Charge Redistribution in Mechanochemical Reactions for Solid Interfaces.

Mechanochemical strategies are widely used in various fields, ranging from friction and wear to mechanosynthesis, yet how the mechanical stress activates the chemical reactions at the electronic level is still open. We used first-principles density functional theory to study the rule of the stress-modified electronic states in transmitting mechanical energy to trigger chemical responses for different mechanochemical systems. The electron density redistribution among initial, transition, and final configurations is defined to correlate the energy evolution during reactions. We found that stress-induced changes in electron density redistribution are linearly related to activation energy and reaction energy, indicating the transition from mechanical work to chemical reactivity. The correlation coefficient is defined as the term "interface reactivity coefficient" to evaluate the susceptibility of chemical reactivity to mechanical action for material interfaces. The study may shed light on the electronic mechanism of the mechanochemical reactions behind the fundamental model as well as the mechanochemical phenomena.

Single-Chain Inherent Elasticity of Macromolecules: From Concept to Applications.

"The Tao begets the One. One begets all things of the world." These words of wisdom from Tao Te Ching are of great inspiration to scientists in polymer materials science and engineering: The "One" means an individual polymer chain while polymer materials consist of numerous chains. The understanding of the single-chain mechanics of polymers is crucial for the bottom-up rational design of polymer materials. With a backbone and side chains, a polymer chain is more complex than a small molecule. Moreover, an individual polymer chain is usually placed in a complicated environment (such as solvent, cosolute, and solid surface), which significantly affects the behaviors of the chain. With all these factors, it is hard to fully understand the elastic behaviors of polymers. Herein, we will first introduce the concept of the single-chain inherent elasticity of polymers, which is a fundamental property determined by the polymer backbone. Then, the applications of inherent elasticity in quantifying the effects of side chains and surrounding environment will be summarized. Finally, the challenges in related fields at present and potential research directions in the future will be discussed.

Crystalline Unipolymer Monolayer with High Modulus and Conductivity.

The synthesis of crystalline polymer with a well-defined orientated state and a two-dimensional crystalline size beyond a micrometer will be essential to achieve the highest physical feature of polymer material but remain challenging. Herein, we show the synthesis of the crystalline unipolymer monolayer with an unusual ultrahigh modulus that is higher than the ITO substrate and high conductance by simultaneous electrosynthesis and manipulation. We find that the polymer monolayer has fully extended in the vertical and unidirectional orientation, which is proposed to approach their theoretically highest density, modulus, and conductivity among all aggregation formations of the current polymer. The modulus and current density can reach 40 and 1000 times higher than their amorphous counterpart. It is also found that these monolayers exhibit the bias- and length-dependent multiple charge states and asymmetrically negative differential resistance (NDR) effect, indicating that this unique molecular tailoring and ordering design is promising for multilevel resistive memory devices. Our work demonstrates the creation of a crystalline polymer monolayer for approaching the physical limit of polymer electronic materials and also provides an opportunity to challenge the synthetically iterative limit of an isolated ultra-long polymer.

Environment-dependent single-chain mechanics of synthetic polymers and biomacromolecules by atomic force microscopy-based single-molecule force spectroscopy and the implications for advanced polymer materials.

"The Tao begets the One. One begets all things of the world." This quote from Tao Te Ching is still inspiring for scientists in chemistry and materials science: The "One" can refer to a single molecule. A macroscopic material is composed of numerous molecules. Although the relationship between the properties of the single molecule and macroscopic material is not well understood yet, it is expected that a deeper understanding of the single-chain mechanics of macromolecules will certainly facilitate the development of materials science. Atomic force microscopy-based single-molecule force spectroscopy (AFM-SMFS) has been exploited extensively as a powerful tool to study the single-chain behaviors of macromolecules. In this review, we summarize the recent advances in the emerging field of environment-dependent single-chain mechanics of synthetic polymers and biomacromolecules by means of AFM-SMFS. First, the single-chain inherent elasticities of several typical linear macromolecules are introduced, which are also confirmed by one of three polymer models with theoretical elasticities of the corresponding macromolecules obtained from quantum mechanical (QM) calculations. Then, the effects of the external environments on the single-chain mechanics of synthetic polymers and biomacromolecules are reviewed. Finally, the impacts of single-chain mechanics of macromolecules on the development of polymer science especially polymer materials are illustrated.

