苯并噻唑基修饰的开链Cu2+比色探针的合成及性能

以N-苯基二乙醇胺和2-巯基苯并噻唑为原料通过亲核取代反应合成了一种新型的苯并噻唑基修饰的开链冠醚类化合物1,并用核磁共振氢谱, 核磁共振碳谱及元素分析方法对合成产物进行了表征。利用紫外光谱仪考察了化合物1与多种金属离子（Mn²⁺、Co²⁺、Cu²⁺、Zn²⁺、Ni²⁺ 、Fe³⁺、 Hg²⁺、Cr³⁺、Al³⁺）在乙腈溶液中的光谱变化,并探究了化合物1处理过的滤纸条在水溶液中对金属离子的识别效果,通过核磁共振氢谱讨论了化合物1与金属离子形成配合物的作用机理。实验发现,化合物1的乙腈溶液中添加Cu²⁺后溶液颜色变为棕色,明显区别于添加其他离子;在水溶液中,特制的滤纸条遇到Cu²⁺会呈现黄色,而遇其他离子均无颜色变化。结果表明,化合物1仅对Cu²⁺具有选择性,且能通过裸眼进行识别,是一种高效、简便的Cu²⁺探针。     

Influence of the SiO2/Al2O3 ratio on the synthesis and physicochemical characteristics of levyne-type zeolite

Levyne-type zeolites were synthesized from gels of initial compositions 4.5Na₂O-6MeQI-xAl₂O₃ 30SiO₂-500H₂O, with MeQ = methylquinuclidinium and 0.6 ≤ x ≥ 3 at 150 ≤ t ≥ 190 °C. The ²⁹Si NMR spectra show the presence of two crystallographically different sites in the structure. The ²⁷Al NMR spectra also suggest the presence of two different tetrahedral Al atoms incorporated in the structure. A rather high amount of defect groups SiOM and Si(OM)₂ with M = MeQ, Na and/or H are present in the precursor samples. The Si(OM)₂ groups are eliminated during calcination, and a certain amount of SiOM still persists after calcination. The combined ¹³C NMR and thermal analysis data allowed one to interpret the nature of the two different types of MeQ⁺ ions occluded in the levyne channels.     

TEABr directed synthesis of ZSM-12 and its NMR characterization

Synthesis of ZSM-12 using tetraethylammonium bromide (TEABr) as the template was investigated. Among the various parameters that affect the crystallization of ZSM-12, aluminum content of the gel, OH⁻/SiO₂ and TEA/SiO₂ ratios were the important determinants. Systematic variations of these parameters revealed that the TEABr-assisted synthesis had many similarities to the synthesis using TEAOH template reported earlier, with the exception that the OH⁻/SiO₂ ratios had to be maintained at lower values. Furthermore, the OH⁻/SiO₂ ratios favorable for ZSM-12 formation lie in a very narrow range. The source of alkalinity also affected the rate of crystallization and the composition of the product. The crystallization was found to be faster and better incorporation of aluminum in the zeolite framework was obtained when NaOH was used to provide alkalinity rather than KOH. Successful synthesis of highly crystalline ZSM-12 samples with Si/Al ratio around 30 was achieved using a minimal amount of relatively inexpensive TEABr (TEA/SiO₂=0.125).

Aluminum-27 NMR spectroscopy unambiguously revealed that all aluminum atoms are incorporated in the zeolite framework in tetrahedral coordination. The NMR line-widths of aluminum signals of the calcined samples were significantly larger than those with template incorporated samples. Spin-lattice relaxation times, conventional and rotating frame, as well as magic angle spinning (MAS) cross-polarization data with variable contact time support that there is a significant proton reservoir in the aluminum framework. The NMR data indicate that many distorted tetrahedral sites are formed upon removal of the template and some of these sites contain Al–OH moieties.     

桥联茂金属催化1-癸烯聚合及其产物结构与性能

采用桥联茂金属催化体系rac-Et(1-Ind)₂ZrCl₂/Al(ⁱBu)₃/[Me₂NHPh]⁺[B(C₆F₅)₄]^-催化1-癸烯聚合,考察了茂金属浓度、Al/Zr摩尔比、B/Zr摩尔比、温度、反应时间对反应转化率、黏度和摩尔质量的影响.当反应条件为1-癸烯20mL、甲苯20mL、Zr/烯摩尔比8×10^-5、Al/Zr摩尔比80、B/Zr摩尔比1.5、温度80℃、反应时间1h时,转化率达到96.2%.采用¹³C NMR和¹H NMR表征了产物的结构,优化条件下所得的聚合产物具有高黏度指数(259)和低分子量分布(2.088),可作为理想的润滑油基础油的原料.     

