The open-close mechanism of M2 channel protein in influenza A virus:A computational study on the hydrogen bonds and cation-π interactions among His37 and Trp41

The M2 protein from influenza A virus is a tetrameric ion channel. It was reported that the permeation of the ion channel is correlated with the hydrogen bond network among His37 residues and the cation-π interactions between His37 and Trp41. In the present study,the hydrogen bonding network of 4-methyl-imidazoles was built to mimic the hydrogen bonds between His37 residues,and the cation-π interactions between 4-methyl-imidazolium and indole systems were selected to represent the interac-tions between His37 and Trp41. Then,quantum chemistry calculations at the MP2/6-311G level were carried out to explore the properties of the hydrogen bonds and the cation-π interactions. The calcula-tion results indicate that the binding strength of the N-H···N hydrogen bond between imidazole rings is up to -6.22 kcal·mol-1,and the binding strength of the strongest cation-π interaction is up to -18.8 kcal·mol-1(T-shaped interaction) or -12.3 kcal·mol-1(parallel stacking interaction). Thus,the calcu-lated binding energies indicate that it is possible to control the permeation of the M2 ion channel through the hydrogen bond network and the cation-π interactions by altering the pH values.     

Study on the Cation-π Interactions between Ammonium Ion and Aromatic π Systems

The nature and strength of the cation-π interactions between NH4^＋ and toluene, p-cresol, or Me-indole were studied in terms of the topological properties of molecular charge density and binding energy decomposition. The results display that the diversity in the distribution pattern of bond and cage critical points reflects the profound influence of the number and nature of substituent on the electron density of the aromatic rings. On the other hand, the energy decomposition shows that dispersion and repulsive exchange forces play an important role in the organic cation （NH4^＋）-π interaction, although the electrostatic and induction forces dominate the interaction. In addition, it is intriguing that there is an excellent correlation between the electrostatic energy and ellipticity at the bond critical point of the aromatic π systems, which would be helpful to further understand the electrostatic interaction in the cation-π complexes.     

Research Progress of Regulation of Driving Forces in Short Peptide Supramolecular Self-Assembly北大核心CSCD

Some short peptides can spontaneously self-assemble into various nanostructures via the synergistic driving forces of non-covalent interactions. These non-covalent interactions,including electrostatic interaction,hydrogen bonding,aromatic interactions and other non-covalent interactions,are usually highly coupled together. Through rational sequence design and proper modification of short peptide molecules,the driving forces could be regulated purposively,and the nanostructures and morphologies of the self-assemblies could be controlled accordingly,and thus so as to achieve the fabrication of peptide-based supramolecular biomaterials and develop their functions. In this paper,the effects of hydrogen bonding,π-π stacking, electrostatic interaction,hydrophobic interaction,metal ion coordination and chiral center on the self-assembly behavior of peptide self-assembly have been reviewed. The driving force regulation strategies, including sequence design,pH and concentration adjustment and metal ion coordination,and the resulted nanostructures have also been discussed. We also make the outlooks on the development of peptide-based supramolecular biomaterials with specific functions in biomedicines and biocatalysis. © 2022, Science Press (China). All rights reserved.     

Terminal protection of small molecule-linked ssDNA-SWNT nanoassembly for sensitive detection of small molecule and protein interaction

The interactions between small molecules and proteins constitute a critical regulatory mechanism in many fundamental biological processes.A novel biosensing strategy has been developed for sensitive and selective detection of small molecule and protein interaction on the basis of terminal protection of small molecule-linked ssDNA-SWNT nanoassembly.The developed strategy is demonstrated using folate and its binding protein folate receptor(FR) as a model case.The results reveal the developed technique displays superb resistance to non-specific binding,very low detection limit as low as subnanomolar,and a wide dynamic range from 100 pmol/L to 500 nmol/L of FR.Thus,it may offer a simple,cost-effective,highly selective and sensitive platform for homogeneous fluorescence detection of small molecule-protein interaction and related biochemical studies.     

