Synthesis of chlorophyll-a derivatives possessing (un)substituted 13-exo-methylene moiety and their optical properties

Chlorophyll-a derivatives possessing an un/mono/disubstituted methylene moiety at the 13¹-position were prepared by (un)substituted methylation of the 13-carbonyl group and successive dehydration. Substitution of the 13¹-oxo to the methylene group slightly blue-shifted electronic absorption and emission bands in a solution and decreased chemical stability to give an oxidation product cleaved at the E-ring. Further mono/disubstitution at the methylene terminal increased wavelengths of absorption and emission maxima as well as oxidative tolerance.     

二甲基亚砜对乙酸气相色谱保留时间的影响及其机理

通过气相色谱、红外光谱分析和量子化学计算,探究溶于二甲基亚砜（DMSO）中乙酸保留时间发生波动的原因。 结果显示,乙酸保留时间变化与DMSO体积等量递增呈线性关系,R²=0.99301;根据红外光谱分析得出,DMSO和乙酸之间生成了氢键,以DMSO-乙酸分子的形式通过色谱柱;根据Gaussian09程序计算结果,DMSO电子密度大的部分给予电子,与乙酸之间形成了氢键,而DMSO电子密度小的部分容易获得电子与具有强偶极矩的色谱柱固定液聚乙二醇产生作用力,吸附在固定液上。因此,在上述一系列复杂的分子间作用力的共同影响下,乙酸保留时间发生了波动,且随着溶剂DMSO体积比增加,乙酸保留时间不断延长。     

Efficient Copper‐Catalyzed Direct Intramolecular Aminotrifluoromethylation of Unactivated Alkenes with Diverse Nitrogen‐Based Nucleophiles

A mild, convenient, and step‐economical intramolecular aminotrifluoromethylation of unactivated alkenes with a variety of electronically distinct, nitrogen‐based nucleophiles in the presence of a simple copper salt catalyst, in the absence of extra ligands, is described. Many different nitrogen‐based nucleophiles (e.g., basic primary aliphatic and aromatic amines, sulfonamides, carbamates, and ureas) can be employed in this new aminotrifluoromethylation reaction. The aminotrifluoromethylation process allows straightforward access to diversely substituted CF₃‐containing pyrrolidines or indolines, in good to excellent yields, through a direct difunctionalization strategy from the respective acyclic starting materials. Mechanistic studies were conducted and a plausible mechanism was proposed.     

Metal‐Free Oxidative Radical Addition of Carbonyl Compounds to α,α‐Diaryl Allylic Alcohols: Synthesis of Highly Functionalized Ketones

A metal‐free direct alkylation of simple carbonyl compounds (ketones, esters, and amides) with α,α‐diaryl allylic alcohols is described. The protocol provides facile access to highly functionalized dicarbonyl ketones by a radical addition/1,2‐aryl migration cascade. The regioselectivity of the reaction was precisely controlled by the nature of the carbonyl compound.     

Isolation of a Neutral Boron‐Containing Radical Stabilized by a Cyclic (Alkyl)(Amino)Carbene

Utilizing a cyclic (alkyl)(amino)carbene (CAAC) as a ligand, neutral CAAC‐stabilized radicals containing a boryl functionality could be prepared by reduction of the corresponding haloborane adducts. The radical species with a duryl substituent was fully characterized by single‐crystal X‐ray structural analysis, EPR spectroscopy, and DFT calculations. Compared to known neutral boryl radicals, the isolated radical species showed larger spin density on the boron atom. Furthermore, the compound that was isolated is extraordinarily stable to high temperatures under inert conditions, both in solution and in the solid state. Electrochemical investigations of the radical suggest the possibility to generate a stable formal boryl anion species.     