Synthesis of aluminophosphate molecular sieve AlPO4-11 nanocrystals

AlPO₄-11 nanocrystals, 0.05×0.08 μm in size, were synthesized by optimizing the following chemical parameters: the crystallization temperature and time, the H₂O content, the molar ratio of phosphorus to organic template (P₂O₅/R), and the HF content. The products were characterized by powder X-ray diffraction and scanning electron microscope. AlPO₄-11 nanocrystals could not be obtained by optimizing only the crystallization temperature, time and the water content, but obtained by optimizing the molar ratio of P₂O₅/R, the organic template, and the HF content.     

Synthesis, characterization and hydrolysis of an aliphatic polycarbonate by terpolymerization of carbon dioxide, propylene oxide and maleic anhydride

Terpolymerization of propylene oxide (PO), carbon dioxide (CO₂) and maleic anhydride (MA) was carried out by using a polymer-supported bimetallic complex (PBM) as a catalyst. A degradable aliphatic poly(propylene carbonate maleate) (PPCM) was synthesized, and determined by FT-IR, ¹H NMR, ¹³C NMR, DSC, TGA and WAXD measurements. The influences of various reaction conditions such as molar ratio of the monomers, reaction time and reaction temperature on the terpolymerization progress were investigated. The results showed that MA was inserted into the backbone of CO₂–PO successfully. The viscosity, glass transition temperature and decomposition temperature of the terpolymers were much higher than those of poly(propylene carbonate) (PPC). Because of the existence of the MA ester unit, PPCM had stronger degradability than PPC in a pH 7.4 phosphate-buffered solution. MA offered an ester structural unit that gave the terpolymers remarkable degradability. And the degradation rate of the backbone increased with the insertion of MA into the terpolymers.     

AHT型磷酸铝分子筛的合成及表征

以不同链长的有机胺为模板,选用不同的铝源,采用水热法合成AHT型分子筛。考察铝源、原料摩尔比和有机模板剂对AHT型磷酸铝分子筛（AlPO₄-H2）合成的影响,并利用XRD、SEM、BET、TG/DTG等技术对合成的AHT构型磷酸铝分子筛进行表征。结果表明,在所测试的4种铝源中,只有以拟薄水铝石为铝源时才能获得AHT型分子筛;反应混合物中水的含量对AHT型磷酸铝分子筛的合成具有显著的影响,当n(H₂O)/n(Al₂O₃)大于或小于20时,均有杂相生成;在优化的条件下,以烷基链长度大于4的有机胺为模板剂,均能获得纯相的AHT型磷酸铝分子筛。当有机胺烷基链长度小于或等于4时,有机胺的最大伸展长度达不到AHT型磷酸铝分子筛的晶胞参数c值,无法合成纯相AHT型磷酸铝分子筛。合成的AHT型磷酸铝分子筛形貌为针状或棒状,结构骨架中磷铝摩尔比为1,是一种典型的磷酸铝分子筛。该分子筛具有良好的酸碱稳定性,但高温容易导致其结构转变。     

Synthesis and characterization of urea bridged hybrid periodic mesoporous organosilica materials

Urea bridged organic–inorganic hybrid mesoporous SiO₂ materials (U-BSQMs) were synthesized through a sol–gel procedure by co-condensation of bis(triethoxysilyl propyl) urea (BSPU) under basic conditions using cetyltrimethylammonium bromide (CTAB) as organic template. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the mesoporous structure of the sample. Fourier-transform infrared spectroscopy (FT-IR), solid state CP-MAS NMR spectroscopy of ²⁹Si (²⁹Si CP-MAS NMR) and ¹³C (¹³C CP NMR) indicated that most of the Si–C bonds are unbroken during the synthesis process. The N₂ adsorption–desorption results revealed that these hybrid mesoporous SiO₂ materials have bimodal distribution of pores with pore diameters of 2.4 and 3.8 nm, respectively. Thermogravimetric analysis (TG) demonstrated that about 16% Si–C bonds have been broke during the synthesis progress. This kind of material is expected to find possible application in ion supporting, drug delivery and catalysis.     