One-dimensional Chain Dibenzo-18-crown-6 Complex: [K(DB18-C-6)]_2[Pt(SCN)_6]·2H_2O·C_2H_4Cl_2 Assembled by Cation-π Interactions

IntroductionCation- π interactions have come to be appreci-ated as an important noncovalent binding force inmany areas of modern chemistry,such as materialdesign,molecular biology,host- guest and supra-molecular chemistry[1_ 3 ] .These interactions havebeen investigated in the gas phase[4] ,in aqueousmedia by using synthetic receptors[5,6] ,in a numberof protein systems[1,5,7] and in many metal complex-es provided by crystallographic studies[8_ 16] .Cations thatshow cation-π interactions,inc…     

Self-assembly of Bis[2-(2-hydroxyphenyl)-pyridine]Copper(Ⅱ) Induced by C-H…π and π…π Stacking Interaction

Introduction The control of molecular assembly in the solid state is an important theme of modern chemistry.It is in this regard that there is an activity in the area of supramolecular structures at present.The self-assembly of molecules can form well-defined supramolecular structures under the influence of drive forces such as hydrogen bonds[1-3],metal-ligand coordination bonds[4-6] and π…π stacking interactions[7-10].Word et al.have described the co-ordination chemistry of polydentate chelating ligands which contain mixed pyridine-phenol donor sets[11].Some unusual structures of transition metal pyridine-phenol complexes have been established in which non-covalent interactions such as hydrogen bonding and π…π stacking appear to play a dominant part.These observations suggest that it might be possible to construct supramolecular structures with a metal pyridine-phenol system.To explore this idea we have begun to investigate the self-assembly properties of metal pyridine-phenol complexes.Herein we present the self-assembly properties of Cu(pp)2[pp=2-(2-hydroxyphenol)-pyridine] under different conditions.     

Synthesis and Crystal Structure of an Ion-pair Supramolecular Associate 2,9-Diformyl- 1,10-phenanthrolinebis- （2,6-dimethylanil）cobalt（Ⅱ） Perchlorate

1 INTRODUCTION The well-defined supramolecular systems with infinite molecules assembled in the solids have at- tracted considerable attention in the fields of che- mical, biological and materials science[1～3], in which the intermolecular non-covalent weak forces have been mainly investigated and recognized as hydro- gen bonds and π-π stacking interactions[4]. In addi- tion to those weak interactions, the anion-cation in- teraction has also been studied in a few supramo- lecular species…     

Theoretical Investigation for Unexpected Transition Metal-π Interaction Enhanced Fluorescence in Cu-π-diborene

Unexpected transition metal(TM)-π interaction enhanced fluorescence in Cu-π-diborene complexes is a novel phenomenon compared with other metal enhanced fluorescence. In order to discover the mechanism, theoretical investigation was carried out for Cu-π-diborene as well as diborene. Simulation results show the main decay method in diborene and Cu-π-diborene are internal conversion(IC) and fluorescence(FL), respectively. TM-π interaction leads to larger HOMO-LUMO gap of Cu-π-diborene than that of the free diborene, which results in lower IC rates and makes them smaller than the FL rates. At the same time, ISC rates are always smaller than IC and FL rates, which cause enhanced fluorescence of Cu-π-diborene. More interestingly, even though Cu-π-diborene shows enhanced fluorescence, intersystem crossing(ISC) in Cu-π-diborene is enhanced from diborene. The theoretical analysis shows the competition among IC, FL and ISC is the key factor for TM-π interactions enhanced fluorescence, which also shows that cation-π complexes have potential to be used as luminescent probes.     

A new class of ion-ion interaction: Z-bond

The hydrogen-bond interactions in ionic liquids have been simply described by the conventional hydrogen-bond model of A–H···B. Coupling with the strong electrostatic force, however, hydrogen bond between the cation and anion shows particular features in the geometric, energetic, electronic, and dynamic aspects, which is inherently different from that of the conventional hydrogen bond. A general model could be expressed as +[A–H···B]-, in which A and B represent heavy atoms and "+" and "–" represent the charges of the cation containing A atom and anion containing B atom, respectively. Because the structure shows a "zig-zag" motif, this coupling interaction is defined here as the Z-bond. The new model could be generally used to describe the interactions in ionic liquids, as well as bio-systems involved in ions, ionic reaction, and ionic materials.     

Quasi-solid-state polymer plastic crystal electrolyte for subzero lithium-ion batteries

Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)have attracted considerable attention as solid-state electrolytes owing to their high ionic conductivities similar to those of liquid electrolytes,excellent contacts with the electrodes,and good mechanic properties.As a crucial property of a solid-state electrolyte,the ionic conductivity of the PPCE directly depends on the interactions between the constituent parts including the polymer,lithium salt,and SN.A few studies have focused on the effects of polymer–lithium–salt and polymer–SN interactions on the PPCE ionic conductivity.Nevertheless,the impact of the lithium–salt–SN combination on the PPCE ionic conductivity has not been analyzed.In particular,tuning of the lithium-salt–SN interaction to fabricate a subzero PPCE with a high low-temperature ionic conductivity has not been reported.In this study,we design and fabricate five PPCE membranes with different weight ratios of Li N(SO2 CF3)2(Li TFSI)and SN to investigate the effect of the Li TFSI–SN interaction on the PPCE ionic conductivity.The ionic conductivities of the five PPCEs are investigated in the temperature range of–20 to 60°C by electro-chemical impedance spectroscopy.The interaction is analyzed by Fourier-transform infrared spectroscopy,Raman spectroscopy,and differential scanning calorimetry.The Li TFSI–SN interaction significantly influences the melting point of the PPCE,dissociation of the Li TFSI salt,and thus the PPCE ionic conductivity.By tuning the Li TFSI–SN interaction,a subzero workable PPCE membrane having an excellent low-temperature ionic conductivity(6×10-4 S cm–1 at 0°C)is obtained.The electro-chemical performance of the optimal PPCE is evaluated by using a Li Co O2/PPCE/Li4 Ti5 O12 cell,which confirms the application feasibility of the proposed quasisolid-state electrolyte in subzero workable lithium-ion batteries.     

