Dynamics of Carbonium Ions Solvated by Molecular Hydrogen: CH5+(H2)n (n = 1, 2, 3)

The dynamics of the carbonium ion (CH(5)(+)), a highly reactive intermediate with no equilibrium structure, was studied by measuring the infrared spectra for internally cold CH(5)(+)(H(2))n(n = 1, 2, 3) stored in an ion trap. First-principle molecular dynamics methods were used to directly simulate the internal motion for these ionic complexes. The combined experimental and theoretical efforts substantiated the anticipated scrambling motion in the CH(5)(+) core and revealed the effect of the solvent molecular hydrogen in slowing down the scrambling. The results indicate the feasibility of using solvent molecules to stabilize the floppy CH(5)(+) ion in order to make it amenable to spectroscopic study.     

CH5+: the infrared spectrum observed

Protonated methane, CH5+, has unusual vibrational and rotational behavior because its three nonequivalent equilibrium structures have nearly identical energies and its five protons scramble freely. Although many theoretical papers have been published on the quantum mechanics of the system, a better understanding requires spectral data. A complex, high-resolution infrared spectrum of CH5+ corresponding to the C-H stretching band in the 3.4-micrometer region is reported. Although no detailed assignment of the individual lines was made, comparison with other carbocation spectra strongly suggests that the transitions are due to CH5+.     

Quantum deconstruction of the infrared spectrum of CH5+

We present two quantum calculations of the infrared spectrum of protonated methane (CH5+) using full-dimensional, ab initio-based potential energy and dipole moment surfaces. The calculated spectra compare well with a low-resolution experimental spectrum except below 1000 cm(-1), where the experimental spectrum shows no absorption. The present calculations find substantial absorption features below 1000 cm(-1), in qualitative agreement with earlier classical calculations of the spectrum. The major spectral bands are analyzed in terms of the molecular motions. Of particular interest is an intense feature at 200 cm(-1), which is due to an isomerization mode that connects two equivalent minima. Very recent high-resolution jet-cooled spectra in the CH stretch region (2825 to 3050 cm(-1)) are also reported, and assignments of the band origins are made, based on the present quantum calculations.     

8种新疆产干果的红外光谱特征研究

分析了新疆产8种干果的红外光谱特征。这8种干果可分为两类，其红外图谱在官能团区有很大差异。巴旦木、核桃仁、花生仁、带壳杏仁富含蛋白质和脂类物质，红外图谱显示出在2914，2847cm^-1附近的CH伸缩振动和1742cm^-1附近的C=O伸缩振动；枸杞子、红枣、葡萄干和无花果干富含多糖、蛋白类物质，其红外图谱显示出在3370cm^-1附近的OH变形振动、NH伸缩振动和2920cm^-1附近的CH伸缩振动。     

Probing the structure of metal cluster-adsorbate systems with high-resolution infrared spectroscopy

High-resolution infrared laser spectroscopy was used to obtain rotationally resolved infrared spectra of adsorbate-metal complexes. The method involves forming the bare metal clusters in helium nanodroplets and then adding a molecular adsorbate (HCN) and recording the infrared spectrum associated with the C-H stretching vibration. Rotationally resolved spectra were obtained for HCN-Mg(n) (n = 1 to 4). The results suggest a qualitative change in the adsorbate-metal cluster bonding with cluster size.     

基于PDS算法的不同光照下模型传递研究

针对在室外光照对样品使用近红外光谱检测带来误差的问题,提出基于模型传递来减少检测误差的方法。以圆黄梨为样品,分析样品在室内、室外阴影下的近红外光谱,建立室内光谱的PLS模型。采用分段直接校正(Piecewise Direct Standardization,PDS)算法,减小室内外光谱差距,使得室内PLS模型能预测室外光谱。结果表明,在室内建立的模型能预测经PDS算法传递后的室外光谱,预测决定系数(R2)和标准差(Root Mean Square Error of Prediction,RMSEP)分别为0.64和0.565 27,能有效地解决室外光照对光谱检测影响的问题。     

Biogenic methane, hydrogen escape, and the irreversible oxidation of early Earth

The low O2 content of the Archean atmosphere implies that methane should have been present at levels approximately 10(2) to 10(3) parts per million volume (ppmv) (compared with 1.7 ppmv today) given a plausible biogenic source. CH4 is favored as the greenhouse gas that countered the lower luminosity of the early Sun. But abundant CH4 implies that hydrogen escapes to space (upward arrow space) orders of magnitude faster than today. Such reductant loss oxidizes the Earth. Photosynthesis splits water into O2 and H, and methanogenesis transfers the H into CH4. Hydrogen escape after CH4 photolysis, therefore, causes a net gain of oxygen [CO2 + 2H2O --> CH4 + 2O2 --> CO2 + O2 + 4H(upward arrow space)]. Expected irreversible oxidation (approximately 10(12) to 10(13) moles oxygen per year) may help explain how Earth's surface environment became irreversibly oxidized.     