利用13C NMR技术探究叔胺溶液中HCO3-的生成

利用¹³C NMR技术对CO₂捕获叔胺溶剂进行了碳元素的定量研究,主要考察了对胺溶剂解吸热影响较大的HCO₃^-的生成规律。重点对叔胺分子结构中羟基官能团(-OH)、羟烷基数目、烷基支链及氮原子(N)所连接烷基链大小对胺溶剂生成HCO₃^-的影响。在20℃条件下分别对1 mol·L^-1具有不同CO₂负载的1-二甲基氨基-2-丙醇(1DMA2P)、N-甲基二乙醇胺(MDEA)、3-二甲氨基-1-丙醇(3DMA1P)、二乙氨基-2-丙醇(1DEA2P)、N,N-二乙基乙醇胺(DEEA)、N,N-二甲基乙醇胺(DMMEA)及三乙醇胺(TEA)溶液进行了¹³C NMR测试研究。实验结果显示:在相同浓度的叔胺水溶液中,同一CO₂负载下的叔胺-CO₂-水体系中HCO₃^-的含量顺序为:DMMEA > MDEA>3DMA1P > 1DMA2P > TEA > DEEA > 1DEA2P。通过对各叔胺分子结构中N原子的电子云密度大小及空间位阻效应分析,得出如下结论:3DMA1P分子中-OH官能团离N原子的距离大于其在DMMEA分子中的距离,导致其生成了较少的HCO₃^-;DMMEA分子中N原子上连接的烷基链小于DEEA分子中N原子上的烷基链,导致DMMEA溶液中生成了更多的HCO₃^-;MDEA分子中羟烷基数目少于TEA分子中的羟烷基数目,且MDEA比TEA多了一个甲基,导致MDEA溶液中含有更多的HCO₃^-;3DMA1P相比1DMA2P、DEEA相比1DEA2P分子中都少了一个甲基支链,导致3DMA1P溶液相比1DMA2P溶液、DEEA溶液相比1DEA2P溶液生成了更多的HCO₃^-。     

左旋海松酸的分离及其理化数据测试

采用胺化法从松脂中分离左旋海松酸,然后利用超声波辅助左旋海松酸粗品重结晶进行纯化,通过单因素和正交试验优化左旋海松酸分离的工艺条件,得到的最佳工艺条件为：无水乙醇用量20 mL(1 g左旋海松酸),结晶温度0 ℃,超声波频率为53 kHz,重结晶次数为2次,此条件下得到的左旋海松酸纯度达97%。超声波辅助左旋海松酸重结晶,大幅度缩短了晶体成核时间,5~6 h可得到晶型细小均匀分散的长方型片状透明晶体。通过红外光谱(FT-IR)、核磁共振(¹H NMR, ¹³C NMR)、气相色谱-质谱联用(GC-MS)表征了纯化后左旋海松酸的分子结构,依据氧弹量热法、TG-DSC法和基团贡献法分析得到左旋海松酸的标准摩尔生成焓(Δ_fH_m^?)-700.23 kJ/mol和熔化焓94.99 kJ/mol。     

Control of ordered structure and morphology of cubic mesoporous silica SBA-1 via direct synthesis of thiol-functionalization

Well-ordered cubic mesoporous silicas SBA-1 functionalized with thiol groups have been synthesized via co-condensation of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) templated by cetyltriethylammonium bromide (CTEABr) under strongly acidic conditions. Various synthesis parameters such as HCl concentration, synthesis temperature, and time for hydrothermal treatment were systematically investigated as a function of MPTMS contents. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), solid-state ¹³C and ²⁹Si NMR spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and nitrogen sorption measurements. Direct evidence of the presence of chemically attached thiol moieties was provided by solid-state ²⁹Si and ¹³C NMR spectroscopy. A high degree of structural ordering was still retained when MPTMS loading was incorporated up to 20 mol% in the synthesis mixture. Increasing the synthesis temperature and the time for the hydrothermal treatment not only increased the degree of framework cross-linking, but also did not lead to the undesirable phase transformation as often observed in the conventional synthesis of pure silica SBA-1. SEM results reveal that the morphology of thiol-functionalized SBA-1 depends on the HCl concentration used in the synthesis. The sample prepared with a low acid concentration exhibits a highly isotropic morphology with more facets than that of pure silica SBA-1, whereas it changes to a spherical shape as the acid concentration is increased. The maximum content of the attached thiol group (–SH) in the mesoporous framework is 2.39 mmol/g. The thiol-functionalized SBA-1 mesoporous materials are efficient Hg²⁺ adsorbents.     

