A Single Excitation‐Duplexed Imaging Strategy for Profiling Cell Surface Protein‐Specific Glycoforms

This work develops a site‐specific duplexed luminescence resonance energy transfer system on cell surface for simultaneous imaging of two kinds of monosaccharides on a specific protein by single near‐infrared excitation. The single excitation‐duplexed imaging system utilizes aptamer modified upconversion luminescent nanoparticles as an energy donor to target the protein, and two fluorescent dye acceptors to tag two kinds of cell surface monosaccharides by a dual metabolic labeling technique. Upon excitation at 980 nm, only the dyes linked to protein‐specific glycans can be lit up by the donor by two parallel energy transfer processes, for in situ duplexed imaging of glycoforms on specific protein. Using MUC1 as the model, this strategy can visualize distinct glycoforms of MUC1 on various cell types and quantitatively track terminal monosaccharide pattern. This approach provides a versatile platform for profiling protein‐specific glycoforms, thus contributing to the study of the regulation mechanisms of protein functions by glycosylation.     

纳米荧光探针用于核酸分子的检测及成像研究

核酸,包括脱氧核糖核酸和核糖核酸,在生物的生长、发育、突变、炎症、癌症等正常或异常的生命活动中发挥着重要的作用,它们的异常表达与多种疾病的发生、发展也密切相关.因此,发展准确、有效的方法实现核酸分子的检测,对深入探究核酸的功能调控以及相关疾病的早期检测与治疗都具有重要的意义.荧光检测法与荧光成像技术具有灵敏度高、时空分辨率高等优点,为实时、准确的检测核酸分子提供了有力的工具.本文着重综述了近年来发展的纳米荧光探针用于疾病相关核酸分子的检测与细胞和活体成像工作的研究进展,最后提出了进一步构建新型纳米荧光探针用于核酸检测面临的挑战、未来发展方向与展望.     

Vibronically resolved electronic circular dichroism spectra of (R)-(+)-3-methylcyclopentanone: a theoretical study

The vibrationally resolved electronic circular dichroism (ECD) spectra of the two dominant conformers of (R)-(+)-3-methylcyclopentanone in gas phase are computed by density functional response theory, with a full account of Franck-Condon and Herzberg-Teller vibrational contributions at the harmonic level. Proper inclusion of the latter contributions was made possible by the recent implementation of effective-scaling computations of vibrational overlaps and of analytical gradients of time dependent DFT. The Coulomb-attenuated Becke three parameters Lee-Yang-Parr (CAM-B3LYP) functional reproduces both the position and the intensity of the experimental peaks, providing a remarkable improvement over the spectra obtained with the popular hybrid B3LYP functional, and allowing a confident assignment of the CD fine vibrational structure. Franck-Condon and Herzberg-Teller contributions are discussed in detail. The computed decrease of the CD intensity in the gas phase upon increase of the temperature of the sample follows the trend observed experimentally in different solvents.     

Ab initio study of the one- and two-photon circular dichroism of R-(+)-3-methyl-cyclopentanone

One- and two-photon circular dichroism spectra of R-(+)-3-methyl-cyclopentanone, a system that has been the subject of recent experimental studies of (2+1) resonance-enhanced multiphoton ionization circular dichroism, have been calculated with an origin-invariant density functional theory approximation in the region of the lowest electronic excited states, both for the gas phase and for a selection of solvents. A polarizable continuum model is used in the calculations performed on the solvated system. Two low-lying conformers are analyzed, and a comparison of the intensities and characteristic features is made with the corresponding two-photon absorption for each species, also for the Boltzmann-averaged spectra. The effect of the choice of geometry, basis set, and exchange-correlation functional is carefully analyzed. It is found that a density functional theory approach using the Coulomb attenuating method variant of Becke's three-parameter exchange and the Lee-Yang-Parr correlation functionals with correlation-consistent basis sets of double-zeta quality can reproduce the experimental electronic circular dichroism spectra very well. The features appearing in experiment are characterized in terms of molecular excitations, and the differences in the response of each state in the one- and two-photon processes are highlighted.     

Photoinduced Oxidation Reaction of Benzotrifluoride with OH Radical by the Laser Flash Method

The optical transient and kinetics characterizations of the transients formed in the reaction of OH with benzotrifluoride (BTF) were performed by a laser flash photolysis technique. The results indicated that the formation of π‐type adduct of C₆H₅(OH)CF₃ was the major reaction channel, and the δ‐type adduct of C₆H₅CF₃OH formation was an additional minor process in the oxidation reaction of BTF attacked by OH radicals yielded from the photolysis of H₂O₂. Addition of OH to the CF₃ group led to the fluoride ion elimination to yield α,α‐difluorophenylcarbinol (C₆H₅CF₂OH). Trifluoromethylphenol (HOC₆H₄CF₃) of meta‐, para‐ and ortho‐substituted isomers resulted from the addition of OH to the BTF aromatic ring.     

