2,3,6-三氨基-5-硝基吡啶的合成与应用

以2,6-二氨基-3,5-二硝基吡啶(DADNP)为原料,选择性还原制得关键中间体2,3,6-三氨基-5-硝基吡啶,同时对其影响因素进行探究,并做稳定性分析.实验表明:以DADNP为底物,水合肼与自制多硫化钠为还原液,回流反应2h,得纯度为99.2%的目标产物,产品收率为58.4%.并将此化合物成功应用于AB型新单体前体4-(N-(2,6-二氨基-5-硝基吡啶3-基)氨基甲酰基)苯甲酸甲酯(ANPCB)的合成(粗品纯度95.12%,收率60.3%)及AB型单体骨架分子4-(5-氨基-6-硝基-1H-吡啶并[2,3-d]咪唑-2-基)苯甲酸甲酯(ANPIB)的探索研究中.所有产物结构经13 C-NMR、MS和FTIR分析表征确认.     

4,7-二甲基香豆素的合成及潜在靶标

为优化合成4,7-二甲基香豆素的最佳反应条件、激发潜在药物靶标,以间甲酚和乙酰乙酸乙酯为原料,二氯甲烷为溶剂,硫酸为催化剂,采用Pechmann缩合反应合成4,7-二甲基香豆素。利用Discovery Studio软件对4,7-二甲基香豆素进行潜在药物作用靶标模拟研究。用正交实验法确定了4,7-二甲基香豆素的较优反应条件为:硫酸与间甲酚质量比为2.5,反应温度为20℃,二氯甲烷与间甲酚体积质量比为15 mL/g时,4,7-二甲基香豆素摩尔收率为63.9%。4,7-二甲基香豆素的潜在靶标可能为糖原合成酶激酶-3β。     

生物碱apptamine的全合成研究

生物碱aaptamines具有广泛的生物活性,有着重要的医药研究价值.以高藜芦胺为起始原料,经酰化、Bischler-Napieralski反应、氧化、硝化得到6,7-二甲氧基-8-硝基异喹啉-1-甲醛(9).化合物9经Henry反应,用叔丁醇钾作碱催化与硝基甲烷反应得到1-(6,7-二甲氧基-8-硝基异喹啉)-2-硝基乙醇(10),化合物10再在DMAP催化、乙酸酐作用下脱水成(E)-6,7-二甲氧基-8-硝基-1-(2-硝基乙烯基)异喹啉(11),最后铁粉还原关环成功合成了aaptamine,总收率为28%.aaptamine盐酸盐结构经1H NMR、13C NMR和HRMS表征确认,其他中间体结构均经1H NMR、13C NMR表征确认.     

杀虫剂双苯氟脲的合成研究

以2-氯-14-硝基苯酚为原料,经还原反应合成2-氯-4-氨基苯酚,再与全氟甲基乙烯基醚加成3-氯-4-[1,1,2-三氟-2-(三氟甲氧基)乙氧基]苯胺;将2,6-二氟苯甲酰胺与草酰氯酰化合成2,6-二氯苯甲酰异氰酸酯,再与3-氯-14-[1,1,2一三氟-2-(三氟甲氧基)乙氧基]苯胺加成得到杀虫剂双苯氟脲,总收率为68.9%.     

来那度胺中间体的水相合成

传统的N-溴代丁二酰亚胺(NBS)α-溴代反应是用光引发偶氮二异丁腈(AIBN)产生自由基,在四氯化碳或者其它氯化有机溶剂中进行.在水介质中,采用加热到80～85℃、控制搅拌速度为20～30 r/min产生自由基引发α-溴代反应的方法合成来那度胺中间体:2-溴甲基-3-硝基苯甲酸甲酯.该反应条件下2-甲基-3-硝基苯甲酸甲酯转变为熔融态,在水中形成两相,目标产物产率可达80%,纯度为93%.不需要光照和有毒溶剂,2-溴甲基-3-硝基苯甲酸甲酯容易通过可变速度搅拌和耐酸设备进行工业化生产.     

1-氨基-2-硝基胍3,5-二硝基-1,2,4-三唑盐的合成及性能研究

以水合肼、双氰胺和硝基胍三种化合物为起始原料,通过缩合反应和复分解反应制备了一种新型含能材料一1-氨基-2-硝基胍3,5-二硝基-1,2,4-三唑盐;通过热重曲线和差示扫描量热曲线(TG-DSC)研究了目标化合物的热行为;利用密度泛函理论(DFT),在B3LYP/6-31+G**基组水平下预估了1-氨基-2-硝基胍3,5-二硝基-1,2,4-三唑盐的爆轰性能。研究结果表明,在反应时间4 h,反应温度55℃的条件下,1-氨基-2-硝基胍3,5-二硝基-1,2,4-三唑盐的产率最高可达89.9%;DSC曲线表明1-氨基-2-硝基胍3,5-二硝基-1,2,4-三唑盐在217.1℃左右有一个剧烈的放热峰,说明该化合物具有较高的热稳定性;通过Kamlet-Jacobs公式计算得到1-氨基-2-硝基胍3,5-二硝基-1,2,4-三唑盐的爆速为8.42 km/s,爆压为29.8 GPa。     

