2HDNPPb恒容燃烧能的测定及其在RDX-CMDB推进剂中的应用

利用精密转动弹热量计测定了2-羟基-3,5-二硝基吡啶铅盐(2HDNPPb)的燃烧能ΔcU,其结果为(-7 265.08±3.97)J/g。据此计算的标准摩尔燃烧焓和标准摩尔生成焓分别为(-4 425.81±2.43)kJ/mol和(-870.47±2.76)kJ/mol。利用均匀设计法,研究了2HDNPPb、2-羟基-3,5-二硝基吡啶铜盐(2HDNPCu)和炭黑(CB)在RDX-CMDB推进剂燃烧中的复合催化作用,发现当3种组分的加入量分别为1.0%、0.6%和0.6%时,推进剂在所测压强范围内有最高燃速,并且压强指数较低。     

1,5-二氨基四唑含能配合物的制备、表征及其催化性能研究

合成出2种以1,5-二氨基四唑(DAT)为配体,苦味酸根为外界,钴和铜为中心离子的含能配合物,并对其结构进行了表征.运用示差扫描热分析(DSC)方法,就目标化合物对高氯酸铵(AP)、奥克托金(HMX)和六硝基六氮杂异伍兹烷(HNIW)热分解的影响进行了研究.利用电荷耦合器件(CCD)燃速测定系统,研究了目标化合物对缩水...     

5,5′-二硝基-3,3′-偶氮基-1-氢-1,2,4-三唑（DNAT）的合成和性能研究

以3,5-二氨基-1,2,4-三唑为原料,经过重氮化、选择性还原、酸性氧化3步,合成出目标化合物5,5′-二硝基-3,3′-偶氮基-1-氢-1,2,4三唑(DNAT),通过红外光谱、元素分析、质谱分析进行了结构鉴定,并进行了DSC-TGA、燃烧性能分析、感度测试等性能研究。实验结果表明,5,5′-二硝基-3,3′-偶氮基-1-氢-1,2,4-三唑(DNAT)化合物具有密度高(1.88 g/cm3)、正的生成焓(446.448 kJ/mol)、热稳定性能好的特点,是一种性能良好的高氮含能化合物。     

二(2,2-二硝基丙基)硝胺的合成及热性能

以2,2-二硝基丙醇为原料,经缩合、硝化反应合成了二(2,2-二硝基丙基)硝胺(BDNPN)。用红外光谱、核磁共振、元素分析对中间体及目标化合物的结构进行了表征。优化了反应条件,硝化反应的最佳条件为nBDNPA:nHNO3=1∶30,反应温度为50℃,反应时间为1 h,收率92.1%。用DSC和TG-DTG考察了目标化合物的热性能。结果表明,BDNPN的热分解峰温为212.3℃,具有较好的热稳定性。     

5,5'-二硝基-3,3'-偶氮基-1-氢-1,2,4-三唑(DNAT)的合成和性能研究

以3,5-二氨基-1,2,4-三唑为原料,经过重氮化、选择性还原、酸性氧化3步,合成出目标化合物5,5'-二硝基-3,3'-偶氮基-1-氢-1,2,4三唑(DNAT),通过红外光谱、元素分析、质谱分析进行了结构鉴定,并进行了DSC-TGA、燃烧性能分析、感度测试等性能研究.实验结果表明,5,5'-二硝基-3,3'-偶氮基-1-氢-1,2,4-三唑(DNAT)化合物具有密度高(1.88 g/cm3)、正的生成焓(446.448 kJ/mol)、热稳定性能好的特点,是一种性能良好的高氮含能化合物.     

