Molecular characteristics and structure–activity relationships of food-derived bioactive peptides

Peptides are functional active fragments of proteins which can provide nutrients needed for human growth and development,and they also have unique physiological activity characteristics relative to proteins.Bioactive peptides contain a great deal of development potential.More specifically,food-derived bioactive peptides have the advantages of a wide variety of sources,unique structures,high efficiency and safety,so they have broad development prospects.This review provides an overview of the current advances regarding the preparation,functional characteristics,and structure–activity relationships of food-derived bioactive peptides.Moreover,the prospects for the future development and application of food-derived bioactive peptides are discussed.This review may provide a better understanding of foodderived bioactive peptides,and some constructive inspirations for further research and applications in the food industry.

Design strategies and structure‐performance relationships of heterogeneous catalysts for selective hydrogenation of 1,3‐butadiene

Selective hydrogenation of 1,3‐butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector.Catalyst design is crucial to achieve a virtually alkadiene‐free product while avoiding over‐hydrogenating valuable olefins.In addition to the great industrial relevance,this demanding selectivity pattern renders 1,3‐butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia.Nonetheless,critical reviews on the catalyst development are extremely lacking in literature.In this review,we aim to provide the reader an in‐depth overview of different catalyst families,particularly the precious metal‐based monometallic catalysts(Pd,Pt,and Au),developed in the last half century.The emphasis is placed on the development of new strategies to design high‐performance architectures,the establishment of structure‐performance relationships,and the reaction and deactivation mechanisms.Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.

A Quantitative Structure Property Relationship for Prediction of Flash Point of Alkanes Using Molecular Connectivity Indices

Many structure-property/activity studies use graph theoretical indices, which are based on the topological properties of a molecule viewed as a graph. Since topological indices can be derived directly from the molecular structure without any experimental effort, they provide a simple and straightforward method for property prediction. In this work the flash point of alkanes was modeled by a set of molecular connectivity indices （Х）, modified molecular connectivity indices （ ^mХ^v ） and valance molecular connectivity indices （ ^mХ^v ）, with ^mХ^v calculated using the hydrogen perturbation. A stepwise Multiple Linear Regression （MLR） method was used to select the best indices. The predicted flash points are in good agreement with the experimental data, with the average absolute deviation 4.3 K.

Quantitative Structure-chromatographic Retention Relationship for Polychlorinated Dibenzothiophenes and Their Corresponding Sulfones

Polychlorinated dibenzothiophenes（PCDTs）and their corresponding sulfone（PCDTO2）compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations of electrostatic potentials（ESPs）on molecular surface have been performed for all 135 PCDTs and 135 PCDTO2 congeners at the HF/6-31G*level of theory.A number of statistically-based parameters have been extracted.Linear relationship between gas-chromatographic retention index（RI）and the structural descriptors have been established by multiple linear regression.The result shows that two descriptors derived from positive electrostatic potential on molecular surface, ■ and π,together with the molecular volume(Vmc)and the energy of the lowest unoccupied molecular orbital(ELUMO)can be well used to express the quantitative structure-retention relationship（QSRR）of PCDTs and PCDTO2.Predictive capability of the two models has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient(RCV)of 0.996 and 0.997,respectively.Furthermore,the predictive power of the models is further examined for the external test set.Correlation coefficients（R）between the observed and predicted RI values for the external test set are 0.997 and0.998,respectively,validating the robustness and good prediction of our model.The QSRR model established may provide again a powerful method for predicting chromatographic properties of aromatic organosulfur compounds.

