稀土元素和硝酸所形成的萃合物的红外光谱。     

Size and Shape Effect of Gold Nanoparticles in “Far‐Field” Surface Plasmon Resonance

The “far‐field” surface plasmon resonance (FSPR) of metal nanoparticles, which have built a facile way to emission enhancement of red, green, blue, and white with nice reproducibility, has big potential application in solution‐processed organic light‐emitting diodes (OLEDs). According to the theory of the “far‐field” effect, the reflectivity of the metal surface and the phase shift at the reflection play an important role in enhancing ratio, which strongly relate to the size and shape of nanoparticles. In this work, gold nanospheres with different sizes and nanorods are synthesized in order to determine the size and shape effect of FSPR. The results demonstrate that the one with higher reflectivity in a certain range induces a better emission enhancement in the luminous efficiency and the maximum brightness. The nanoparticles with bigger sizes and shape of rods have higher reflectivity, which is consistent with the simulation based on FSPR effect. The phase shifts of different nanoparticles are optimized by the distance between gold nanoparticles and emitters. The metal NPs with a high reflectivity and the applicable phase shift will have big potential for the emission enhancement in OLEDs.     

Manipulation of organic “needles” using an STM operated under SEM control

Nano-sized P4P (para-quaterphenylene) organic crystallites grown on a gold substrate were removed and redeposited using the tip of an STM. The controlled lift-off of the needle-shaped crystallites was imaged by a simultaneously operated SEM. The forces exerted by the metal STM tip on the nano-crystal during this nano-manipulation process could be determined by monitoring the deflection of the STM tip. After the lift-off process the former contact area was imaged using the STM. These STM micrographs clearly demonstrate that the region between the needles is covered by a P4P layer with a thickness of at least 3 nm.