N，N′-二硝基哌嗪的热分解机理及动力学研究

采用高压差示扫描量热(PDSC)、热重分析(TGA)和快速扫描傅立叶变换红外光谱(FTIR)等分析技术,研究了N,N'-二硝基哌嗪(DNP)的热分解机理;采用原位热裂池的FTIR技术分析分解过程的凝聚相变化,最终获得其热分解动力学方程和热分解与化学反应的具体过程.研究表明,0.1 MPa下DNP发生挥发,不能正常分解;而在2、4、6 MPa下DNP的分解过程较简单,先在217 ℃处出现一强吸热峰,它是由DNP熔融过程引起的,它随压强的变化不大,而后在244.2～251.7 ℃之间出现的主要放热峰,主放热峰之后300 ℃左右处有一小肩峰出现,且随着压强增大逐渐明显,这说明DNP在较高压强下出现了二次分解反应.采用3种不同计算方法所得的DNP分解活化能为103～124 kJ*mol-1;最后经过分析计算得到了DNP热分解机理函数.     

聚[2,5-二羟基-1,4-苯撑吡啶并二咪唑]单体的合成优化及提纯研究

研究了液晶高分子聚[2,5-二羟基-1,4-苯撑吡啶并二咪唑](PIPD)的2个单体2,5-二羟基对苯二甲酸(DHTA)和2,3,5,6-四氨基吡啶(TAP)盐酸盐的制备与提纯,并通过对比实验确定出最优的合成与提纯路线.通过IR、~1H NMR、~(13)C NMR、HPLC、DSC和元素分析确定了产物为目的产物.     

含能增塑剂对PBT弹性体微相分离及力学性能的影响

采用红外光谱(IR)、力学性能测试等方法研究了含能增塑剂丁基硝氧乙基硝胺(Bu-NENA)和双(2,2-二硝基丙基)缩甲醛/双(2,2-二硝基丙基)缩乙醛混合物(BDNPF/A,两者质量比为1∶1)对3,3-二叠氮甲基氧丁环/四氢呋喃共聚醚(PBT)弹性体微相分离和力学性能的影响。结果表明,Bu-NENA对PBT弹性体的微相分离影响较大,随增塑比的增大,游离羰基比例提高,同时有序氢键化羰基比例显著减小,增塑比为1.0时有序氢键化羰基比例几乎为0,导致弹性体抗拉强度显著降低;BDNPF/A对PBT弹性体的微相分离特性则没有明显影响。两种含能增塑剂复配时,随着复配增塑剂中BDNPF/A比例的增加,弹性体的抗拉强度随之增大。     

高能硼氢燃烧剂与固体推进剂常用组分相容性的DSC法研究

采用差示扫描量热法(DSC)和表观活化能变化率,研究了高能硼氢燃烧剂(十氢十硼酸双四乙基铵,BHN)与缩水甘油叠氮聚醚(GAP)、黑索今(RDX)、奥克托金(HMX)、3-硝基-1,2,4-3-己基铅(NTO-Pb)、六硝基六氮杂异伍兹烷(CL-20)、铝粉(Al,12.18μm)、镁粉(Mg,200～325目)、3,4-二硝基呋咱基氧化呋咱(DNTF)和N-脒基脲二硝酰胺盐(GUDN)等含能组分的相容性;同时,还研究了BHN与聚对苯二甲酸乙二醇酯(PET,M=6 000)、聚乙二醇(PEG,M=10 000)、二异氰酸酯(N-100)、端羟基聚丁二烯(HTPB)、己二酸铜(AD-Cu)、2,4-二羟基苯甲酸铜(β-Cu)、邻苯二甲酸铅(φ-Pb)、炭黑(CB)、三氧化二铝(A12O3)、l,3-二甲基-1,3-二苯基脲(C2)、癸二酸二异辛酯(DOS)和高氯酸钾(KP)等惰性材料的相容性。研究结果表明,BHN与NTO-Pb、CL-20、A1、Mg、PET、PEG、N-100、HTPB、CB、Al2O3、C2、DOS和KP相容性较好,与GAP和HMX轻微敏感;AD-Cu、β-Cu和φ-Pb敏感,而与RDX、DNTF和GUDN不相容。由此可见,BHN与固体推进剂的主要组分相容性良好,可在HTPB/AP/Al体系的复合固体推进剂中应用。     