Quantitative Structure-retention Relationship Study of Polychlorinated Dibenzothiophenes by Molecular Electronegativity Distance Vector(MEDV)

Polychlorinated dibenzothiophenes（PCDTs） are classified as persistent organic pollutants in the environment,so the analysis of PCDTs by their gas chromatographic behaviors is of great significance.Quantitative structure-retention relationship（QSRR） analysis is a useful technique capable of relating chromatographic retention time to the molecular structure.In this paper,a QSRR study of 37 PCDTs was carried out by using molecular electronegativity distance vector（MEDV） descriptors and multiple linear regression（MLR） and partial least-squares regression（PLS） methods.The correlation coefficient R of established MLR,PLS models,leave-one-out（LOO） cross-validation（CV）,Q2ext were 0.9951,0.9942,0.9839（MLR） and 0.9925,0.9915,0.9833（PLS）,respectively.Results showed that the model exhibited excellent estimate capability for internal sample set and good predictive capability for external sample set.By using MEDV descriptors,the QSRR model can provide a simple and rapid way to predict the gas-chromatographic retention indices of polychlorinated dibenzothiophenes in conditions of lacking standard samples or poor experimental conditions.

Studies on a Novel Characteristic Atom-pair Holographic Code Applied to Quantitative Structure-chromatographic Retention Relationship of Organic Compounds

6 Atomic fragment types of organic compound have been defined, and the multilevel atom-pair frequency matrix has been constructed according to the occurrence number in pairs of atomic fragments with different bond lengths in the molecule. On the basis of them, a novel molecular coding technique： characteristic atom-pair holographic code （CAHC）, is obtained. To some extent, this method exhibits a large number of benefits at the same time. For example, it can calculate 2D molecular topological descriptor easily, operate without difficulty and possess definite physicochemical meaning of 3D molecular structural characterization methods, and may fetch the complicated information of molecule, etc. Therefore, it is appropriate for the study on quantitative structure-property/activity relationship （QSPR/QSAR） of medicines and biological molecules. We attempt in this paper to utilize the method of CAHC to the quantitative prediction of reversed-phase liquid chromatogram （RPLC） retention data of 33 purine derivatives and 24 steroids. The fitting multiple correlation coefficient R2, cross-validated multiple correlation coefficient Q2 and predicted ability Q^2 pred over test set＇s samples of obtained partial least-square （PLS） regression model are respectively 0.990, 0.893 and 0.977, 0.897, 0.941.

Molecular Modeling and Design of Arylthioindole Derivatives as Tubulin Inhibitors

Three-dimensional quantitative structure activity relationship （3D-QSAR） and docking studies of a series of arylthioindole derivatives as tubulin inhibitors against human breast cancer cell line MCF-7 have been carried out. An optimal 3D-QSAR model from the comparative molecular field analysis （CoMFA） for training set with significant statistical quality （R2=0.898） and predictive ability （q2=0.654） was established. The same model was further applied to predict pIC50 values of the compounds in test set, and the resulting predictive correlation coefficient R2（pred） reaches 0.816, further showing that this CoMFA model has high predictive ability. Moreover, the appropriate binding orientations and conformations of these compounds interacting with tubulin are located by docking study, and it is very interesting to find the consistency between the CoMFA field distribution and the 3D topology structure of active site of tubulin. Based on CoMFA along with docking results, some important factors improving the activities of these compounds were discussed in detail and were summarized as follows： the substituents R3-R5 （on the phenyl ring） with higher electronegativity, the substituent R6 with higher eleetropositivity and bigger bulk, the substituent R7 with smaller bulk, and so on. In addition, five new compounds with higher activities have been designed. Such results can offer useful theoretical references for experimental works.

Pharmacokinetic evaluation,molecular docking and in vitro biological evaluation of 1,3,4-oxadiazole derivatives as potent antioxidants and STAT3 inhibitors

1, 3, 4-Oxadiazole derivatives(4 a–5 f) were previously synthesized to investigate their anticancer properties.However, studies relating to their antioxidant potential and signal transducer and activator of transcription(STAT) inhibition have not been performed. We investigated previously synthesized 1, 3, 4-oxadiazole derivatives(4 a–5 f) for various radical scavenging properties using several in vitro antioxidant assays and also for direct inhibition of STAT3 through molecular docking. The data obtained from various antioxidant assays such as 2, 2,-diphenyl-1-picrylhydrazyl radical(DPPH), nitric oxide, hydrogen peroxide, and superoxide anion radical revealed that among all the derivatives, compound 5 e displayed high antioxidant activities than the standard antioxidant L-ascorbic acid. Additionally, the total reduction assay and antioxidant capacity assay further confirmed the antioxidant potential of compound 5 e. Furthermore, the molecular docking studies performed for all derivatives along with the standard inhibitor STX-0119 showed that binding energy released in direct binding with the SH2 domain of STAT3 was the highest for compound 5 e(-9.91 kcal/mol).Through virtual screening, compound 5 e was found to exhibit optimum competency in inhibiting STAT3 activity. Compound 5 e decreased the activation of STAT3 as observed with Western blot. In brief, compound5 e was identified as a potent antioxidant agent and STAT3 inhibitor and effective agent for cancer treatment.