Inspecting fluctuation and coordination around chromophore inside green fluorescent protein from water to nonpolar solvent.

Green fluorescent protein (GFP) is a widely used biomarker that demands systematical rational approaches to its structure function redesign. In this work, we mainly utilized atomistic molecular dynamics simulations to inspect and visualize internal fluctuation and coordination around chromophore inside GFP, from water to nonpolar octane solvent. We found that GFP not only maintains its ß-barrel structure well into the octane, but also sustains internal residue and water coordination to position the chromophore stably while suppress dihedral fluctuations of the chromophore, so that functional robustness of GFP is achieved. Our accompanied fluorescence microscope measurements accordingly confirmed the GFP functioning into the octane. Furthermore, we identified that crucial water sites inside GFP along with permeable pores on the ß-barrel of the protein are largely preserved from the water to the octane solvent, which allows sufficiently fast exchanges of internal water with the bulk or with the water layer kept on the surface of the protein. By additionally pulling GFP from bulk water to octane, we suggest that the GFP function can be well maintained into the nonpolar solvent as long as, first, the protein does not denature in the nonpolar solvent nor across the polar-nonpolar solvent interface; second, a minimal set of water molecules are in accompany with the protein; third, the nonpolar solvent molecules may need to be large enough to be nonpermeable via the water pores on the ß-barrel.

Force-Induced Transition of π-π Stacking in a Single Polystyrene Chain.

Although π-π interactions have been studied for several decades, the quantification of the strength of π-π interactions in a macromolecule remains a big challenge. Herein, we utilize single-molecule atomic force microscopy and steered molecular dynamics simulations to study the π-π interactions in polystyrene (PS). It is found that in high vacuum, the single-chain mechanics of PS differs largely from that of polyethylene (PE). Accordingly, the strength of intrachain π-π interactions in PS is estimated to be 0.7 kcal/(mol stack), which is much lower than that in a small-molecule system (benzene dimer, 2-3 kcal/(mol stack)). Further study shows that in high vacuum, there are two types of π-π stacking in the single PS chain, i.e., the every-other-moiety (E) type and the adjacent-moiety (A) type. Upon force stretching, a transition from E-type to A-type π-π stacking can be observed.

Towards Unveiling the Exact Molecular Structure of Amorphous Red Phosphorus by Single-Molecule Studies.

Since the discovery of amorphous red phosphorus (a-red P) in 1847, many possible structures have been proposed. However, the exact molecular structure has not yet been determined because of its amorphous nature. Herein several methods are used to investigate basic properties of a-red P. Data from scanning tunneling microscopy (STM) and gel permeation chromatography (GPC) confirm that a-red P is a linear inorganic polymer with a broad molecular weight distribution. The theoretical single-molecule elasticities of the possible a-red P structures are obtained by quantum mechanical (QM) calculations. The experimental single-molecule elasticity of a-red P measured by single-molecule AFM matches with the theoretical result of the zig-zag ladder structure, indicating that a-red P may adopt this structure. Although this conclusion needs further validation, this fundamental study represents progress towards solving the structure of a-red P. It is expected that the strategy utilized in this work can be applied to study other inorganic polymers.

Supramolecular Chemistry and Mechanochemistry of Macromolecules: Recent Advances by Single-Molecule Force Spectroscopy.

Atomic force spectroscopy (AFM)-based single-molecule force spectroscopy (SMFS) was invented in the 1990s. Since then, SMFS has been developed into a powerful tool to study the inter- and intra-molecular interactions of macromolecules. Using SMFS, a number of problems in the field of supramolecular chemistry and mechanochemistry have been studied at the single-molecule level, which are not accessible by traditional ensemble characterization methods. In this review, the principles of SMFS are introduced, followed by the discussion of several problems of contemporary interest at the interface of supramolecular chemistry and mechanochemistry of macromolecules, including single-chain elasticity of macromolecules, interactions between water and macromolecules, interactions between macromolecules and solid surface, and the interactions in supramolecular polymers.

