高效液相色谱法测定密胺餐具中甲醛单体迁移量

采用高效液相色谱法测定密胺餐具中的甲醛迁移量。样品经乙酸(4+96)溶液浸泡提取后,加入2,4-二硝基苯肼,与浸泡液中的甲醛反应生成2,4-二硝基苯腙,以C18色谱柱为分离柱,以甲醇-水(7+3)溶液为流动相进行等度洗脱,检测波长为350 nm。甲醛的质量浓度在0.01~40.0 mg·L-1范围内呈线性,测定下限(10S/N)为0.01 mg·L-1。对空白样品进行加标回收试验,回收率在99.8%~101%之间,相对标准偏差(n=10)均不大于0.6%。方法适用于密胺餐具中甲醛迁移量的检测。     

Multipore Zeolites: Synthesis and Catalytic Applications

In the last few years, important efforts have been made to synthesize so‐called “multipore” zeolites, which contain channels of different dimensions within the same crystalline structure. This is a very attractive subject, since the presence of pores of different sizes would favor the preferential diffusion of reactants and products through those different channel systems, allowing unique catalytic activities for specific chemical processes. In this Review we describe the most attractive achievements in the rational synthesis of multipore zeolites, containing small to extra‐large pores, and the improvements reported for relevant chemical processes when these multipore zeolites have been used as catalysts.     

载体表面酸碱性质对无碱水溶液中Au催化的甘油氧化反应产物选择性的调控作用

甘油(GL)是一种重要的生物平台分子,通过催化选择氧化反应将其转化为具有高附加值化学品是可持续发展化学化工的重要课题之一.以Au为催化剂的GL水相选择氧化反应可以生成甘油酸(GLA)、二羟基丙酮(DHA)、羟基丙二酸(TTA)、羟基乙酸(GCA)和乳酸(LA)等多种产物.通常,该反应需要碱(NaOH)存在时才能进行,产物往往以GLA为主(选择性40%-70%),副产物主要有GCA, TTA和草酸(OA).一般认为,可溶性碱(OH-)是通过夺取GL分子中羟基上的质子而诱发反应的.尽管在Au催化的反应体系中从未检测到有甘油醛(GLD)生成, GLD和/或DHA被认为是该反应的中间物种.本课题组前期工作表明,氧化物(TiO2, Al2O3, ZrO2, CuO等)负载的纳米Au催化剂能够在无碱(无外加OH-)水溶液中选择性催化GL氧化生成DHA(而不是GLA).因此, OH-的存在与否很可能会改变水溶液中Au催化剂上GL氧化反应的途径.本文试图回答当GL的水溶液中不存在NaOH时, Au催化剂载体的表面酸碱性质是否也会对GL氧化反应的选择性产生调控作用.我们选用Mg/Al比(x)不同的MgO-Al2O3样品为Au催化剂的载体,以尿素为沉淀剂,采用沉积沉淀法制备了相应的Au/MgO-Al2O3(x)催化剂样品.采用X射线衍射、电感耦合等离子体-原子发射光谱仪、透射电镜以及N2吸附-脱附等温线等对MgO-Al2O3(x)和/或Au/MgO-Al2O3样品的物相、元素组成、Au颗粒大小以及比表面积等进行了表征分析;采用NH3和CO2程序升温脱附(TPD)分别对MgO-Al2O3(x)载体表面的酸、碱性进行了测定. NH3-TPD和CO2-TPD结果表明,随着Mg/Al比x从0增加至4.8, MgO-Al2O3(x)的表面酸量从0.94降到0.20μmol/m2,而其表面碱量却从0.05剧增至0.80μmol/m2.因此,载体中MgO含量越多或Mg/Al比越大,其酸性越弱而碱性越强.在无碱水溶液中的催化反应结果表明, Au/MgO-Al2O3(x)上GL氧化反应的主要产物为DHA, GLA以及GCA等.随着x值(催化剂表面碱性)不断增大,产物DHA的选择性从约80%下降到10%左右,而GLA的选择性却从约4%增加至约50%.当载体为酸性最强的Al2O3(x =0)时,产物DHA的选择性为最高(80%).由此可见,载体表面的酸碱性质决定了无碱水溶液中Au催化剂上的GL氧化产物的分布. 此外,当保持Au粒子的尺寸基本不变(如3.1或6.6 nm左右),而改变载体的酸碱性质时, Au/MgO-Al2O3催化GL氧化反应的活性(TOF)可相差8-9倍.本文还通过改变Au/MgO-Al2O3样品焙烧温度,制备了表面酸碱性质相同而颗粒大小不同的三个Au/MgO-Al2O3(0.2)催化剂,考察了Au粒径对GL氧化反应选择性的影响.在这三个催化剂上, Au颗粒的平均尺寸分别为2.8,3.2和6.6 nm, GL氧化反应的产物选择性近乎相同(DHA和GLA的选择性分别为65%和15%左右),但平均尺寸为6.6 nm Au粒子的催化活性(TOF)是3.2 nm Au粒子的1.6倍,2.8 nm Au粒子的2.7倍.因此,本文建立了载体表面酸碱性质与无碱水溶液中GL氧化产物选择性之间的关系,通过改变载体表面酸碱性质实现了对无碱水溶液中Au催化剂上GL氧化反应选择性的调控.尽管载体酸碱性质和Au粒子尺寸都对Au/MgO-Al2O3催化剂的本征活性有重要影响,但载体酸碱性质的影响更显著.     