Relationship between structure and anti-oxidation of tocopherol with molecular orbit theory

目的：探索不同分子结构的生育酚和一些酚类化合物所具抗氧化作用的构效关系．方法：采用分子力学和量子化学从头计算方法，研究分析不同分子的电子结构与抗氧化活性关系．结果：生育酚的抗氧化活性与易释放活泼氢有关，活性大小与ＯＨ间电子集居数、前线轨道能级及反应终态能量下降值有关，各种生育酚模型分子的羟基ＯＨ间电子集居数排列顺序α＜γ≤β＜δ，与文献报道抗氧化活性的结论相一致．

Computation of Structure Activity and Design of Chalcone Derivatives

Based on the antitumor activity of chalcone derivatives and their structure, the structure-activity relationship of chalcone derivatives was analyzed by CoMFA (comparative molecular field analysis) method and then the 3D-QSAR (the three dimensional quantitative structures activity relationship) model was established. The analytical results showed that the model had good stability and prediction ability with cross-validated Q2 and non-cross-validated R2 values of 0.527 and 0.995, respectively. The contour map of the model explained the relationship between the structure of chalcone derivatives and antitumor activity, and could be analyzed to design antitumor chalcone derivatives. We designed some structure of chalcone derivatives and calculated their antitumor activity. In this paper, 24 chalcone derivatives were studied by CoMFA, 3D-QSAR, molecular design, which provided theoretical for designing good activities chalcone derivatives.

Correlation between Chromatograph Capacity Factors and Structural Parameters of Indole Derivatives

Sixteen indole derivatives have been computed at B3LYP/6-31 IG^＊＊ level using density functional theory （DFF）. Based on linear solvation energy theory, the structural parameters were employed to present correlation between the parameters of chromatograph capacity factor （CCF） and molecular structural parameters. As a result, the correlation equation of the reversed phased high performance liquid chromatograph capacity factor to the intercept lgk＇w and slope S of CCF were obtained, from which the correlation coefficients of lgk＇w to the structural parameters are r^2 = 0.9596 and q^2 = 0.9262. While the correlation coefficients of the parameter S r^2 q^2 with structures are = 0.9750 and = 0.9252. Moreover, the effect of water as solvent on the present two models was also considered using SCRF method, and the result shows that the predicting capacity of correlation equation of lgkw＇ increases, while that of the model for S decreases slightly. Both two correlation equations achieved in this work are more advantageous than those using theoretical descriptors from molecular connectivity indices.

Quantitative Structure-activity Relationship Models of Monomer Reactivity

The reactivity parameters,Q and e,in the Q-e scheme reflect the reactivities of a monomer(or a radical)in free-radical copolymerizations.By applying multiple linear regression(MLR)analysis,the optimal quantitative structure-activity relationship(QSAR)model for the reactivity parameter lnQ was developed based on five descriptors(NAF,NOF,EαLUMO,EβHOMO,and EβLUMO)and 69 monomers with the root mean square(rms)error of 0.61.The optimal MLR model of the parameter e obtained from five descriptors(TOcl,NpN,NSO,EαHOMO and DH)and 68 monomers produced rms error of 0.42.Compared with previous models,the two optimal MLR models in this paper show satisfactory statistical characteristics.The feasibility of combining 2D descriptors obtained from the monomers and 3D descriptors calculated from the radical structures(formed from monomers+H )to predict parameters Q and e has been demonstrated.