SYNERGISTIC INTERACTIONS ON PHENOL ADSORPTION FROM AQUEOUS SOLUTIONS BY POLYMERIC ADSORBENTS

In this paper, the adsorption behaviors of phenol on polymeric adsorbents (Amberlite XAD4, NDA101, and D301)were investigated in batch system at 293, 303, and 313K, respectively. As the results shown, the adsorption isotherms of phenol on all adsorbents can be well fitted by Langmuir and Freundlich equations, which indicate a favorable and exothermic process. The adsorption capacity on a newly developed aminated adsorbent, NDA101, on which adsorption could be achieved by both hydrogen bonding interaction and π-π interaction, are higher than that on a weak base adsorbent, D301, on which adsorption could be achieved by hydrogen bonding interaction only, and on a nonpolar adsorbent, XAD4, on which adsorption could be achieved by π-π interaction only. The results of this paper indicate that the synergistic effect of some weak interactions, which occur simultaneously would contribute more to the adsorption than that occur individually.     

The Behavior of Carbonized Polymer Dots at the Nano-Bio Interface and Their Luminescent Mechanism:A Physical Chemistry Perspective

Carbonized polymer dots(CPDs)have been widely applied in biomedical fields,such as imaging,diagnosis and drug delivery.Since the complex,non-equilibrated and dynamic nature of biological systems inevitably affect the predesigned properties of CPDs,then efficiency and ultimate outcome of CPDs in biological identity will be transformed by the ubiquitous nano-bio interactions.Herein,our recent progress about elucidating the behavior of CPDs at nano-bio interface from the perspective of physical chemistry has been summarized in the review,mainly at the bio-macromolecular,cellular membrane and cellular levels,which is crucial for characterize their relative cytotoxicity and clinical transformation.Moreover,we mainly focused on the quantitative relationship of nano-bio interactions between CPDs with biological identity and related thermodynamics parameters during this process is also obtained from advanced isothermal titration calorimetry technique.Finally,our recent study about the photoluminescence origin is also included in this review,which favors modulating the photoluminescence of CPDs.     

A laser light scattering study of the interaction between human serum albumin and ampicillin sodium

1 Introduction Studies on the interaction of the complexes formed between proteins and amphiphilic molecules in aque- ous solutions have become a new focus and great pro- gress has been made in recent years[1―5]. An under- standing of these systems is of great importance in many biological processes and clinical use of drugs. The globular anionic protein human serum albumin (HSA) is widely used as a protein model in many studies[1―4,6]. Its principal function is to transport fatty acids an…     

Pillararene-based fluorescent sensors for the tracking of organic compounds

Fluorescent chemosensors based on pillararene complexes represent a new, promising branch in sensor technology. Because of CH-π interactions, aliphatic chains are well suited for the columnar cavities of pillararenes and bulky or sheet-like(sub)structures can be arranged on the portals. Thus, pillararenes form versatile receptors and an alteration of the fluorescence behavior upon complexation ensures the function of these chemosensors as the reporter. Although this field of research exists only since a few years, remarkable chemosensors were developed for substances as diverse as medical drugs,biochemicals, herbicides and explosives.     

A Peptide Binder of E3 Ligase Adaptor SPOP Disrupts Oncogenic SPOP-Protein Interactions in Kidney Cancer Cells

