Huiling Zhao

Ab initio investigation of the first hydration shell of protonated glycine

The first hydration shell of the protonated glycine is built up using Monte Carlo multiple minimum conformational search analysis with the MMFFs force field. The potential energy surfaces of the protonated glycine and its hydration complexes with up to eight water molecules have been scanned and the energy-minimized structures are predicted using the ab initio calculations. First, three favorable structures of protonated glycine were determined, and the micro-hydration processes showed that water can significantly stabilize the unstable conformers, and then their first hydration shells were established. Finally, we found that seven water molecules are required to fully hydrate the first hydration shell for the most stable conformer of protonated glycine. In order to analyse the hydration process, the dominant hydration sites located around the ammonium and carboxyl groups are studied carefully and systemically. The results indicate that, water molecules hydrate the protonated glycine in an alternative dynamic hydration process which is driven by the competition between different hydration sites. The first three water molecules are strongly attached by the ammonium group, while only the fourth water molecule is attached by the carboxyl group in the ultimate first hydration shell of the protonated glycine. In addition, the first hydration shell model has predicted most identical structures and a reasonable accord in hydration energy and vibrational frequencies of the most stable conformer with the conductor-like polarizable continuum model.

Exploring the complex mechanical properties of xanthan scaffolds by AFM-based force spectroscopy

Summary The polysaccharide xanthan has been extensively studied owing to its potential application in tissue engineering. In this paper, xanthan scaffold structures were investigated by atomic force microscope (AFM) in liquid, and the mechanical properties of the complex xanthan structures were investigated by using AFM-based force spectroscopy (FS). In this work, three types of structures in the xanthan scaffold were identified based on three types of FS stretching events. The fact that the complex force responses are the combinations of different types of stretching events suggests complicated intermolecular interactions among xanthan fibrils. The results provide crucial information to understand the structures and mechanical properties of the xanthan scaffold.

Direct force producing uniform ultra-thin chitosan films by atomic force microscopy

Biopolymer chitosan plays an important role in functional nanomaterials, tissue engineering and other biological applications. Chitosan thin films have also been involved in many optical phenomena in living organisms, which potentially allows the use of chitosan for optical applications. However, it is rather difficult to produce uniform thin chitosan films because of its intrinsic viscoelasticity. Here we report the fabrication of uniform ultra-thin chitosan films with a thickness of several nanometres using a two-step physical approach with the help of spin coating and mechanical manipulation.

Investigation of the non-covalent interactions of molecular self-assembly by scanning tunneling microscopy using the association of aromatic structures in pyrene-4,5,9,10-tetraone and phenanthrene-9,10-dione molecules

The self-assembled molecular monolayers of aromatic molecules (pyrene-4,5,9,10-tetraone (PT) and phenanthrene-9,10-dione (PD)) were investigated at the liquid/solid (1-phenyloctane/graphite) interface using scanning tunneling microscopy (STM). High resolution STM images revealed that PT tended to build a chevron pattern with individual peanut-shaped molecule; moreover, PD was apt to form a simple linear chain with single pearl-like molecule. Density functional theory (DFT) calculations employing the state-of-the art method of PBE + vdWsurf revealed that the hydrogen bonding from molecule–molecule interactions (PT–PT, PD–PD) and van der Waals (vdW) forces from building molecule–substrate (PT–graphite, PD–graphite) interactions played noticeable roles in the construction of these supramolecular architectures. By comparing the chemical structural differences between these two types of molecular building blocks, this study concisely and explicitly demonstrates that the advantages, such as structural symmetry and functional groups, possessed by building molecules promote the efficient synergy of multiple intermolecular non-covalent interactions and the feasible self-assembly of different supramolecular monolayers on diverse surfaces.

Nanomechanics of phospholipid LB film studied layer by layer with AFM

BackgroundPhospholipid, a main component of cell membrane, has been explored as a model system of the cell membrane and temporary scaffold materials in recent studies. The mechanical properties of phospholipid layers are essentially interesting since it is involved in several biological processes.ResultsHere, the nanomechanical properties such as indentation force, adhesion force and DMT (Derjaguin-Müller-Toporov) modulus of 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) Langmuir-Blodgett (LB) films were analyzed layer by layer with Atomic Force Microscope (AFM) under deionized water condition.ConclusionsThe penetration distances in the indentation force curves are equal to the thicknesses of phospholipid films, and the yield forces of DSPC LB films in deionized water are smaller than that of similar lipid films in buffered solutions due to the influence of ions. Moreover, the DMT modulus of upper layer DSPC LB film is different from that of monolayer DSPC LB film due to the influence of their different substrates. Our results suggest that environment such as surrounding ions and substrate will strongly influence the measured nano-mechanical properties of the lipid bilayer, especially that of the down layer.Graphical AbstractA process about the exploration of nanomechanics of DSPC LB film.