Molecular Structural Characterization and Quantitative Prediction of Reduced Ion Mobility Constants for Diversified Organic Compounds

Based on two-dimensional topological structures, a novel molecular electronegativity interaction vector with hybridization （MEHIV） was developed to describe atomic hybridization state in different molecular environments. Five quantitative models by MEHIV characterization and multiple linear regression modeling were successfully established to predict reduced ion mobility constants （Ko） of alkanes, aromatic hydrocarbons, fatty alcohols, fatty aldehydes and ketones and carboxylic esters. The correlation coefficients Roy by leave-one-out cross-validation are 0.792, 0.787, 0,949, 0.972 and 0.981, respectively, and the standard deviations SDcv are 0.067, 0.086, 0.064, 0.043 and 0.042, respectively. These results suggested that MEHIV is an excellent topological index descriptor with many advantages such as straightforward physicochemical meaning, high characterization competence, convenient expansibility and easy manipulation.

动态现场原位(operando)表征技术在多相催化反应中的应用与进展

动态现场原位(operando)表征是在接近过程工业反应条件下,揭示催化反应机理及工业催化剂结构演变的新兴动态结构解析技术。本文综述了operando表征技术在多相催化反应中的应用及发展趋势,从operando红外、operando拉曼、operando X射线衍射、operando穆斯堡尔谱、operando X射线吸收谱及operando X射线光电子能谱6个方面概述了operando技术的最新进展。此外,还介绍了正在兴起的operando联用技术,该技术综合多种operando技术为一体,能够在反应过程中对催化剂的结构全貌进行深度表征,实现工业催化剂的理性设计,将成为未来多相催化研究的重要手段。然而,目前operando技术的时间分辨率和空间分辨率仍需进一步提升,其巨大潜力依然有待开发。

QSRR Study on the Components of Styrax Japonicus Sieb Flowers Using Improved Molecular Electronegativity-distance Vector (I-MEDV)

Atoms in most organic molecules are often carbon,oxygen,nitrogen,sulfur,halogens,etc. Based on the three-dimensional structure of a molecule,a molecular structural characterization（MSC） method called improved molecular electronegativity-distance vector（I-MEDV） was developed. It was used to describe the structures of 37 compounds of styrax japonicus sieb flowers. Through multiple linear regression（MLR）,a QSRR model was built up. The correlation coefficient（R1） of the model was 0.980. Then,4 vectors were selected to build another model through the method of stepwise multiple regression（SMR） ,and the correlation coefficient（R2） of the model was 0.975. Moreover,all the two models were evaluated by performing the crossvalidation with the leave-one-out（LOO） procedure and the correlation coefficients（Rcv） were 0.948 and 0.968,respectively. The results show that the I-MEDV could successfully describe the structures of organic compounds. The stability and predictability of the models were good.

Operando拉曼光谱技术在铁基费托合成和二氧化碳加氢反应中的应用

催化剂是多相催化反应的核心,由于催化反应的复杂性,人类对于催化剂活性相的认知十分有限。反应过程中催化剂构-效关系的构建对于理解催化反应过程和改进催化剂至关重要,动态现场原位(Operando)技术能实时监测催化剂结构演变并在线检测反应产物,促进工业催化剂的理性设计。本文首先介绍了催化反应和动态现场原位表征技术的发展历史,并结合近期的研究进展,描述了Operando拉曼技术在铁基费托合成(Fischer-Tropsch synthesis(FTS))和二氧化碳加氢两种典型催化反应中的应用,展示了不同预处理和前驱体条件下,催化剂的结构演变过程及构-效关系。然而,目前Operando技术的时间分辨率和空间分辨率仍需进一步提升,此外,Operando技术在固液,气液催化反应中仍具有巨大的开发潜力。

Fragility Curves of Existing RC Buildings Based on Specific Structural Performance Levels

