Tuning the Reactivity of Isocyano Group: Synthesis of Imidazoles and Imidazoliums from Propargylamines and Isonitriles in the Presence of Multiple Catalysts

The reaction of propargyl amines with tert‐butylisonitrile in the presence of a catalytic amount of both Yb(OTf)₃ and AgOTf afforded imidazoles, whereas the same reaction with primary and secondary alkylisonitriles, as well as arylisonitriles, in the presence of three metal salts [Yb(OTf)₃/AgOTf/KOTf] resulted in the 1,3,4,5‐tetrasubstituted imidazoliums in excellent yields. Both chiral amines and chiral isonitriles can be used to provide corresponding chiral heterocycles without racemization. In this multiple catalytic system, Yb(OTf)₃ catalyzed the insertion of isonitriles to the N? H bond of amines, AgOTf catalyzed the 5‐exo‐dig cyclization of the resulting amidine nitrogen to the tethered triple bond, and KOTf promoted the salt metathesis, thus providing at the same time the counterion to the imidazolium. Against common knowledge, the isocyano group acted in these reactions as a polarized triple bond instead of conventional carbene‐like function.     

Magnetic mixed hemimicelles solid‐phase extraction coupled with high‐performance liquid chromatography for the extraction and rapid determination of six fluoroquinolones in environmental water samples

In this study, a mixed hemimicelle solid‐phase extraction method based on Fe₃O₄ nanoparticles coated with sodium dodecyl sulfate was applied for the preconcentration and fast isolation of six fluoroquinolones in environmental water samples before high‐performance liquid chromatography determination. The main factors affecting the extraction efficiency of the analytes, such as amount of surfactant, amount of Fe₃O₄ nanoparticles, extraction time, sample volume, sample pH, ionic strength, and desorption conditions, were investigated and optimized. The method has detection limits from 0.05 to 0.1 ng/mL and good linearity (r ≥ 09948) in the range 0.1–200 ng/mL depending on the fluoroquinolone. The enrichment factor is ～200. The recoveries (at spiked levels of 1, 5, and 50 ng/mL) are in the range of 79–120%.     

Syntheses,Structures, and Luminescent Properties of d10 Coordination Polymers with 2‐(4‐Carboxyphenyl)‐imidazo[4, 5‐f]‐1, 10‐phenanthroline and 1, 3‐Benzenedicarboxylate Derivatives

Four Zn^II/Cd^II coordination polymers (CPs) based on 2‐(4‐carboxy‐phenyl)imidazo[4, 5‐f]‐1, 10‐phenanthroline (HNCP) and different derivatives of 5‐R‐1, 3‐benzenedicarboxylate (5‐R‐1, 3‐BDC) (R = NO₂, H, OH), [Zn(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 1 ), [Cd(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 2 ), [Zn(HNCP)(1, 3‐BDC)(H₂O)₂]_n ( 3 ), and {[Zn(HNCP)(5‐OH‐1, 3‐BDC)(H₂O) · H₂O}_n ( 4 ) were synthesized under hydrothermal conditions. Compounds 1 – 4 were determined by elemental analyses, IR spectroscopy, and single‐crystal and powder X‐ray diffraction. Compounds 1 and 2 are isomorphous, presenting a 4‐connected uninodal (4, 4)‐sql 2D framework with threefold interpenetration, which are further extended into the three‐dimensional (3D) supramolecular architecture through π ··· π stacking interactions between the aryl rings of 5‐NO₂‐1, 3‐BDC. Compared to compound 1 , 3 is obtained by using different reaction temperatures and metal‐ligand ratios, generating a 3D framework with –ABAB– fashion via π ··· π stacking interactions. Compound 4 is a 1D chain, which is further extended into a 3D supramolecular net by hydrogen bonds and π ··· π stacking interactions. The thermogravimetric and fluorescence properties of 1 – 4 were also explored.     