The E3 ligase adaptor SPOP,overexpressed in the nucleus but frequently dislocated into the cytoplasm in all clear cell Renal Cell Carcinomas(ccRCC),serves as a regulatory hub to promote kidney cancer through the ubiquitination and degradation of multiple downstream cancer proteins.Recently,our identification of a selective small-molecule inhibitor of the SPOP-phosphatase and tensin homolog(PTEN)interaction has demonstrated that the oncogenic SPOP-protein interaction would be a druggable target specific to ccRCC therapy.To our knowledge,this is the first time such a small-molecule inhibitor has been developed.Herein,we have identified a peptide binder for the SPOP-MATH domain that disrupts the oncogenic SPOP-protein interactions in kidney cancer cells.Computational design and biophysical characterization yielded peptide Pep38 that binds to the MATH domain of SPOP and competes on PTEN-binding to SPOP in vitro.The X-ray complex structure reveals that the peptide binder features the following combination:one,a mimic of the native peptide binder and two,an additionalβ-strand motif in sequence,which could contribute to increased binding affinity.In order to improve cellular permeability,we fused Pep38 with the delivery peptide TAT to prepare peptide TAT38,which inhibits the endogenous substrate binding to SPOP and suppresses the proliferation of the ccRCC cells.Our identification of the peptide inhibitors for SPOP-protein interactions provides further validation that the oncogenic SPOP-signaling pathway in ccRCC could be a druggable target specifically applicable to the therapy of kidney cancers.     

Thiourea Based Tweezer Anion Receptors for Selective Sensing of Fluoride Ions

Three 3,3＇-di（4-substituted-phenyl）-1,1＇-isophthaloylbis（thiourea） compounds were designed as novel neutral anion receptors, and synthesized by simple steps in good yields. The single crystal structure of receptor 1 shows that a solvent molecule was captured by the host molecule through intermolecular hydrogen bonding. Moreover, it was self-assembled as a supramolecular system for the presence of abundant inter- and intramolecular hydrogen bonding and π-π interactions between phenyl groups. Their application as anion receptors has been examined by UV-Vis and ^1H NMR spectroscopy, showing that they had a higher selectivity for fluoride than other halides. The host and guest formed a 1 ： 1 stoichiometry complex through hydrogen bonding interactions in the first step, then following a process of deprotonation in presence of an excess of F^- in the solvent of DMF.     

Theoretical study of the intermolecular hydrogen bond interaction for furan-HCl and furan-CHCl_3 complexes

The importance of intermolecular interactions in biology and material science has prompted chemists to explore the nature of the variety of such interactions. The strongest of these interac-tions are the hydrogen bonds, which play an important role in determining the molecular confor-mation, crystal packing, and the structure of biological systems such as nucleic acids. Extensive experimental and theoretical efforts[1—5] have been devoted to the studies of this type of interac-tions, such as …     

Advances on supramolecular assembly of cyclometalated platinum(Ⅱ) complexes

Organoplatinum(Ⅱ) compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent approach to create well-ordered supramolecular architectures with tunable properties,which underpin the role of solvent-directed approach for the design of functional materials.In this minireview,the recent advances on supramolecular self-assembly of cyclometalated platinum(Ⅱ) complexes have been discussed.During the self-assembly process,non-covalent Pt-Pt and π-π interactions play crucial roles in controlling the structures and functions of the resulting assemblies.     

CLOUD POINT CURVES OF POLY(ETHYLENE GLYCOL)/POLY(PROPYLENE GLYCOL) MIXTURES AND THEIR THERMODYNAMIC EXPLANATION

In the study of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) mixtures not only a bimodal shape but also a reverse trend of the dependence on molecular weight of the cloud point curves were observed.This trend indicates that the miscibility of the studied mixtures decreases as the molecular weight of one component decreases. The excess volumes of the mixtures show that the interaction parameter between two components decreases at first and increases after passing a minimum as the concentration of one component increases. This supports the explanation of Koningsveld on the bimodal shape of cloud point curves. Based on a binary interaction model a formula was derived revealing that the interaction between PPG and the end group of PEG and the hydrogen bonding interaction between ether and hydroxy end group inner or inter PEG molecules are not favorable for mixing. The latter interaction is an "attractive" force in PEG molecules. The two interactions are responsible for the observed abnormal dependence.     

Structural Determination of Bis-histidinopeptide Zinc Complexes by 15N NMR (HMBC) Spectra

Polynitrogen receptors such as bis-histidine peptides possess strong ability to bind metals, which play much important roles in medicinal, bioinorganic, bioorganic, biomimetic and supramolecular chemistry. In order to investigate the interaction of these hosts with a variety of neutral, cationic and anionic guests, several techniques, for example, NMR,potentiometric tirations and monocrystal X-ray diffraction have been employed. Among them NMR is a powerful technique for unraveling the structure of polynitrogen receptors as long as they are in solution where the rapid tumbling of molecules averages out the anisotropies such as chemical shift and dipole-dipole interactions. General 1H NMR approach has been widely used for the study of host-guest interaction, but it is difficult for the accurate measurement in complexes structures, particularly metal complexes structures in which how the polynitrogen receptors bind metal, and which nitrogen binds metal and so on.