Novel carboxylated oligothiophenes as sensitizers in photoelectric conversion systems

Novel carboxylated oligothiophenes with different thiophene units were designed and synthesized as photosensitizers in dye-sensitized solar cells (DSSCs) for efficient opto-electric materials. The introduction of -COOH into thiophene molecules can lead to a red shift of UV-visible absorption, increase light-harvesting efficiency, and enhance photoinduced charge transport by forming efficient covalent bonds to the substrate surface. A red shift of the absorption spectrum of oligothiophene is also achieved by the increase in the number of thiophene units. The DSSCs based on the oligomers have excellent photovoltaic performances. Under 100 mW cm(-2) irradiation a short-circuit current of 10.57 mA cm(-2) and an overall energy conversion efficiency of 3.36 % is achieved when pentathiophene dicarboxylated acid was used as a sensitizer. The incident photo-to-current conversion efficiency (IPCE) has a maximum as high as 80 %. In addition, photovoltage and photocurrent transients show that slow charge recombination in DSSCs is important for efficient charge separation and excellent photoelectric conversion properties of the oligomers. These initial and promising results suggest that carboxylated oligothiophenes are efficient photosensitizers.     

Energy transfer rates and impact sensitivities of two classes nitramine explosives molecules

Some explosives are stable molecules with large energy barriers to chemical reaction, and in shock or impact initiation, a sizable amount of phonon energy must be converted to the molecular internal higher vibrations by multiphonon up pumping. To investigate the relationship between impact sensitivities and energy transfer rates, the number of doorway modes of explosive molecules is estimated by a simple theory in which the rate is proportional to the number of normal mode vibrations. We evaluated frequencies of normal mode vibrations of 13 explosive molecules which are CHNO nitramine-contained and have not been analyzed previously. The number of doorway modes in the regions of 200–700 cm⁻¹ was evaluated by the direct counting method. For more clear investigation of the relationship we have classified these 13 nitramine explosive molecules, by the number of nitramine group they contained, into two groups. There are eight molecules that contained one nitramine group and five molecules that contained poly-nitramine groups. It is found that the number of doorway modes shows a linearly correlation to the impact sensitivities derived from drop hammer tests. This result is in agreement with that of several previous works. Besides, it is also noted in our study that in those nitramine explosives molecules with similar molecular structure (similar number nitramine group they contained) and similar molecular weight, the correlation between the sensitivity and the number of doorway modes is higher. We found that the vibrational frequency of ω corresponds to nitro group motions of every molecule is contributed to the number of doorway modes in the regions of 200–700 cm⁻¹.     

大豆中二硝基苯胺类除草剂多残留的气相色谱法定量检测及质谱确证

建立以凝胶渗透色谱法（GPC）和固相萃取法（SPE）及气相色谱法（GC）联用技术测定大豆中10种二硝基苯胺类除草剂（氟乐灵、乙氟灵、环丙氟、氯乙氟灵、仲丁灵、异乐灵、二甲戊乐灵、二硝胺、氨基丙氟灵和磺乐灵）多残留检测方法。目标农药经正己烷饱和的乙腈提取，凝胶渗透色谱除去大豆中大部分油脂及色素，再经Florisil柱净化和富集，依次用6mL二氯甲烷和6mL二氯甲烷＋丙酮（99＋1）洗脱。目标农药采用电子捕获检测（GC／ECD），外标法定量，并经质谱（MS）确证。两个添加水平重复6次，回收率分别为74％～105％和59％～105％；相对标准偏差〈20％；检出限为1．8～7．6μg／kg；定量限为6～38μg/kg。     

SINGLE AND BINARY ADSORPTION PERFORMANCE OF SALICYLIC ACID AND 5-SULFOSALICYLIC ACID ONTO HYPERCROSSLINKED POLYMERIC ADSORBENTS

Single and binary adsorption behaviors of salicylic acid and 5-sulfosalicylic acid onto hypercrosslinked polymeric adsorbents, i.e. NDA-101 and NDA-99 were investigated. The Freundlich model can successfully describe all the adsorption isotherms tested, which indicates a favorable and exothermic adsorption process. The adsorption of salicylic acid relies on π-π interaction, while the electrostatic interaction further influences the adsorption of 5-sulfosalicylic acid onto NDA-99. The adsorptive capacity of salicylic acid on NDA-99 decreases but increases on NDA-101 with 5-sulfosalicylic acid as the background component in a binary solute system. The amount of 5-sulfosalicylic acid adsorbed was decreased with the increase in initial concentration of salicylic acid on both adsorbents. The competition for the adsorption sites is considered to be predominant in the solid-to-liquid interaction process. The adsorption selectivity of salicylic acid onto NDA-101 is higher than onto NDA-99 by more than an order of magnitude. Thus, combination technique involving NDA-101 followed by NDA-99 can be effectively applied to separate and recover salicylic acid and 5-sulfosalicylic acid from wastewater.     

Normalized Dynamic Characterization and Application of Multiple Heat Storage Materials Based on Standard Thermal Resistance北大核心CSCD

基于标准热阻和能量流法,推导出储热材料与换热流体的瞬态换热热阻,通过类比电路分析法,获得了储热-换热过程的瞬态热量流模型及动态响应时间常数。进一步引入节点温度,重新定义换热热阻,获得了储热与换热过程耦合的三阶电路瞬态热量流模型,求解得到了加热、储热和释热三类时间常数,可用于协同表征储热材料中储热与释热的快慢程度,从而实现了多类储热材料的归一化动态表征。通过数值模拟验证与应用对比分析,发现基于多时间常数的归一化动态模型用于表征储热材料的动态特性是可行的,可直接对不同换热、储热材料进行对比分析。案例分析发现与固体储热材料换热时,液态金属的动态换热能力优于熔融盐,而相比于水蒸气和CO₂,空气与陶瓷材料换热能更快达到稳态。     

Effective electromagnetic and chiral parameters of chiral composite material

The effective parameters of chiral composite are studied using a simple model, that is, randomly oriented non-interacting wire helices embedded in a nonchiral host medium. It is found that both the effective permittivity and permeability are independent on the handedness of the chiral objects while the effective chirality admittance is dependent. It is also found that when the ratio of the radius of the chiral helix to its pitch is about 0.23, maximum chirality admittance is achieved. The effective parameters of equichiral sample are also discussed.     

Study of spontaneous combustion coals by GC and GC-MS

Organic geochemical characteristics of 3 Chinese spontaneous combustion coals have been carried out by means of GC and GC-MS analysis. It has been observed that more compounds with low to medium carbon number, such as terpenoids and others can be found in spontaneous combustion coals than in normal samples.     

Preparation of multisubstituted allenes from allylsilanes

[reaction: see text] A three-step route of converting allylsilanes to functionalized allenes was developed. Thermal decomposition of 1,1-dibromo-2-(silylmethyl)cyclopropanes, which were quantitatively prepared by treatment of allylsilane derivatives with CHBr3/KO(t)Bu, afforded substituted 2-bromo-1,3-butadienes with elimination of bromosilanes. The Pd-catalyzed reaction of the bromodienes with soft nucleophiles gave the allene derivatives. Previously inaccessible tri- and tetrasubstituted allenes can be prepared by this method as well.