Detection of C5 in the Circumstellar Shell of IRC+10216

The C(5) molecule has been identified in the infrared spectrum of the prototypical obscured carbon star, IRC+10216. In addition to their astrophysical importance, pure carbon chain molecules such as C(5) are of interest in the chemistry of flames and propellants.     

不同营养源对人工湿地基质生物膜培养液pH值的影响

采用恒温摇床培养方法,研究了不同营养源(处理1:尿素+乙酸钠;处理2:亚硝酸钠+乙酸钠;处理3:硝酸钾+乙酸钠;处理4:碳酸氢铵;处理5:硫酸铵+碳酸氢钠;处理6:磷酸二氢钾+碳酸氢钠)对复合垂直流人工湿地基质生物膜培养液pH值的影响,探讨了pH值变化过程中生物膜脱氢酶活性和多糖含量的变化规律.结果表明,处理1、4以及5中培养液pH值先下降然后再上升,但下降和上升的幅度不同.处理2、3以及6中培养液pH值添加碳源前在7.30～7.40之间缓慢变化,添加碳源后均上升至9.00左右.在培养液pH值变化的过程中,生物膜脱氢酶活性和多糖含量也发生改变.处理1、2、3中生物膜脱氢酶活性均在pH值上升的过程中达到最高值,而处理4、5、6中脱氢酶活性随pH值的变化呈下降趋势.对于所设6个处理,除处理4中多糖含量在整个试验过程中基本不变外,其余5个处理中多糖含量均在pH值上升过程中一直增加.     

5-羟色胺对断奶腹泻仔鼠小肠组织学结构的影响

为研究5-羟色胺(5-HT)增多是否通过影响肠黏膜屏障引起断奶仔鼠的腹泻,检测断奶腹泻仔鼠小肠绒毛高度(VH)、隐窝深度(CD)变化。采用21d刚断奶ICR仔鼠,分为6组,第1组为正常对照组,第2组为应激腹泻组,番泻叶(0.4kg/L)按体重15mL/kg灌胃同时后肢束缚应激处理,第3组为氢溴酸西肽普兰(CH)对照组,用CH进行腹腔注射处理,第4组CH+腹泻组,CH药物处理4h后进行应激腹泻处理;第5组对氯苯丙氨酸(PCPA)对照组,PCPA腹腔注射;第6组PCPA+应激腹泻组,PCPA药物处理4h后进行应激腹泻处理。连续处理5日后处死小鼠,取十二指肠、空肠、回肠,4%多聚甲醛固定、石蜡包埋,制作石蜡切片,HE染色,测量肠绒毛高度、隐窝深度。由HE染色结果发现,应激腹泻组、CH+应激腹泻组和PCPA+应激腹泻组与正常对照组相比,肠绒毛顶端出现充血,绒毛变短,裸露固有层等病理现象。与正常对照组相比,应激性腹泻组小鼠肠绒毛高度降低:十二指肠,空肠,回肠分别降低14.80%(P0.01),6.89%(P0.01)和19.31%(P0.01),隐窝深度分别升高14.09%(P0.01)、4.85%(P0.05)、11.53%(P0.01),故VH和CD的比值(V/C)降低:CH处理组与应激腹泻组小鼠变化趋势相同;而PCPA处理组则无明显变化。与应激腹泻小鼠相比,CH+应激腹泻组小鼠肠绒毛高度降低,尤其空肠显著降低11.18%(P0.01),隐窝深度升高,尤其十二指肠显著升高4.86%(P0.05),故V/C值也降低,而PCPA+应激腹泻组小鼠绒毛高度升高,分别为4.83%(P0.05),4.15%(P0.01),10.60%(P0.01),隐窝深度降低,分别为27.46%(P0.01)、19.21%(P0.01)、16.74%(P0.01),故V/C值升高。断奶腹泻仔鼠小肠黏膜机械屏障遭到破坏,而肠道内5-HT含量的升高也会使断奶仔鼠出现腹泻现象,同时小肠绒毛高度降低,隐窝深度增加。因此5-HT升高可能通过损伤断奶仔鼠小肠的绒毛高度和隐窝深度,从而引发腹泻。     