Vanadyl–aluminum binary phosphate: Al/V ratio influence on their structure and catalytic behavior in the 2-propanol conversion

The synthesis of aluminum–vanadium–phosphorus (AlVPO) systems by sol–gel method was carried out with several P/Al/V molar ratios. They were calcined at 450–550 °C as previously applied in the synthesis of amorphous AlPO₄ catalysts. Materials were characterized by chemical analysis, thermogravimetric analysis, X-ray diffraction, UV-Vis, ³¹P and ²⁷Al MAS NMR, scanning electron microscopy and nitrogen adsorption. The textural properties and morphology of AlVPO materials were influenced by the Al/V ratio and thermal treatment. As the porosity of the solids decreased, both the BET surface areas as well as their primarily amorphous character did as well, while the vanadium content and calcination temperature increased. After calcination, the presence of two pure phosphate phases, AlPO₄ (-cristobalite) and β-VOPO₄, was observed. Their catalytic behavior in the conversion of 2-propanol was studied. Both the activity for 2-propanol conversion and the selectivity values to propene and propanone were also greatly affected by the Al/V ratio values. Thus, the activity of the AlVPO systems increased with the aluminum content, whereas the 2-propanone selectivity decreased slightly. On the basis of kinetic study we conclude that dehydration to propene and dehydrogenation to propanone could proceed via different active sites and mechanisms.     

霍林河褐煤化学结构特性的13C NMR与FTIR对比分析

采用¹³C NMR及FTIR对霍林河褐煤的化学结构特性进行深入分析,通过¹³C NMR计算得到霍林河褐煤包含34.32%的脂肪族碳、61.25%的芳香族碳以及4.43%的羰基碳。平均每个芳环团簇包含1~2个芳香环,每个芳香环中平均碳原子取代数为3~4。平均亚甲基碳链数为1.4,烷链支化度为25.47%,说明脂肪族多以短链分支形式存在。通过对霍林河褐煤红外光谱进行分峰拟合,计算得到煤的FTIR结构参数（平均亚甲基碳链数、芳香环取代度、烷链支化度）与¹³C NMR计算结果相吻合。虽然芳碳率（f_ar-F=55.37%）与¹³C NMR计算结果存在一定的偏差,但是FTIR很大程度上仍然可以反映煤的碳骨架结构特性。     

Preparation and characterization of crosslinked polyimide–poly(dimethylsiloxane)s

Crosslinked polyimide–poly(dimethylsiloxane)s with theoretical content of the siloxane phase up to 60 wt% were prepared. The starting materials were p-aminophenyltrimethoxysilane terminated polyamic acids with number average molecular weight of 10,000 g mol⁻¹, based on 4,4′-oxydiphthalic anhydride and 4,4′-oxydianiline and dimethoxydimethylsilane. The structure of the prepared polymeric materials was analyzed using ²⁹Si and ¹³C NMR solid-state spectroscopy. Their thermal and mechanical properties, chemical resistance and density were evaluated. The influence of the basic catalysts employed (ammonium hydroxide) on the course of the reaction and properties of the materials was also studied.     

Crystalline galliosilicate molecular sieves with the beta structure

Crystalline galliosilicates with the beta structure have been synthesized from alkali-free hydrogels with the composition Ga₂O₃:xSiO₂:12(TEA)₂O:1285H₂O, where x=40, 60, 80 and 100. The addition of an alkali (Ga₂O₃/Na₂O=1.0) to the hydrogel in the form of sodium gallate decreased crystallization times at 135°C to 10 days from 14 days. Crystallization reactions are not stoichiometric and the crystals' silica-to-gallia ratio (SGR) is always less than that in the parent hydrogel. Thermal analysis has shown that TEA ions first decompose and are then thermally desorbed, probably in the form of Hofmann decomposition products. Residual hydrocarbons are burned at T>400°C. The calcined crystals have surface area in the 500–625 m² g⁻¹ range. FTIR experiments with chemisorbed pyridine have shown that the isomorphous substitution of Al(IV) with Ga(IV) atoms decreases the acid-site strength and changes the relative B/L acid-site ratio of the crystals. IR spectra at a desorption temperature of 500°C revealed that all the pyridine desorbed from B sites but not from L sites in Ga-beta, whereas the Al-beta analog retained pyridine on both L and B sites. Microcalorimetry experiments with ammonia at 150°C have revealed the existence of different acid-site (B+L) strengths and site populations. The total number of sites available to NH₃ chemisorption and the number of strong acid sites show the same dependence on the SGR value of the crystals. ²⁹Si MAS-NMR spectra contain a resonance at −111 ppm attributed to T(4Si,0Ga) groups and a second resonance at −102 ppm attributed to T(3Si,1Ga) groups. ⁷¹Ga NMR spectra confirm that Ga(IV) is the dominant species and that Ga(VI) formation depends, in part, on the thermal pretreatment applied to the crystals. ¹H NMR results have revealed that after calcination in air at 500°C, there are residual hydrocarbon compounds in the beta microporous structure. This can be avoided if the organic template is decomposed in nitrogen at 500°C for 1 h and the decomposition products are removed oxidatively by a second calcination step in air at 550°C for 2 h.     