钝感GAP微烟推进剂的能量性能计算

根据推进剂配方理论计算程序计算了含N-脒基脲二硝酰胺(FOX-12)、1,1-二氨基-2,2-二硝基乙烯(FOX-7)、3-硝基-1,2,4-三唑-5-酮(NTO)、三氨基三硝基苯(TATB)、3,4-二硝基呋咱基氧化呋咱(DNTF)、黑索今(RDX)、二硝酰胺铵(ADN)等高能钝感氧化剂及1,2,4-丁三醇三硝酸酯(BTTN)、二缩三乙二醇二硝酸酯(TEGDN)、三羟甲基乙烷三硝酸酯(TMETN)、N-丁基-2-硝酸酯乙基硝胺(Bu-NENA)等钝感增塑剂的几种单元推进剂和钝感微烟推进剂的能量性能。计算结果表明,所列的7种含能氧化剂中,由RDX和DNTF形成的单元推进剂的标准理论比冲分别为2 696.4 N.s/kg和2 610.2 N.s/kg,明显优于其他几种氧化剂。当采用DNTF部分取代GAP推进剂中的RDX或ADN后,推进剂的理论比冲、密度和特征速度相应提高。由于DNTF的感度低于RDX,因此DNTF引入推进剂中,对提高钝感GAP微烟推进剂的能量性能是有益的。     

Subcritical water extractor for Mars analog soil analysis

Abstract Technologies that enable rapid and efficient extraction of biomarker compounds from various solid matrices are a critical requirement for the successful implementation of in situ chemical analysis of the martian regolith. Here, we describe a portable subcritical water extractor that mimics multiple organic solvent polarities by tuning the dielectric constant of liquid water through adjustment of temperature and pressure. Soil samples, collected from the Yungay region of the Atacama Desert (martian regolith analogue) in the summer of 2005, were used to test the instrument's performance. The total organic carbon was extracted from the samples at concentrations of 0.2-55.4 parts per million. The extraction data were compared to the total organic carbon content in the bulk soil, which was determined via a standard analytical procedure. The instrument's performance was examined over the temperature range of 25-250 degrees C at a fixed pressure of 20.7 MPa. Under these conditions, water remains in a subcritical fluid state with a dielectric constant varying between approximately 80 (at 25 degrees C) and approximately 30 (at 250 degrees C).     

基于时频原子方法的雷达辐射源个体识别

针对雷达辐射源个体识别问题,提出一种时频原子分解的特征提取方法.该方法针对主振放大式发射机,首先根据锁相环频率合成器相位噪声的功率谱,模拟含有特定相位噪声的辐射源信号.然后基于时频原子分解原理并采用膜算法将带有相位噪声的辐射源信号在正弦原子库中进行一次分解.最后利用分解后的原子提取出正弦原子能量特征和原子频率偏差特征,...     

Fate of prebiotic adenine

Equilibrium adsorption isotherm data for the purine base adenine has been obtained on several prebiotically relevant minerals by frontal analysis using water as a mobile phase. Adenine is far displaced toward adsorption on pyrite (FeS2), quartz (SiO2), and pyrrhotite (FeS), but somewhat less for magnetite (Fe3O4) and forsterite (Mg2SiO4). The prebiotic prevalence of these minerals would have allowed them to act as a sink for adenine; removal from the aqueous phase would confer protection from hydrolysis as well, establishing a nonequilibrium thermodynamic framework for increased adenine synthesis. Our results provide evidence that adsorption phenomena may have been critical for the primordial genetic architecture.     