氟虫腈所含主要微量杂质的相关研究

[目的]分析氟虫腈产品所含的主要微量杂质。[方法]利用MS、NMR、IR等光谱分析技术对用拜尔公司工艺生产的氟虫腈产品所含的主要微量杂质进行初步分析和结构鉴定。[结果]氟虫腈成品中所含的主要杂质是(±)-5-氨基-1-(2,6-二氯-α,α,α-三氟-p-甲苯基-)-4-三氟甲基磺酰基-3-氰基吡唑。追溯杂质的来源,发现该杂质和氟虫腈最后一步生产工艺的氧化反应有关。不加催化剂,仅用双氧水则氧化反应不完全,导致成品中未完全反应的(±)-5-氨基-1-(2,6-二氯-α,α,α-三氟-p-甲苯基-)-4-三氟甲硫基-3-氰基吡唑含量增加。采用间氯过氧化苯甲酸这种氧化剂成本太高。采用双氧水/三氟乙酸这种混合氧化剂同时加入硼酸作抗腐蚀剂,效果较好。[结论]该研究为氟虫腈实际生产工艺的改良提供了指导意见。     

Deuterated methane observed on saturn

Absorptions for the V(2) band of deuterated methane (CH(3)D) have been observed in the 5-micron spectrum of Saturn, obtained with a Fourier transform spectrometer. Analysis of the band yields a CH(3)D abundance of 2.6 +/- 0.8 centimeter-amagat and a temperature of 175 +/- 30 K for the mean level of spectroscopic line formation. This temperature indicates that a substantial portion of Saturn's flux at 5 microns is due to thermal radiation, and that we are therefore looking fairly deep into its atmosphere, as is the case for the Jupiter 5-micron window. This CH(3)D abundance leads to a deuteriumlhydrogen ratio of about 2 x 10(-5) in Saturn's atmosphere. This ratio is much lower than the terrestrial value but comparable to that determined for Jupiter and may be taken as representative of the deuteriumlhydrogen ratio in the solar system at the time of its formation.     

Parent volatiles in comet 9P/Tempel 1: before and after impact

We quantified eight parent volatiles (H2O, C2H6, HCN, CO, CH3OH, H2CO, C2H2, and CH4) in the Jupiter-family comet Tempel 1 using high-dispersion infrared spectroscopy in the wavelength range 2.8 to 5.0 micrometers. The abundance ratio for ethane was significantly higher after impact, whereas those for methanol and hydrogen cyanide were unchanged. The abundance ratios in the ejecta are similar to those for most Oort cloud comets, but methanol and acetylene are lower in Tempel 1 by a factor of about 2. These results suggest that the volatile ices in Tempel 1 and in most Oort cloud comets originated in a common region of the protoplanetary disk.     

稻麦两熟制农田不同土壤耕作方式对稻季CH_4排放的影响

【目的】研究稻麦两熟制农田不同土壤耕作方式对水稻生长季CH4排放的影响,为长江下游稻麦两熟制农田温室气体减排提供对策。【方法】采用裂区设计,利用静态暗箱-气相色谱法研究麦季土壤耕作方式(免耕、旋耕和翻耕)和稻季土壤耕作方式(旋耕和翻耕)对水稻生长季CH4排放的影响。【结果】稻麦两熟制农田不同土壤耕作方式下水稻生长季CH4排放呈先升高后降低的变化趋势,移栽至有效分蘖临界叶龄期CH4累积排放量占全生育期排放总量的比例为64.73%—86.84%。水稻生长季CH4排放总量麦季免耕极显著高于麦季旋耕和麦季翻耕,平均增加53%和24%;稻季翻耕较稻季旋耕平均增加CH4排放量10%,差异达显著水平。不同土壤耕作处理稻季CH4排放总量为:麦季免耕+稻季翻耕麦季免耕+稻季旋耕麦季翻耕+稻季翻耕麦季翻耕+稻季旋耕麦季旋耕+稻季翻耕麦季旋耕+稻季旋耕,"单位产量的CH4排放量"表现趋势相同。水稻生长期内CH4排放通量的季节变化和土壤Eh呈极显著负相关,CH4排放总量与0—5cm耕层土壤有机质含量呈极显著正相关。【结论】麦季土壤耕作方式和稻季土壤耕作方式对水稻生长季CH4排放总量有显著或极显著影响,在长江下游稻麦两熟制农田采用周年旋耕措施能有效减少水稻生长季CH4的排放。     