Characterization of Inter- and Intramolecular Interactions of Amyloid Fibrils by AFM-Based Single-Molecule Force Spectroscopy

Amyloids are fibrous protein aggregates defined by shared specific structural features. Abnormal accumulation of amyloid in organs leads to amyloidosis, which results in various neurodegenerative diseases. Atomic force microscopy (AFM) has proven to be an excellent tool investigating amyloids; it has been extensively utilized to characterize its morphology, assembly process, and mechanical properties. This review summarizes studies which applied AFM to detect the inter- and intramolecular interactions of amyloid fibrils and classified the influencing factors of amyloid’s nanomechanics in detail. The characteristics of amyloid fibrils driven by inter- and intramolecular interactions, including various morphologies of amyloid fibrils, self-assembly process, and the aggregating pathway, are described. Successful examples where AFM provided abundant information about inter- and intramolecular interactions of amyloid fibrils in different environments are presented. Direct force measurement of intra- or intermolecular interactions utilizing an AFM-based tool, single-molecular force spectroscopy (SMFS), is introduced. Some mechanical information such as elasticity, adhesiveness, and strength was obtained by stretching amyloid fibrils. This review helps researchers in understanding the mechanism of amyloidogenesis and exploring the properties of amyloid using AFM techniques.

Atomic Force Microscopy Based Tip-Enhanced Raman Spectroscopy in Biology

Most biological phenomena occur at the nanometer scale, which is not accessible by the conventional optical techniques because of the optical diffraction limitation. Tip-enhanced Raman spectroscopy (TERS), one of the burgeoning probing techniques, not only can provide the topography characterization with high resolution, but also can deliver the chemical or molecular information of a sample beyond the optical diffraction limitation. Therefore, it has been widely used in various structural analyses pertaining to materials science, tissue engineering, biological processes and so on. Based on the different feedback mechanisms, TERS can be classified into three types: atomic force microscopy based TERS system (AFM-TERS), scanning tunneling microscopy based TERS system (STM-TERS) and shear force microscopy based TERS system (SFM-TERS). Among them, AFM-TERS is the most widely adopted feedback system by live biosamples because it can work in liquid and this allows the investigation of biological molecules under native conditions. In this review, we mainly focus on the applications of AFM-TERS in three biological systems: nucleic acids, proteins and pathogens. From the TERS characterization to the data analysis, this review demonstrates that AFM-TERS has great potential applications to visually characterizing the biomolecular structure and crucially detecting more nano-chemical information of biological systems.

Dual-delivery of FGF-2/CTGF from Silk Fibroin/PLCL-PEO Coaxial Fibers Enhances MSC Proliferation and Fibrogenesis

The success of mesenchymal stem cell transplantation is highly dependent on their survival and controlled fate regulation. This study demonstrates that dual-delivery of connective tissue growth factor (CTGF) and fibroblast growth factor 2 (FGF-2) from a core-shell fiber of Silk Fibroin/poly(L-lactic acid-co-ε-caprolactone)-polyethylene oxide (SF/PLCL-PEO) enhanced fibrogenic lineage differentiation of MSCs. The core-shell structure was confirmed by transmission electron microscopy (TEM), fluorescence microscopy and attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy. A sequential release of FGF-2 and CTGF was successfully achieved in this manner. FGF-2 plays an important role in stem cell proliferation and, meanwhile when accompanied with CTGF, has a slightly additive effect on fibrogenic differentiation of MSCs, whereas CTGF promotes fibrogenesis and alleviates osteogenesis, chondrogenesis and adipogenesis.

Investigating the Co-Adsorption Behavior of Nucleic-Acid Base (Thymine and Cytosine) and Melamine at Liquid/Solid Interface

The co-adsorption behavior of nucleic-acid base (thymine; cytosine) and melamine was investigated by scanning tunneling microscopy (STM) technique at liquid/solid (1-octanol/graphite) interface. STM characterization results indicate that phase separation happened after dropping the mixed solution of thymine-melamine onto highly oriented pyrolytic graphite (HOPG) surface, while the hetero-component cluster-like structure was observed when cytosine-melamine binary assembly system is used. From the viewpoints of non-covalent interactions calculated by using density functional theory (DFT) method, the formation mechanisms of these assembled structures were explored in detail. This work will supply a methodology to design the supramolecular assembled structures and the hetero-component materials composed by biological and chemical compound.