Regulating Molecular Recognition with C‐Shaped Strips Attained by Chirality‐Assisted Synthesis

Chirality‐assisted synthesis (CAS) is a general approach to control the shapes of large molecular strips. CAS is based on enantiomerically pure building blocks that are designed to strictly couple in a single geometric orientation. Fully shape‐persistent structures can thus be created, even in the form of linear chains. With CAS, selective recognition between large host and guest molecules can reliably be designed de novo. To demonstrate this concept, three C‐shaped strips that can embrace a pillar[5]arene macrocycle were synthesized. The pillar[5]arene bound to the strips was a better host for electron‐deficient guests than the free macrocycle. Experimental and computational evidence is provided for these unique cooperative interactions to illustrate how CAS could open the door towards the precise positioning of functional groups for regulated supramolecular recognition and catalysis.     

Morphology‐Controlled Synthesis of Organometal Halide Perovskite Inverse Opals

The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology‐control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology‐control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene‐based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites.     

Ultraviolet C radiation influences the robustness of RNA integrity measurement

The analytical and clinical validity of analyses of RNA samples destined for clinical diagnosis and therapeutic management is directly impacted by RNA quality. RNA is affected by heat, enzymatic degradation, and Ultraviolet (UV) light. RNA from three eukaryotic cell lines was degraded by heat, RNase, or UV light. RNA integrity values obtained with the benchmark Agilent Bioanalyzer 2100 system were compared with those from the more recent QIAxcel Advanced system. The application of this novel method has allowed us to unravel differences between RNA biophysical and biochemical degradation modes. Agilent RNA integrity number (RIN) and QIAxcel RIS were comparable in heat‐degraded and RNase III‐degraded RNA. Agilent RIN and QIAxcel RIS were comparable at a RIN decision level of 7 in UV‐degraded RNA but not overall. The QIAxcel RIS method was more precise than Agilent RIN for RIN<8, while the inverse was true for RIN≥8. Greater degradation of mRNA and rRNA in UV‐damaged samples hampered the Agilent RIN calculation algorithm. Overall, RIS was more robust than RIN for assessing RNA integrity. The ΔΔCt‐values for heat‐ and UV‐degraded RNA samples showed slightly higher correlation with RIS than with RIN. RNA integrity can be used to categorize RNA samples for suitability for downstream gene expression analyses, independently of the RNA degradation mechanism. The new method QIAxcel is more robust and therefore allows more accurate categorization of compromised RNA samples.     

Sonochemical Synthesis of Gold Nanoparticles by Using High Intensity Focused Ultrasound

The sonochemical synthesis of gold nanoparticles (GNPs) with different shapes and size distributions by using high‐intensity focused ultrasound (HIFU) operating at 463 kHz is reported. GNP formation proceeds through the reduction of Au³⁺ to Au⁰ by radicals generated by acoustic cavitation. TEM images reveal that GNPs show irregular shapes at 30 W, are primarily icosahedral at 50 W and form a significant amount of nanorods at 70 W. The size of GNPs decreases with increasing acoustic power with a narrower size distribution. Sonochemiluminescence images help in the understanding of the effect of HIFU in controlling the size and shapes of GNPs. The number of radicals that form and the mechanical forces that are generated control the shape and size of the GNPs. UV/Vis spectra and TEM images are used to propose a possible mechanism for the observed effects. The results presented demonstrate, for the first time, that the HIFU system can be used to synthesise size‐ and shape‐controlled metal nanoparticles.     

Laser Sculpting of Atomic sp,sp2, and sp3 Hybrid Orbitals

Atomic sp, sp², and sp³ hybrid orbitals were introduced by Linus Pauling to explain the nature of the chemical bond. Quantum dynamics simulations show that they can be sculpted by means of a selective series of coherent laser pulses, starting from the 1s orbital of the hydrogen atom. Laser hybridization generates atoms with state‐selective electric dipoles, opening up new possibilities for the study of chemical reaction dynamics and heterogeneous catalysis.     

Maintenance of residual activity of Bt toxin by using natural and synthetic dyes: a novel approach for sustainable mosquito vector control

Mosquito control protein from Bacillus thuringiensis gets inactivated with exposure to sunlight. To address this issue, the potential of synthetic and natural dye was investigated as sunlight protectants. Bt SV2 in absence of dyes when exposed to sunlight showed reduced effectiveness against the fourth instars of mosquito larvae. Whereas acriflavin, congo red and violacein were able to maintain 86.4%, 91.6% and 82.2% mosquito larvicidal efficacy of Bt SV2 against IVth instars larvae of Anopheles stephensi Meigen after exposure to sunlight. Similarly, beetroot dye, acriflavin, congo red and violacein maintained 98.4%, 97.1%, 90.8% and 70.7% larvicidal activities against Aedes aegypti Linnaeus after sunlight exposure. Prodigiosin was found to be the best photo-protectant by simultaneously protecting and enhancing Bt activity by 6.16% and 22.16% against A. stephensi and A. aegypti, respectively. Combination of dyes with Bt formulations can be a good strategy for mosquito control programmes in tropical and sub-tropical regions.