Effects of Water on the Single-Chain Elasticity of Poly(U) RNA.

Water, the dominant component under the physiological condition, is a complicated solvent which greatly affects the properties of solute molecules. Here, we utilize atomic force microscope-based single-molecule force spectroscopy to study the influence of water on the single-molecule elasticity of an unstructured single-stranded RNA (poly(U)). In nonpolar solvents, RNA presents its inherent elasticity, which is consistent with the theoretical single-chain elasticity calculated by quantum mechanics calculations. In aqueous buffers, however, an additional energy of 1.88 kJ/mol·base is needed for the stretching of the ssRNA chain. This energy is consumed by the bound water rearrangement (Ew) during chain elongation. Further experimental results indicate that the Ew value is uncorrelated to the salt concentrations and stretching velocity. The results obtained in an 8 M guanidine·HCl solution provide more evidence that the bound water molecules around RNA give rise to the observed deviation between aqueous and nonaqueous environments. Compared to synthetic water-soluble polymers, the value of Ew of RNA is much lower. The weak interference of water is supposed to be the precondition for the RNA secondary structure to exist in aqueous solution.

Why a lotus-like superhydrophobic surface is self-cleaning? An explanation from surface force measurements and analysis.

The unique self-cleaning feature of the lotus-like superhydrophobic (SH) surface attracted worldwide interest in recent years. However, the mechanism of the self-cleaning phenomena remains unclear. Here, we attempt to provide a comprehensive understanding of why self-cleaning of the particles with a broad range of size can be realized on the lotus-like SH surfaces. After measurements and analysis of the force involved at the interface, we conclude that there are four main preconditions for self-cleaning: (1) contact angle (CA) > 90°, (2) low enough sliding angle, (3) low enough adhesion force, and (4) proper particle size. However, as far as the lotus-like SH surface and typical dust are concerned, all the preconditions will be satisfied automatically. We also observe that the particles with a broad range of size (from submicron level to the millimeter level) and density (virtually no limit) can be driven by a water droplet on the lotus-like SH surface. This interesting finding may be helpful for the design of novel engineering system at the micron-millimeter scale in the future.

Single-chain mechanics of poly(N,N-diethylacrylamide) and poly(N-isopropylacrylamide): comparative study reveals the effect of hydrogen bond donors.

The single-chain mechanics of two similar thermosensitive polymers, poly(N,N-diethylacrylamide) (PDEAM) and poly(N-isopropylacrylamide) (PNIPAM), have been studied by atomic force microscopy-based single-molecule force spectroscopy (SMFS). In a typical nonpolar organic solvent, octane, both of the polymers show the same inherent elasticity, although they have different substitutional groups. However, the mechanics of the two polymers presents large differences in water. The energies needed for the rearrangement of the bound water during elongation at room temperature are estimated by the SMFS method at the single-chain level, which is ~1.13 ± 0.10 and ~5.19 ± 0.10 kJ/mol for PDEAM and PNIPAM, respectively. In addition, PNIPAM shows a temperature-dependent single-chain mechanics when the temperature is increased across the lower critical solution temperature (LCST), while PDEAM does not. These differences observed in aqueous solution originate from the different structures of the two polymers. With a hydrogen bond donor in the amide group, PNIPAM will be more hydrated when T < LCST. When T > LCST, PNIPAM will have larger changes in both conformation and hydration. These findings also suggest that PNIPAM is a good candidate for a thermo-driven single-molecule motor, while PDEAM is not.

Inherent stretching elasticity of a single polymer chain with a carbon-carbon backbone.

We study the single-chain elasticities of three kinds of neutral polymers with a carbon-carbon (C-C) backbone by atomic force microscopy-based single-molecule force spectroscopy in a nonpolar solvent (octane), aiming at measuring the inherent chain elasticity of this very important class of polymers. The finding that the single-chain elasticities of all three polymers in octane are virtually identical in the entire force region implies that the side chains of the polymers have no detectable effects on the single-chain elasticity. By utilizing the single-chain elasticity from quantum mechanics calculations, the freely rotating chain model can provide the best fitting curve when each C-C bond is set to be the rotating unit. Although there are some exceptions when the side chain is very huge, our work provides a general result for the inherent elasticity of single neutral flexible polymer chains with C-C backbones.