Al, N, C and H NMR spectra and negative-ion electrospray mass spectra of the 2:1 aluminium(III) complexes of azo dyes derived from anthranilic acid

The ²⁷Al, ¹⁵N, ¹³C and ¹H NMR spectra in DMSO and mass spectra of 2:1 aluminium(III) complexes (1b–4b) derived from anthranilic acid azo coupling products with 4-tert.butylphenol (1a), 2-naphthol (2a) acetoacetanilide (3a) 3-methyl-1-phenylpyrazol-5-one (4a) were measured and analysed. It was found that the aluminium atom was six-coordinated, being bound to two oxygens and the nitrogen originating from anthranilic acid.     

铝源前驱体对离子热法合成磷酸铝分子筛的影响

以离子液体1-乙基-3-甲基-咪唑溴盐为溶剂和模板剂,选用不同的铝源,在常压下合成AlPO4-11分子筛. 考察了在不同铝源条件下,物料配比、晶化时间和晶化温度对合成AlPO4-11分子筛的影响. 产物通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)等表征手段进行了表征. 结果表明铝源性质的不同导致了合成规律和合成机理的不同. 以异丙醇铝为铝源合成分子筛时,所需最佳P/Al比为3/1,分子筛的晶化速率较慢;而以碱式乙酸铝为铝源合成分子筛时,物料的P/Al摩尔比相对较低(1.5/1),分子筛的合成具有更快的晶化速率.     

Development of structural characterization and physicochemical behaviour of triphenylamine blocks

A novel multitriphenylamine substituted derivatives, possessing the respective photochromic groups were synthesized by Stille cross-coupling methodology. The hyperbranched structures have been characterized by ¹H NMR, ¹³C NMR. Obtained structures show good stability in common organic solvents such as CHCl₃, toluene and CH₂Cl₂ and exhibit excellent thermal stability. Electrochemical results and theoretical calculation suggest that oxidation and reduction start from the side of amine and branching five member heterocycle ring moieties, respectively.     

Spectroscopic analysis of carbon dioxide and nitrogen mixed gas hydrates in silica gel for CO2 separation

In this study solid-state NMR spectroscopy was used to identify structure and guest distribution of the mixed N₂ + CO₂ hydrates. These results show that it is possible to recover CO₂ from flue gas by forming a mixed hydrate that removes CO₂ preferentially from CO₂/N₂ gas mixture. Hydrate phase equilibria for the ternary CO₂–N₂–water system in silica gel pores were measured, which show that the three-phase H–L_w–V equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO₂ in the vapor phase decreased. ¹³C cross-polarization (CP) NMR spectra of the mixed hydrates at gas compositions of more than 10 mol% CO₂ with the balance N₂ identified that the crystal structure of mixed hydrates as structure I, and that the CO₂ molecules occupy mainly the abundant 5¹²6² cages. This makes it possible to achieve concentrations of more than 96 mol% CO₂ gas in the product after three cycles of hydrate formation and dissociation.     

Template-free synthesis and adsorption properties of microporous crystal AlPO4-H3

A microporous aluminophosphate molecular sieve, AlPO₄-H3, was prepared without using organic templates. It was crystallized at temperatures as low as 90 °C from aluminophosphate gels with a molar ratio of Al₂O₃/P₂O₅1; the addition of seed crystals was essential. AlPO₄-H3 was topotactically and irreversibly converted into AlPO₄-D at 300 °C, which adsorbed water up to 0.2 ml/g at 25 °C, although nitrogen gas was hardly adsorbed at liquid nitrogen temperature.