The heavy atom effect on photocleavage of DNA by mono-hydroxyl halogenated corroles

DNA photocleavage properties of halogenated mono-hydroxyl corrole 1-5 were investigated.It was found that these corroles were able to photocleavage supercoiled pBR 322 DNA（SC） into nicked-circular DNA（NC）.The activity of these corroles follows an order of 4>3>2≈1>5.The photosensitized singlet oxygen（Φ;） quantum yield by these corroles also follows that same order,showing the photocleavage activity is related to the heavy atom effect of halogen atoms on corroles.

Direct demodulation method for heavy atom position determination in protein crystallography

The first step of phasing in any de novo protein structure determination using isomorphous replacement （IR） or anomalous scattering （AD） experiments is to find heavy atom positions. Traditionally, heavy atom positions can be solved by inspecting the difference Patterson maps. Due to the weak signals in isomorphous or anomalous differences and the noisy background in the Patterson map, the search for heavy atoms may become difficult. Here, the direct demodulation （DD） method is applied to the difference Patterson maps to reduce the noisy backgrounds and sharpen the signal peaks. The real space Patterson search by using these optimized maps can locate the heavy atom positions more accurately. It is anticipated that the direct demodulation method can assist in heavy atom position determination and facilitate the de novo structure determination of proteins.

Synthesis,Characterization,and Linear and Nonlinear Optical Properties of Phenylene-vinylene Based Chromophores for Singlet Oxygen Generation

A series of symmetrical and unsymmetrical phenylene-vinylene （PV） based chro- mophores with the molecular configuration of donor-π-donor （D-g-D） were prepared and characterized. Iodine was first introduced into the Jr-conjugation backbone of the PV based chromophores in order to study the heavy atom effect on their linear absorption, two-photon absorption （TPA） properties, as well as singlet oxygen generation properties. TPA cross-sections of these chromophores were investigated by using the two-photon excited fluorescence method. The unsymmetrical chromophores were found to have larger TPA cross-section values compared to their symmetrical counterparts. For one of the unsymmetrical chromophores with the iodine incorporation, a large TPA cross section value with quenched emission was found. The decreased fluorescence quantum yield of a molecule can be ascribed to the increased intersystem crossing, which is favorable for enhancing the singlet oxygen generation. Therefore, the unsymmetrical PV based chromophores with heavy atom incorporation are promising singlet oxygen sensitizers for the photodynamic therapy application.

Achieving highly efficient long-wavelength phosphorescence emission of large singlet-triplet energy gap materials by host-guest doping

High-efficiency long-wavelength phosphorescence emissions of large singlet-triplet energy gap(ΔE_(ST))materials are essential for applications in biology and display.However,few long-wavelength phosphorescence emissions of largeΔE_(ST)materials have been reported due to the weak spin-orbit coupling(SOC)and strong non-radiative transitions.Herein,we develop a strategy to achieve highly efficient long-wavelength room temperature phosphorescence(RTP)emission of largeΔE_(ST)materials,which display bright red RTP emission with above 400μs lifetime and 6.5%phosphorescent quantum efficiency.Our experiments and theoretical calculations reveal that the fishbone-like packing and the zig-zag interactions provide favorable conditions for suppressing the non-radiative transitions of triplet state excitons,and heavy atoms effectively promote the intersystem crossing(ISC)process for highly efficient long-wavelength phosphorescence emission.The universality of the method for highly efficient long-wavelength RTP emission of largeΔE_(ST)materials was further investigated in various guests.Moreover,these materials with largeΔE_(ST)manifest the advantages of large color contrast on the display and utilization potentiality in information encryption.This strategy paves the way for the high contrast display and development of information encryption with RTP emission.