A Small-Molecule AIE Chromosome Periphery Probe for Cytogenetic Studies

The chromosome periphery (CP) is a complex network that covers the outer surface of chromosomes. It acts as a carrier of nucleolar components, helps maintain chromosome structure, and plays an important role in mitosis. Current methods for fluorescence imaging of CP largely rely on immunostaining. We herein report a small-molecule fluorescent probe, ID-IQ , which possesses aggregation-induced emission (AIE) property, for CP imaging. By labelling the CP, ID-IQ sharply highlighted the chromosome boundaries, which enabled rapid segmentation of touching and overlapping chromosomes, direct identification of the centromere, and clear visualization of chromosome morphology. ID-IQ staining was also compatible with fluorescence in situ hybridization and could assist the precise location of the gene in designated chromosome. Altogether, this study provides a versatile cytogenetic tool for improved chromosome analysis, which greatly benefits the clinical diagnostic testing and genomic research.     

Estimation of 47Sc and 177Lu production rates from their natural targets in Kyoto University Research Reactor

Journal of Radioanalytical and Nuclear Chemistry - To assess the capability of Kyoto University Research Reactor to supply the domestic needs of medical isotopes, its neutron flux has been fully...     

Production of 99Mo/99mTc by photonuclear reaction using a natMoO3 target

Journal of Radioanalytical and Nuclear Chemistry - Amount estimation of production of 99Mo required for medical applications was carried out by utilizing an electron linear accelerator with...     

同位素稀释高效液相色谱-串联质谱法测定水体、底泥、鱼及虾中氯硝柳胺残留量

建立了水体、底泥、鱼体自然比例带皮肌肉和虾肌肉中氯硝柳胺(NIC)残留量测定的同位素稀释高效液相色谱-串联质谱(HPLC-MS/MS)法。水样经碱化后以乙酸乙酯提取,其他样品采用0.1%氨水乙腈提取,C_(18)粉进行样品净化。以乙腈-水为流动相,流速为0.3 mL/min,采用Thermo Hypersil Gold C_(18)(150 mm×2.1 mm,5μm)色谱柱进行分离,氯硝柳胺稳定同位素标记物(氯硝柳胺-~(13)C_6)为内标,选择反应监测(SRM)模式扫描,内标法定量。结果表明氯硝柳胺在0.2～200μg/L范围内呈良好线性关系,相关系数(r~2)不小于0.999 5。空白水样在2.5、25、250 ng/L加标水平下的平均回收率为90.5%～109%,相对标准偏差(RSD)为3.2%～11%,检出限(LOD)为1.0 ng/L,定量下限(LOQ)为2.5 ng/L;空白底泥、黄颡鱼自然比例带皮肌肉和克氏原螯虾肌肉在0.5、5.0、50μg/kg加标水平下的平均回收率分别为89.4%～113%、92.8%～110%和94.1%～107%,RSD分别为4.6%～12%、2.8%～11%和3.2%～9.3%,LOD均为0.2μg/kg,LOQ均为0.5μg/kg。该方法的灵敏度、准确度和选择性高,适用于实际水产养殖环境水体、底泥、鱼和虾中氯硝柳胺的残留分析。     

Thermodynamic Control of Domain Swapping by Modulating the Helical Propensity in the Hinge Region of Myoglobin

Domain swapping is an exception to Anfinsen's dogma, and more than one structure can be produced from the same amino acid sequence by domain swapping. We have previously shown that myoglobin (Mb) can form a domain‐swapped dimer in which the hinge region is converted to a helical structure. In this study, we showed that domain‐swapped dimerization of Mb was achieved by a single Ala mutation of Gly at position 80. Multiple Ala mutations at positions 81 and 82 in addition to position 80 facilitated dimerization of Mb by stabilization of the dimeric states. Domain swapping tendencies correlated well with the helical propensity of the mutated residue in a series of Mb mutants with amino acids introduced to the hinge region. These findings demonstrate that a single mutation in the hinge loop to modify helical propensity can control oligomer formation, providing new ideas to create high‐order protein oligomers using domain swapping.