Cyanobacterial emergence at 2.8 gya and greenhouse feedbacks

Apparent cyanobacterial emergence at about 2.8 Gya coincides with the negative excursion in the organic carbon isotope record, which is the first strong evidence for the presence of atmospheric methane. The existence of weathering feedbacks in the carbonate-silicate cycle suggests that atmospheric and oceanic CO2 concentrations would have been high prior to the presence of a methane greenhouse (and thus the ocean would have had high bicarbonate concentrations). With the onset of a methane greenhouse, carbon dioxide concentrations would decrease. Bicarbonate has been proposed as the preferred reductant that preceded water for oxygenic photosynthesis in a bacterial photosynthetic precursor to cyanobacteria; with the drop of carbon dioxide level, Archean cyanobacteria emerged using water as a reductant instead of bicarbonate (Dismukes et al., 2001). Our thermodynamic calculations, with regard to this scenario, give at least a tenfold drop in aqueous CO2 levels with the onset of a methane-dominated greenhouse, assuming surface temperatures of about 60 degrees C and a drop in the level of atmospheric carbon dioxide from about 1 to 0.1 bars. The buildup of atmospheric methane could have been triggered by the boost in oceanic organic productivity that arose from the emergence of pre-cyanobacterial oxygenic phototrophy at about 2.8-3.0 Gya; high temperatures may have precluded an earlier emergence. A greenhouse transition timescale on the order of 50-100 million years is consistent with results from modeling the carbonate-silicate cycle. This is an alternative hypothesis to proposals of a tectonic driver for this apparent greenhouse transition.     

Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life

The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.     

Abiotic synthesis of organic compounds from carbon disulfide under hydrothermal conditions

Abiotic formation of organic compounds under hydrothermal conditions is of interest to bio, geo-, and cosmochemists. Oceanic sulfur-rich hydrothermal systems have been proposed as settings for the abiotic synthesis of organic compounds. Carbon disulfide is a common component of magmatic and hot spring gases, and is present in marine and terrestrial hydrothermal systems. Thus, its reactivity should be considered as another carbon source in addition to carbon dioxide in reductive aqueous thermosynthesis. We have examined the formation of organic compounds in aqueous solutions of carbon disulfide and oxalic acid at 175 degrees C for 5 and 72 h. The synthesis products from carbon disulfide in acidic aqueous solutions yielded a series of organic sulfur compounds. The major compounds after 5 h of reaction included dimethyl polysulfides (54.5%), methyl perthioacetate (27.6%), dimethyl trithiocarbonate (6.8%), trithianes (2.7%), hexathiepane (1.4%), trithiolanes (0.8%), and trithiacycloheptanes (0.3%). The main compounds after 72 h of reaction consisted of trithiacycloheptanes (39.4%), pentathiepane (11.6%), tetrathiocyclooctanes (11.5%), trithiolanes (10.6%), tetrathianes (4.4%), trithianes (1.2%), dimethyl trisulfide (1.1%), and numerous minor compounds. It is concluded that the abiotic formation of aliphatic straight-chain and cyclic polysulfides is possible under hydrothermal conditions and warrants further studies.     

Oxidant enhancement in martian dust devils and storms: implications for life and habitability

We investigate a new mechanism for producing oxidants, especially hydrogen peroxide (H2O2), on Mars. Large-scale electrostatic fields generated by charged sand and dust in the martian dust devils and storms, as well as during normal saltation, can induce chemical changes near and above the surface of Mars. The most dramatic effect is found in the production of H2O2 whose atmospheric abundance in the "vapor" phase can exceed 200 times that produced by photochemistry alone. With large electric fields, H2O2 abundance gets large enough for condensation to occur, followed by precipitation out of the atmosphere. Large quantities of H2O2 would then be adsorbed into the regolith, either as solid H2O2 "dust" or as re-evaporated vapor if the solid does not survive as it diffuses from its production region close to the surface. We suggest that this H2O2, or another superoxide processed from it in the surface, may be responsible for scavenging organic material from Mars. The presence of H2O2 in the surface could also accelerate the loss of methane from the atmosphere, thus requiring a larger source for maintaining a steady-state abundance of methane on Mars. The surface oxidants, together with storm electric fields and the harmful ultraviolet radiation that readily passes through the thin martian atmosphere, are likely to render the surface of Mars inhospitable to life as we know it.     