2-(4,’6’-二甲氧基)嘧啶氧基-6-硝基-N-芳基苄胺衍生物的合成

以硫脲和丙二酸二乙酯为初始原料,经环合等多步反应合成4,6-二甲氧基-甲砜基嘧啶,间硝基邻甲基苯胺经重氮化得到重氮产物间硝基邻甲基苯酚.4,6-二甲氧基-甲砜基嘧啶和间硝基邻甲基苯酚反应得到2-(苄基-6-硝基-苯氧基)-4,’6’-二甲氧基嘧啶,再经溴化反应得到2-(苄基溴-6-硝基-苯氧基)-4,’6’-二甲氧基嘧啶,其与六个取代基苯胺反应,分别得到六个2-(4,’6’-二甲氧基)嘧啶氧基-6-硝基-N-芳基苄胺衍生物,产物经质谱和核磁氢谱检测确定.     

2-(4'''',6''''-二甲氧基)嘧啶氧基-6-硝基 -N-芳基苄胺衍生物的合成

以硫脲和丙二酸二乙酯为初始原料,经环合等多步反应合成4,6-二甲氧基-甲砜基嘧啶,间硝基邻甲基苯胺经重氮化得到重氮产物间硝基邻甲基苯酚.4,6-二甲氧基-甲砜基嘧啶和间硝基邻甲基苯酚反应得到2-(苄基-6-硝基-苯氧基)-4',6'-二甲氧基嘧啶,再经溴化反应得到2-(苄基溴-6-硝基-苯氧基)-4',6'-二甲氧基嘧啶,其与六个取代基苯胺反应,分别得到六个2-(4',6'-二甲氧基)嘧啶氧基-6-硝基-N-芳基苄胺衍生物,产物经质谱和核磁氢谱检测确定.     

4-硝基邻苯二腈的合成

以4-硝基邻苯二甲酰亚胺为原料,经氨化、脱水反应合成了4-硝基邻苯二腈.对4-硝基邻苯二甲酰亚胺的氨化和4-硝基邻苯二甲酰胺的脱水反应条件进行了研究,获得较佳的工艺条件,从而制得了高纯度的4-硝基邻苯二腈,总收率达59.3%,纯度达99.5%.     

4—硝基邻苯二腈的合成

以4-硝基邻苯二甲酰亚胺为原料,经氨化、脱水反应合成了4-硝基邻苯二腈。对4-硝基邻苯二甲酰亚胺的氨化和4-硝基邻苯二甲酰胺的脱水反应条件进行了研究,获得较佳的工艺条件,从而制得了高纯度的4-硝基邻苯二腈,总收率达59 3%,纯度达99 5%。     

Synthesis and Photovoltaic Properties of A Dithieno[6,5-b:10,11-b']-8H-Cyclopentyl[1,2-b:4,3-b']Diphenanthrene based Donor-Acceptor Alternating Copolymer

A novel fused nonacyclic monomer of dithieno[6,5-b:10,11-b']-8 H-cyclopentyl[1,2-b:4,3-b']diphenanthrene(DTCPDP) was synthesized by combining the structural features of ladder-type and multiple fused multi-cyclic aromatics. DTCPDP has a single sp3-hybridized carbon bridge between fused multi-cyclic aromatics. The copolymerization of DTCPDT with the electron accepting unit of 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole(DTBT) via Stille coupling afforded a novel donor-acceptor(D-A) alternating copolymer PDTCPDT-DTBT. The copolymer exhibited good chemical and thermal stabilities, with an optical band gap of 1.82 eV and a low-lying highest occupied molecular orbital(HOMO) energy level of-5.32 eV. When the copolymer was incorporated into polymer: fullerene(PC_(71)BM) blends to fabricate bulk heterojunction polymer solar cell devices, the devices exhibited a moderate maximum power conversion efficiency(PCE) of 5.90%.     

田野考古GIS数据模型研究

以田野考古发掘中的各种三维空间对象为研究背景，进行详细的数据对象分类与描述．基于面向对象的思想，在进行田野考古三维现象剖析的基础上提出了适合考古发掘对象的矢量与栅格集成的混合数据模型，并以地层模型和地物模型分别加以描述和建模，论述了建模方法，即结合地层数据源类型，进行基于多层DEM与QTPV的地层建模，同时根据地物类别、形状和内部堆积进行基于TIN与TEN表示的三维地物建模，并提出了两者的集成方法和实施步骤．研究结果实现了田野考古GIS空间数据模型的统一表达，为田野考古GIS的开发提供了模型支持和基础．     

水轮机转轮三元流场计算方法--准正交面法

介绍了准正交面法，并将该方法应用于水轮机转轮的三元流场计算中，建立了准正交面法计算三元流场的数学模型，且给出了准正交面法迭代求解的总步骤，从而为水轮机特轮的设计探索了一条新的途径．     