仪器分析实验教学新模式开发——以傅里叶红外光谱仪教学为例

天津农学院为了培养学生准确掌握和使用先进分析仪器的能力,开设了仪器分析课程。以傅里叶红外光谱仪教学为例,探讨了改革傅里叶红外光谱仪的实验教学内容、教学模式、教学方法,使学生的实验技能得到提高,培养学生良好的实验素质和严谨的科研作风。     

速生杨木密实化研究

对速生意大利杨木进行密实化处理和物理力学性能测定,观察分析木材红外吸收光谱和微观结构,寻找回弹固定机理.得出最佳工艺条件:压前含水率为饱水状态,压后厚度为2 cm,压缩率为50%,热压温度为190℃,热压时间为30-40m in.采用质量分数为5%的CH蒸煮添加剂软化效果好,具有环保性.处理材厚度吸湿回复率为2.1%,尺寸稳定性好,物理力学性能明显提高.处理材的微观结构只是细胞被挤压,细胞腔变小,细胞壁未受到破坏.本研究的实施是高效利用低质木材的重要手段和有效途径,将带来良好的社会、经济和生态效益.     

氧化淀粉对水溶液中Cd~(2+)的吸附研究

[目的]探讨氧化淀粉对水溶液中Cd2+的吸附效果。[方法]采用30%过氧化氢氧化可溶性淀粉制得氧化淀粉,研究氧化淀粉对水中Cd2+的吸附行为以及影响吸附效果的重要因素,并测定了氧化淀粉对Cd2+的吸附等温线。[结果]氧化淀粉对水中Cd2+的吸附效果受吸附温度、pH、吸收剂用量和吸附时间的影响,其中pH影响最大;最佳吸附条件为pH 5、吸附温度30℃、吸附时间4 h和吸收剂用量3 g,Cd2+去除率达到82.15%。在该试验条件下,氧化淀粉对Cd2+的吸附模式符合Longmuir等温方程。[结论]采用30%过氧化氢制备得到的氧化淀粉对水中的Cd2+具有很好的吸附效果。     

Manipulation of the wettability of surfaces on the 0.1- to 1 -micrometer scale through micromachining and molecular self-assembly

Micromachining allows the formation of micrometer-sized regions of bare gold on the surface of a gold film supporting a self-assembled monolayer (SAM) of alkanethiolate. A second SAM forms on the micromachined surfaces when the entire system-the remaining undisturbed gold-supported SAM and the micromachined features of bare gold-is exposed to a solution of dialkyl disulfide. By preparing an initial hydrophilic SAM from HS(CH(2))(15)COOH, micromachining features into this SAM, and covering these features with a hydrophobic SAM formed from [CH(3)(CH(2))(11)S](2), it is possible to construct micrometer-scale hydrophobic lines in a hydrophilic surface. These lines provide new structures with which to manipulate the shapes of liquid drops.     

稻叶瘟对水稻光谱特性的影响研究

本文通过对4个感染不同等级稻叶瘟的水稻冠层反射光谱进行测试，并对光谱反射曲线进行微分分析，研究了绿光区、红光区和近红外区反射光谱的变异特征。结果表明：绿光区、红光区和近外区的水稻冠层光谱反射率随病情程度的加重分别呈现下降、上升和下降的趋势；绿光吸收边缘的特征波长值发生红移，红光吸收边缘和近红外吸收边缘的特征波长值发生蓝移。受害轻时近红外区反射率变化幅度大，受害重时绿光区和红光区反射率变化幅度大。本研究为应用遥感技术早期探测稻叶瘟的发生提供了实验依据。     

C 2H 5N 4- C 6H 3N 3O-7氢键相互作用的理论研究

运用密度泛函理论方法,在B3LYP/6-311++G**水平上对4-氨基-1,2,4-三唑阳离子(AT)和2,4,6-三硝基苯酚阴离子(PA)形成的氢键二聚体进行理论计算研究.计算得到4种稳定结构的氢键复合物及最稳定异构体D1的振动频率、电子吸收光谱与热力学性质.结果表明,氢键复合物中存在较强的N—H…O与C—H…O红移氢键.经过基组重叠误差和零点振动能校正后,D1的氢键相互作用能为-30.71kJ/mol.热力学计算显示,在298.15K和标准状态下,D1气态氢键复合物分子的形成过程是放热、熵减小的非自发过程,但在低温下能自发进行.D1分子的标准摩尔生成焓和标准摩尔生成自由能分别为98.7,474.4kJ/mol.