Glycine identification in natural jarosites using laser desorption Fourier transform mass spectrometry: implications for the search for life on Mars

The jarosite group minerals have received increasing attention since the discovery of jarosite on the martian surface by the Mars Exploration Rover Opportunity. Given that jarosite can incorporate foreign ions within its structure, we have investigated the use of jarosite as an indicator of aqueous and biological processes on Earth and Mars. The use of laser desorption Fourier transform mass spectrometry has revealed the presence of organic matter in several jarosite samples from various locations worldwide. One of the ions from the natural jarosites has been attributed to glycine because it was systematically observed in combinations of glycine with synthetic ammonium and potassium jarosites, Na(2)SO(4) and K(2)SO(4). The ability to observe these organic signatures in jarosite samples with an in situ instrumental technique, such as the one employed in this study, furthers the goals of planetary geologists to determine whether signs of life (e.g., the presence of biomolecules or biomolecule precursors) can be detected in the rock record of terrestrial and extraterrestrial samples.     

4,6-二氨基间苯二酚盐酸盐合成研究

以三氯苯为原料,经硝化、水解和催化加氢三步反应,合成聚对苯撑苯并双噁唑(PBO)单体4,6-二氨基间苯二酚盐酸盐(DADHC)。研究了各中间体和单体合成中的影响因素,确定了各步反应的最佳工艺参数。对合成的各中间体和单体采用元素分析(EA)、傅立叶变换红外光谱(FT-IR)、氢核磁(1H NMR)、碳核磁(13C NMR)和高效液相色谱(HPLC)等方法进行了表征分析。结果表明,各中间体和单体均达到预定要求,纯度和收率较高。研制了一套单体防氧化分离Pd/C过滤装置,实现了Pd/C催化剂的回收再利用,解决了单体易氧化、Pd/C易失活难题,提高了生产效率,降低了生产成本。     

Immunological detection of small organic molecules in the presence of perchlorates: relevance to the life marker chip and life detection on Mars

The proposed ExoMars mission, due to launch in 2018, aims to look for evidence of extant and extinct life in martian rocks and regolith. Previous attempts to detect organic molecules of biological or abiotic origin on Mars have been unsuccessful, which may be attributable to destruction of these molecules by perchlorate salts during pyrolysis sample extraction techniques. Organic molecules can also be extracted and measured with solvent-based systems. The ExoMars payload includes the Life Marker Chip (LMC) instrument, capable of detecting biomarker molecules of extant and extinct Earth-like life in liquid extracts of martian samples with an antibody microarray assay. The aim of the work reported here was to investigate whether the presence of perchlorate salts, at levels similar to those at the NASA Phoenix landing site, would compromise the LMC extraction and detection method. To test this, we implemented an LMC-representative sample extraction process with an LMC-representative antibody assay and used these to extract and analyze a model sample that consisted of a Mars analog sample matrix (JSC Mars-1) spiked with a representative organic molecular target (pyrene, an example of abiotic meteoritic infall targets) in the presence of perchlorate salts. We found no significant change in immunoassay function when using pyrene standards with added perchlorate salts. When model samples spiked with perchlorate salts were subjected to an LMC-representative liquid extraction, immunoassays functioned in a liquid extract and detected extracted pyrene. For the same model sample matrix without perchlorate salts, we observed anomalous assay signals that coincided with yellow coloration of the extracts. This unexpected observation is being studied further. This initial study indicates that the presence of perchlorate salts, at levels similar to those detected at the NASA Phoenix landing site, is unlikely to prevent the LMC from extracting and detecting organic molecules from martian samples.