Emulating Titin by a Multidomain DNA Structure.

Titin, a giant protein containing multiple tandem domains, is essential in maintaining the superior mechanical performance of muscle. The consecutive and reversible unfolding and refolding of the domains are crucial for titin to serve as a modular spring. Since the discovery of the mechanical features of a single titin molecule, the exploration of biomimetic materials with titin-emulating modular structures has been an active field. However, it remains a challenge to prepare these modular polymers on a large scale due to the complex synthesis process. In this study, we propose modular DNA with multiple hairpins (MH-DNA) as the fundamental block for the bottom-up design of advanced materials. By analyzing the unfolding and refolding dynamics of modular hairpins by atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS), we find that MH-DNA shows comparable stability to those of polyproteins like titin. The unique low hysteresis of modular hairpin makes it an ideal molecular spring with remarkable mechanical efficiency. On the basis of the well-established DNA synthesis techniques, we anticipate that MH-DNA can be used as a promising building block for advanced materials with a combination of superior structural stability, considerable extensibility, and high mechanical efficiency.

Nanoscopic Characterization Reveals that Bulk Amorphous Elementary Boron Is Composed of a Ladder-like Polymer with B4 as the Structural Unit.

As the initially discovered allotrope of boron, amorphous elementary boron (AE-B) has been reported for more than two centuries. Several possible structures of AE-B have been proposed during the past decades. Due to its noncrystalline nature, however, the structure of AE-B has not yet been determined. We notice that AE-B can be dissolved in organic solvents, although the solubility is very low. After surface adsorption from solution, the individual or the self-assembled structure of AE-B molecules can be characterized at the single-molecule or nanoscopic level, which may be helpful to reveal the molecular structure of AE-B. Atomic force microscopy (AFM) imaging shows that AE-B is a chain-like molecule with a thickness (or height) of 0.17 ± 0.01 nm, which agrees well with the diameter of a B atom, demonstrating that the structure of an AE-B molecule contains only one layer of B atoms. Results from high-resolution transmission electron microscopy (HRTEM) indicate that AE-B molecules can be self-assembled into a nanosheet with parallel lines. The width of each line is 0.27 nm, and the periodical length along the chain axial direction is 0.32 ± 0.01 nm. These results indicate that AE-B is composed of a ladder-like inorganic polymer with B4 as the structural unit. This conclusion is supported by the single-chain elasticity obtained by single-molecule AFM and quantum mechanical calculations. We expect that this fundamental study is not only an ending of the two-century-old scientific mystery but also the beginning of the research and applications of AE-B (ladder B) as a polymeric material. The research strategy may be also used to study other amorphous inorganic materials.

Unexpected temperature-dependent single chain mechanics of poly(N-isopropyl-acrylamide) in water.

Poly(N-isopropyl-acrylamide) (PNIPAM) is a paradigm thermally sensitive polymer, which has a lower critical solution temperature (LCST) of ~32 °C in water. Herein by AFM-based single molecule force spectroscopy (SMFS), we measured the single chain elasticity of PNIPAM across the LCST in water. Below LCST, the force curves obtained at different temperatures have no remarkable difference; while above LCST, an unexpected temperature dependent elasticity is observed, mainly in the middle force regime. We found that 35 °C is a turning point of the variation: from 31 to 35 °C, the middle parts of the force curves drop gradually, whereas from 35 to 40 °C, the middle parts rise gradually. A possible mechanism for the unexpected temperature dependent mechanics is proposed. The single chain contraction against external force upon heating from 35 to 40 °C may cast new light on the design of molecular devices that convert thermal energy to mechanical work.

Single-chain polymers achieved from radical polymerization under single-initiator conditions.