二氧化硅脱除羟基的动力学研究

醇盐水解法制备的纳米二氧化硅粉体中含有大量羟基,结合差热分析,采用Doyle-Ozawa法和Kissinger法研究二氧化硅粉体脱除羟基的动力学,得到反应表观活化能为134.78kJ.mol-1;并采用Coats-Redfern法进行验证,结果为140.22 kJ.mol-1.采用SEM和XRD对样品进行检测,表明非晶态二氧化硅样品颗粒大小没有变化,晶态没有改变.     

富勒烯C72分子静电势以及Sc2@C72的理论研究

已制备出来的富勒烯都遵循分离五元环规则(IPR)。C72虽然满足五元环分离规则具有D6d对称结构,然而迄今为止还没有实现其宏观量的合成,人们称之为“遗失的碳笼”。但人们合成出了内掺金属M@C72(M=Ca,La等),证实了C72的存在[1-4]。最近用两步高性能液体色谱方法又成功地分离出La2     

Shape-specific detection based on fluorescence resonance energy transfer using a flexible water-soluble conjugated polymer

We present the detection of the shape-specific conformation of DNA based on the fluorescence resonance energy transfer (FRET) by using a novel flexible water-soluble cationic conjugated polymer (CCP). The flexible backbone of CCP has more conformational freedom with the potential to be responsive to analyte shape by electrostatic interaction between flexible CCP and negatively charged DNA. The analyte shape dependent recognition is accomplished by structural changes that compressed or extended the flexible CCP. The morphology-dependent spectral properties of the novel flexible polymer related to the analyte shapes are investigated in detail, where two types of chromophores, referred to as "isolated" segment and "packed" segment aggregates, within the flexible polymer are identified by means of ensemble and single molecule measurements upon binding with different geometric DNA. The change in fluorescence intensity upon binding with shape-specific DNA without obvious color shifts makes this novel flexible polymer a suitable CCP donor for FRET measurements. The results provide insights for understanding the spectral properties of flexible water-soluble CCP and CCP/DNA interaction related to the geometry of target analyte.     

β-榄香烯三羰基铼配合物的合成、放射化学合成及抗癌活性研究

以中草药有效成分β-榄香烯为起始原料, 经烯丙位的氯代反应及亲核取代反应在β-榄香烯母体上成功地引入含吡啶基的三齿螯合剂, 并与稳定的三羰基铼配位, 得到了一种新的铼(I)三齿配合物, 在此基础上利用铼的放射性同位素Re-188进行了放射性标记. 反应中间体及最终化合物分别用IR, ¹H NMR, HRMS, HPLC或元素分析进行表征, 并对该化合物进行了初步的体外抗癌活性研究. β-榄香烯三羰基铼配合物的合成、放射化学合成及体外抗癌活性评价, 为探讨β-榄香烯体内靶点和作用机制提供了可能, 并为最终开发基于β-榄香烯的放射性药物奠定了基础.     

The application of amine-terminated silicon quantum dots on the imaging of human serum proteins after polyacrylamide gel electrophoresis (PAGE)

Novel amine-terminated silicon (Si) quantum dots (QDs) were synthesized and applied for the detection of human serum proteins on gels directly after polyacrylamide gel electrophoresis (PAGE). The diameter of these stable amine-terminated Si?QDs was in the range of 0.5-2.0 nm. In this study, the fluorescent imaging conditions, such as the buffer solution, pH value, buffer concentration and quantity of Si?QDs, were optimized and the possible mechanisms of Si?QDs-protein interaction were analyzed. The mode of Si?QDs and human serum albumin association was found to occur by hydrogen bond interactions; this was probably attributed to the interaction between the amino group of amine-terminated Si?QDs and the carboxyl group of proteins. Meanwhile, human serum proteins separated by native 1D and native 2D electrophoresis were detected by Si QD-based fluorescent imaging. Some proteins, such as isoform 1 of α-1-antitrypsin, complement C3 (Fragment) and hemopexin, which were identified by mass spectrometry (MS), were easily detected by using Si?QDs, but not with CBB-R250 staining. The Si?QDs-based fluorescent imaging technique with high resolution is a sensitive and dependable method for direct detection of human serum proteins, and has enormous potential in clinical diagnosis.