In seismic risk mitigation policies, fragility functions of existing buildings play a fundamental role. In this paper, a procedure to develop analytical fragility curves for Moment Resisting Frame Reinforced Concrete buildings is presented. The design of the selected building typologies was performed according to the codes at the time of construction using force-based methods and the state of the practice at the time of construction. A total of 216 building classes were defined, considering different ages, number of storeys, infill panels, plan dimensions, beam stiffness, and concrete strength. The investigated buildings can be considered low-engineered buildings, using no seismic codes or old seismic codes. The seismic capacity of the selected models representing the existing RC buildings has been evaluated through non-linear dynamic simulations. Seismic response has been analyzed, considering various peak and integral intensity measures and various response parameters, such as ductility demands and Interstorey Drift Ratio (IDR). A new relationship among structural performance, damage levels and interstorey drift ratios for each studied type is introduced, which is calibrated using the damage levels described in EMS98. It is important to highlight that in this study, different thresholds of IDR have been associated with different typologies, considering their different ductility member levels after their different structural responses. Fragility Curves (FCs) for the studied structural types are set up, developed and discussed.

Investigation on the differences of four flavonoids with similar structure binding to human serum albumin

Flavonoids are structurally diverse and the most ubiquitous groups of polyphenols distributed in the various plants,which possess intensive biological activities.In this study,the interaction mechanisms between four flavonoids containing one glucose unit with similar molecular weight isolated from the Tibetan medicinal herb Pyrethrum tatsienense,namely.apigenin-7-O-β-D-glucoside（1）,luteolin-7-O-β-D-glucoside（2）.quercetin-7-O-β-D-glucoside（3）.quercetin-3-O-β-D-glycoside（4）.and human serum albumin（HSA）,were investigated by fluorescence.UV-vis absorbance,circular dichroism,and molecular modeling.The effects of biological metal ions Mg2＋,Zn2＋,and Cu2＋ on the binding affinity between flavonoids and HSA were further examined.Structure-activity relationships of four flavonoids binding to HSA were discussed in depth and some meaningful conclusions have been drawn by the experiment data and theoretical simulation.In addition,an interesting phenomenon was observed that the microenvironment of the binding site I in HSA has hardly changed in the presence of 4 differentiating from the other three flavonoids on the basis of conformation investigations.

Structural Characterization and Retention Time Prediction for Components of Essential Oil of Meconopsis Integrifolia Flowers

A molecular structural characterization （MSC） method called reduced molecular electronegativity-distance vector （MEDVR） was used to describe the molecular structures of 55 components of meconopsis integrifolia flowers. By use of stepwise multiple regression （SMR） and partial least square （PLS） methods, a model with the correlation coefficient （R1） of 0.987 and the standard deviation （SD1） of 1.377 could be obtained. Then through multiple linear regression （MLR）, another model with the correlation coefficient （R2） of 0.989 and standard deviation （SD2） of 1.395 could be constructed. Furthermore, in virtue of variable screening by the stepwise multiple regression technique （SMR）, 8 vectors were selected to build up another model with its correlation coefficient （R3） and standard deviation （SD3） of 0.989 and 1.366, respectively. Then all the three models were evaluated by performing cross-validation with the leave-one-out （LOO） procedure, and the correlation coefficients （QCV） were 0.981, 0.976 and 0.979, respectively. The results show that the models constructed could provide estimation stability and favorable predictive ability.

Structural Characterization of Volatile Components of Rosa Banksiae Ait for Estimation and Prediction of Their Linear Retention Indices and Retention Times

The molecular electronegativity-distance vector （MEDV） was used to describe the molecular structure of volatile components of Rosa banksiae Ait, and QSRR model was built up by use of multiple linear regression （MLR）. Furthermore, in virtue of variable screening by the stepwise multiple regression technique, the QSRR models of 10 and 6 variables and linear retention index （LRI） 10, 7 and 6 varieables were built up by combinating MEDV with the Ultra2 column GC retention time （tR） of 53 volatile components of Rosa Banksiae Air. The multiple correlation coefficients （R） of modeling calculation values of QSRR model were 0.906, 0.906, 0.949, 0.943 and 0.949, respectively. The cross-verification multiple correlation coefficients （RCV） were 0.903, 0.904, 0.867, 0.901 and 0.904, respectively. The results show that the models constructed could provide estimation stability and favorable predictive ability.