Effect of oligonucleotide probes substituted by deoxyinosines on the specificity of SNP detection on the DNA microarray

One of the main factors that can affect the quality of microarray results is the microarray hybridization specificity. The key factor that affects hybridization specificity is the design of the probes. In this paper, we described a novel oligonucleotide probe containing deoxyinosines aimed at improving DNA hybridization specificity. We compared different probes to determine the distance between deoxyinosine base and SNPs site and the number of deoxyinosine bases. The new probe sequences contained two set of deoxyinosines (each set had two deoxyinosines), in which the interval between SNP site and each set of deoxyinosines was two bases. The new probes could obtain the highest hybridization specificity. The experimental results showed that probes containing deoxyinosines hybridized effectively to the perfectly matched target and improved the hybridization specificity of DNA microarray. By including a simple washing step after hybridization, these probes could distinguish matched targets from single‐base‐mismatched sequences perfectly. For the probes containing deoxyinosines, the fluorescence intensity of a match sequence was more than eight times stronger than that of a mismatch. However, the intensity ratio was only 1.3 times or less for the probes without deoxyinosines. Finally, using hybridization of the PCR product microarrays, we successfully genotyped SNP of 140 samples using these new labeled probes. Our results show that this is a useful new strategy for modifying oligonucleotide probes for use in DNA microarray analysis.     

Single nucleotide polymorphisms of mitochondrial DNA HVS‐I and HVS‐II in Chinese Bai ethnic group

For forensic and population genetic purposes, a total of 125 unrelated volunteers’ blood samples were collected from Chinese Bai ethnic minority group to analyze sequence variation of two hypervariable segments (HVS‐I and HVS‐II) in the mitochondrial DNA control region. Comparing the HVS‐I and HVS‐II sequences of the 125 Chinese Bais to the Anderson reference sequence, we found 86 polymorphic loci in HVS‐I and 40 in HVS‐II in mitochondrial DNA sequences of the Chinese Bai ethnic minority group, which defined 93 and 53 different haplotypes, respectively. Haplotype diversity and the mean pairwise differences were 0.992 ± 0.003 and 6.553 in HVS‐I, and 0.877 ± 0.027 and 2.407 in HVS‐II, respectively. We defined four macrohaplogroups R, M, N and D with the proportions ranging from 9.6% to 40.0%. With the analysis of the hypervariable domain from nucleotide 16 180–16 193 in HVS‐I, our study revealed new haplotypes of sequence variations. In addition, the Fst metric, phylogenetic tree, and principal component analysis demonstrated a close genetic relationship between the Bai group and Chinese Han populations from South China, Changsha, and Guangdong. The results support that the Bai group is a multiorigin ethnic minority that has merged with the Chinese Han population.     

表面解吸常压化学电离质谱法直接分析牙齿微区表面

采用纳升取样表面解吸常压化学电离质谱法(nano-SDAPCI-MS)结合主成分分析(PCA),建立了一种采用具有微米级针尖的金属取样针直接对龋齿不同部位取样并进行快速质谱分析的方法.数据分析结果表明,同一颗龋齿不同部位的质谱指纹谱图之间存在差异;在不需要样品预处理的前提下通过串联质谱快速测定了龋齿中的乳酸、丙酮酸、苯乙酸和丙酸等成分.采用PCA方法可较好地将龋齿病灶位置与邻近正常组织进行区分,也可对不同牙病及健康牙齿进行区分.本方法可方便地对牙齿进行直接微区分析,为鉴别牙齿疾病及观测治疗效果提供了一种快速、简单的方法,为生物体中微细部位的快速取样及直接质谱分析提供了一种可能的解决方案.     

O2/CO2气氛下稻秆添加磷酸二氢铵对固钾及灰熔融特性的研究

研究了21%O₂/79%CO₂气氛下,磷酸二氢铵对稻秆不同温度下的固钾能力及对灰熔融性的影响。利用电感耦合等离子体发射光谱(ICP-AES)、X射线衍射(XRD)以及扫描电子显微镜(SEM)等检测手段,对稻秆燃烧灰中K元素含量、产物物相以及微观形貌进行分析。固定床燃烧固钾实验表明,添加NH₄H₂PO₄能够有效提高稻秆固钾率,900℃下稻秆自身固钾率为14.65%,添加NH₄H₂PO₄后固钾率为68.79%,可以有效抑制生物质燃烧过程中碱金属以气态形式析出,并缓解了灰结渣现象。700℃燃烧条件下NH₄H₂PO₄和钾反应的主要产物为KPO₃;900℃下反应的主要产物为高熔点物质K₂CaP₂O₇,从微观形貌可以看出NH₄H₂PO₄能够抑制灰颗粒的烧结,添加NH₄H₂PO₄能有效提升稻秆灰熔点。