基于Pro/E的纤维缠绕的三维动态仿真

以复合材料制品纤维缠绕过程为例,介绍了用Pro／E实现三维运动仿真,进行了其传动齿轮、小车运动和缠绕轨迹的动态仿真．     

基于OpenGL的纤维缠绕的三维运动仿真

介绍了用OpenGL实现三维运动仿真的基本思路及步骤，并以复合材料制品纤维缠绕过程动态仿真为例，说明了其实现方法。     

Three-dimensional motion parameters estimation from stereo image sequences based on infrared reflective markers

In this paper,an innovative 3D motion parameters estimation method from stereo image sequences based on infrared(IR) reflective markers is presented.It was assumed that two high speed CCD cameras had been calibrated previously.The method consists of the following steps:1) the coordinate of several markers and depth map for each stereo pair was determined from the sequences of stereo images by relations of markers’ coordinate the correspondence between markers was established,2) the 3D motion parameters of the target was computed based upon the matched markers’ coordinate,and 3) translated 3D motion parameters estimation into the problem of least square according to the movement model of the object to be measured.Without using line,curve or corner correspondence,this method can calculate the depth of these markers feature easily and quickly in contrast to traditional approaches.The two CCD cameras work on 200 f/s,and each processing cost time is about 3 ms.It was found that,by using several markers and a large number of stereo images,this method can improve the computational speed,robustness and numerical accuracy of the motion parameters in comparison with traditional methods.The virtual simulation experiment was conducted using synthesized stereo image sequences based on 6-DOF motion platform and the experimental results proved the validity of our approach and showed that the translation and rotation precision is up to 0.1 mm and 0.1°.     

Numerical simulation for influence of excavation and blasting vibration on stability of mined-out area

Dynamic analysis steps and general flow of fast lagrangian analysis of continua in 3 dimensions （FLAC3D） were discussed. Numerical simulation for influence of excavation and blasting vibration on stability of mined-out area was carried out with FLAC3D. The whole analytical process was divided into two steps, including the static analysis and the dynamic analysis which were used to simulate the influence of excavation process and blasting vibration respectively. The results show that the shape of right upper boundary is extremely irregular after excavation, and stress concentration occurs at many places and higher tensile stress appears. The maximum tensile stress is higher than the tensile strength of rock mass, and surrounding rock of right roof will be damaged with tension fracture. The maximum displacement of surrounding rock is 4.75 mm after excavation. However, the maxi- mum displacement increases to 5.47 mm after the blasting dynamic load is applied. And the covering area of plastic zones expands obviously, especially at the foot of right upper slope. The analytical results are in basic accordance with the observed results on the whole. Damage and disturbance on surrounding rock to some degree are caused by excavation, while blasting dynamic load increases the possibility of occurrence of dynamic instability and destruction further. So the effective supporting and vibration reducing measures should be taken during mining.     

阴极材料对聚合物发光二极管特性的影响

报道了基于聚(9,9 二辛基芴 4,7 二噻基苯并二唑)(PDOF DBT,m(DOF):m(DBT)=85:15)的双层聚合物发光二极管(PLEDs)在使用碱金属、碱土金属和绝缘材料为阴极时表现的各种特性.当以厚度为3nm左右的Ba作为阴极时,器件表现出较好的性能:外量子效率为1.6%,最大的发光亮度接近4000cd m2.结果表明PDOF DBT与这种阴极的交界面具有较好的能级匹配以及电荷注入平衡.     

Two- and three-dimensional chloride ingress into fly ash concrete

2D, 3D chloride ion concentration at the edge and corner zones were systematically investigated for fly ash concretes made with different cement replacement percentage by fly ash (0%, 10%, 20%, 40%, 60%), water to binder ratios (0.3, 0.35, 0.4), and curing ages (28 d, 90 d). An interaction effect caused by 2D and 3D diffusion could obviously be observed through the comparison with 1D testing results. In order to quantify the interaction effect, 2D and 3D diffusion interaction coefficients was proposed in this paper. Finally, the changes of 2D and 3D interaction coefficients with the change in the free chloride ion concentration were given. The above research provide an insight into chloride ion attack on the edge and corner reinforcing bars of concrete structures in the field of civil engineering.     

Kinect与二维激光雷达结合的机器人障碍检测

在Kinect相机和二维激光雷达结合的基础上,提出了一种适用于移动机器人、低成本的障碍物三维感知方法。该方法首先通过Kinect相机和二维激光雷达联合标定建立深度图像点与激光雷达测距点的对应关系,然后,融合二者的检测数据得到环境障碍物位置。具体步骤为:1）Kinect相机与二维激光雷达分别从环境中获取深度图像和二维激光数据;2）将深度图像转换成虚拟二维激光数据;3）根据联合标定得到的对应关系融合虚拟激光数据与二维激光雷达数据,得到障碍物的位置。实物测试证明该方法正确有效,可用于移动机器人对环境障碍物的判断。