A noise and artifact suppression using resampling(NASR)method to facilitate de novo protein structure determination

Background The search of heavy atoms is crucial to the de novo determination of protein structures.Typically,the difference Patterson map is calculated as a first step to solve substructure.However,the pseudo-peaks and noises inherent in such maps arising from the high symmetry and large size of protein structures accompanied with the data collection errors inevitably pose a challenge in accurate real space-based substructure determination.Purpose In order to mitigate such pseudo-peaks and noises and further improve signal-to-noise ratio(SNR)of the difference Patterson map,the noise and artifact suppression using resampling(NASR)method originally proposed in nuclear magnetic resonance is introduced into protein crystallography in this work to optimize the difference Patterson map.Methods The NASR method makes use of the statistical learning theory,which in this work repeatedly samples a fixed portion of diffraction data(sub-dataset)randomly followed by a statistical analysis of the multiple calculated difference Patterson maps to discard pseudo-peaks and noises.Its feasibility is based on the fact that the true vector peaks of the heavy atoms keep static in the multiple random sub-datasets,whereas the pseudo-peaks and noises fluctuate remarkably.And the key of this method lies in the design of a weighting function to distinguish true vector peaks from pseudo-peaks and noises,as well as a proper selection of the parameters associated with the function.Results The introduced NASR method is both numerically and experimentally demonstrated to be feasible in suppressing spurious peaks and non-correlative noises intrinsic to the difference Patterson maps.As a result,the SNR of the difference Patterson maps can be enhanced to some extent to facilitate real space-based substructure determination.Conclusion It is therefore anticipated that the proposed method may provide a meaningful insight into how to denoise the difference Patterson maps,which in turn assists in locating heavy atoms and further facilitates de novo protein structure determination.

Recent progress on pure organic room temperature phosphorescent polymers

So far,pure organic room temperature phosphorescence(RTP)materials are developing rapidly and have become a research hotspot in the scientific community.They are regarded as valuable resources with great potential for development in many fields,such as biomedicine,information multi-level encryption,smart anticounterfeiting,and so on.Among them,a series of pure organic RTP polymer systems emerged at the right moment based on the excellent properties of polymers such as easy processing,low cost,and good biocompatibility.Furthermore,the huge molecular weight,long-chain intertwined structure,and potential interactions with phosphors of polymers make them a focus for RTP emission.Herein,we describe the development history of this system in detail,explore the necessary factors for highly efficient emission from the phosphorescence emission process,and based on the dual effects of enhancing phosphorescence emission and shortening luminescence lifetime brought by heavy atoms,we summarize the internal mechanism and achievements of various researches from the perspective of heavy atom–containing and non-heavy atom systems.

Ab Initio and Density Functional Study on the First Hyperpo-larizabilities of Squaric Acid Homologues

The first hyperpolarizabilities of four squaric acid homologues: squaric acid, 1, 2-dithiosquaric acid, 1, 2-diselenosquaric acid and 1,2-ditellurosquaric acid have been calculated using ab initio and DFT methods. The effects of equilibrium geometries. basis set and electron correlation on the first hyperpolarizabilities of these molecules were investigated. The frequency dispersion effect and solvent effect, which are essential to get reliable outputs in comparison to the experimental results, have also been explored. On the basis of these investigations, it is worthy to point out that the heavy atom effect takes effect for these squaric acid homologues.

Insight understanding into influence of binding mode of carboxylate with metal ion on ligand-centered luminescence properties in Pb-based coordination polymers

In the crystal engineering area,it is important to clearly demonstrating the relationship of structure and certain functionality.Herein,we present the study of the relationship of structure with phosphorescent nature for two new room temperature phosphorescence(RTP) coordination polymers(CPs).[Pb(FDA)(H_(2)O)](1) and [NH_(3)(CH_(3))NH_(2)(CH_(3))_(2)][Pb_(4)(FDA)_(5)](2),where H_(2) FDA is 2,5-furandicarboxylic acid,have been synthesized by solvothermal method using different solvents and Pb^(2+) sources and characterized by microanalysis,powderX-ray diffraction(PXRD),thermogravimetric(TG),IR and UV-vis spectra.The Pb^(2+)ions adopt bicapped triangle prism coordination sphere in 1 and 2,which are connected together via FDA^(2-) ligands into bilayer structure in 1 while pillared-layer framework in 2.The FDA^(2-) ligands show different bridging modes in 1 and 2,leading to distinct coordination interactions between Pb^(2+) ion and FDA^(2-) ligand in both CPs.Both 1 and 2 emit ligand-centered RTP due to the heavy atom of Pb^(2+) ion,with a lifetime and quantum yield of 0.62 ms and 14.9% in 1 versus 1.69 ms and 15.7% in 2.The emission peak shows significant redshift(79 nm) in 2 regarding 1,which arises from their distinction of coordination interactions between Pb^(2+) ion and FDA^(2-) ligand in both CPs.