Radical polymerization from a single initiator molecule in a microenvironment is a nearly ideal system in which bimolecular termination, solution concentration, and viscosity changes could be neglected. In this study, we provide two facile methods of preparing polymers via atom-transfer radical polymerization (ATRP) under single-initiator conditions: tether initiators on planar substrates at superlow density through mixed self-assembled monolayers (SAMs) and encapsulated single initiators in microfluidic droplets. The molecular weight (MW) of the resultant polymers characterized by atomic force microscope-based single-molecule force spectroscopy (AFM-based SMFS) showed that the single-chain ATRP had an extraordinarily faster chain propagation rate (2 unit/s) on planar substrates and gave polymers with much higher MWs (10(5)-10(6) g/mol) than those obtained from traditional ATRP (10(3)-10(5) g/mol). The former method offered a general platform for single-chain polymer synthesis and investigation, and the latter could be amplified to obtain abundant single-chain polymers with ultrahigh molecular weight (UHMW) for commercial applications.

The possible roles of water in the prebiotic chemical evolution of DNA.

There is no doubt that water is pivotal to life. Yet, as the emergence of life is still a big challenge in science, the detailed involvement of water in that process is not well recognized. Following the clues provided by recent single-molecule studies on DNA, we attempt to elucidate the possible roles of water in the prebiotic chemical evolution. Water has long been recognized as an important reactant in the Miller-Urey experiment and then as the only solvent of the primitive soup. Besides that, water also played a vital role in the prebiotic chemical evolution: water is the important criterion in the combinatorial library screening for self-assembling macromolecules. With this notion, the uniformity of biochemistry for all terrestrial life may be explained. A possible roadmap from the inorganic world to the origin of life is also discussed.

Superstretchable Dynamic Polymer Networks.

Superstretchable materials have many applications in advanced technological fields but are difficult to stretch to more than 1000× their original length. A superstretchable dynamic polymer network that can be stretched to 13 000× its original length is designed. It is revealed that superstretchability of the polymer network is derived from the synergistic effect of two different types of dynamic bonds, including a small number of strong dynamic imine bonds to maintain the network integrity during stretching and a large number of weak ionic hydrogen bonds to dissipate energy. This approach provides new insights into the design of superstretchable polymers.

Effects of Water Content of the Mixed Solvent on the Single-Molecule Mechanics of Amylose.

It is generally recognized that water is deeply involved in the structures and functions of DNA and proteins. For polysaccharides, however, the role of water remains unclear. Due to the force-induced conformational transition of the sugar rings, a fingerprint plateau can be observed in the single-chain force-extension (F-E) curves of amylose and some other polysaccharides in aqueous solutions. In this study, the effects of water content of the mixed solvents on the fingerprint plateau of amylose are explored by single-molecule AFM. The experimental results obtained in a series of water/alcohol mixed solvents clearly show that both the appearance and the fingerprint plateau height in the F-E curves of amylose are dependent on the water content. Since water is a good solvent for amylose but alcohols are not, the higher water content of a mixed solvent corresponds to a better solvent quality. Thus, the observed results can be associated with the solvent quality to amylose. The present study implies that water is not only a solvent but also an active constituent in the amylose solution.

Double-stranded DNA dissociates into single strands when dragged into a poor solvent.

DNA displays a richness of biologically relevant supramolecular structures, which depend on both sequence and ambient conditions. The effect of dragging double-stranded DNA (dsDNA) from water into poor solvent on the double-stranded structure is still unclear because of condensation. Here, we employed single molecule techniques based on atomic force microscopy and molecular dynamics (MD) simulations to investigate the change in structure and mechanics of DNA during the ambient change. We found that the two strands are split apart when the dsDNA is pulled at one strand from water into a poor solvent. The findings were corroborated by MD simulations where dsDNA was dragged from water into poor solvent, revealing details of the strand separation at the water/poor solvent interface. Because the structure of DNA is of high polarity, all poor solvents show a relatively low polarity. We speculate that the principle of spontaneous unwinding/splitting of dsDNA by providing a low-polarity (in other word, hydrophobic) micro-environment is exploited as one of the catalysis mechanisms of helicases.