Kinesin light chain 1 stabilizes insulin receptor substrate 1 to regulate the IGF-1-AKT signaling pathway during myoblast differentiation.

The IGF signaling pathway plays critical role in regulating skeletal myogenesis. We have demonstrated that KIF5B, the heavy chain of kinesin-1 motor, promotes myoblast differentiation through regulating IGF-p38MAPK activation. However, the roles of the kinesin light chain (Klc) in IGF pathway and myoblast differentiation remain elusive. In this study, we found that Klc1 was upregulated during muscle regeneration and downregulated in senescence mouse muscles and dystrophic muscles from mdx (X-linked muscular dystrophic) mice. Gain- and loss-of-function experiments further displayed that Klc1 promotes AKT-mTOR activity and positively regulates myogenic differentiation. We further identified that the expression levels of IRS1, the critical node of IGF-1 signaling, are downregulated in Klc1-depleted myoblasts. Coimmunoprecipitation study revealed that IRS1 interacted with the 88-154 amino acid sequence of Klc1 via its PTB domain. Notably, the reduced Klc1 levels were found in senescence and osteoporosis skeletal muscle samples from both mice and human. Taken together, our findings suggested a crucial role of Klc1 in the regulation of IGF-AKT pathway during myogenesis through stabilizing IRS1, which might ultimately influence the development of muscle-related disorders.

First-principles theory of atomic-scale friction explored by an intuitive charge density fluctuation surface.

Atomic-scale friction theory, and even superlubricity, is inseparable from charge redistribution, but lacks a bridge to establish the potential link between them. Here, we first report a quantized charge density fluctuation surface (CDFS) by assembling silicene/graphene and germanene/graphene heterostructures and their corresponding homogeneous bilayers for DFT calculations. By observing the PES morphology, we see that it exhibits a decrease in friction by more than two orders of magnitude. A crucial physical quantity controlling the friction was found to be the charge density fluctuation during the friction process via analyzing the CDFSs. Such CDFS holds a universal applicability in van der Waals materials, and is recommended to explore the friction cooperating with PES. This will be a new idea for exploring whether friction is related to electrical properties by defining the conversion factor K for a wide series of interactions, including metallic, covalent, and van der Waals bonding. In particular, the same conversion factor K exists for van der Waals bonding, and a mutual identification between the CDFS and PES can be achieved.

Quantifying Macroscopic Friction of Diamond-like Carbon Films by Microscopic Adsorption and Removal of Water Molecules.

The adsorption and desorption of water molecules, which affect the physical and chemical properties of the sliding interface, are critical for the friction behaviors of two solid contacts in atmosphere environment. The amount of water adsorbed on the open surface is a function of gas pressure according to an adsorption equation. However, for a confined sliding interface, the variation of surface fraction covered by gas molecules with water vapor pressure and its induced effects on friction have not been figured out. In this work, the macroscopic friction of diamond-like carbon (DLC) films in a water vapor atmosphere is quantified on the basis of microscopic adsorption and removal of water molecules. The studies correlate the fraction of water molecules adsorbed on the interface of self-mated DLC films with water vapor pressure to illustrate the direct relationship between friction coefficient and gas pressure by first-principles calculations and model fitting. The calculated results revealed that chemisorption and physisorption of water molecules occur on the surfaces of hydrogen-free DLC films (ta-C) and hydrogenated DLC films (HCF). Then, the relation between friction and gas pressure was built by employing a fractional coverage model based on the linear adsorption equation and gas removal. The obtained model agrees well with the typical experimental results about the steady-state friction coefficient of both highly hydrogenated DLC film (HCF) and tetrahedral amorphous carbon (ta-C) film during sliding at various water vapor pressures. In addition, it gave the curves of fractional surface coverage as a function of water vapor pressure. These results show that the frictional coefficient of DLC films could be predicted on the basis of fractional surface coverage as well as the intrinsic characters on surface chemistry. We suggest that the model may be thus extended to understand and predict the friction of DLC films under a specific gas pressure at a low load and speed.

Silver-Catalyzed Synthesis of Benzyl Ethers via Alkoxylation of Benzylic C(sp3 )-H Bonds.

Alkoxylation of benzylic C(sp3 )-H bonds has become one of the most important tools for the construction of benzyl ethers from feedstock chemicals. Herein, we reported a silver catalyzed alkoxylation of benzylic C(sp3 )-H bonds employing potassium persulfate as an oxidant at room temperature. This strategy showed good functional-group tolerance, site selectivity, and chemoselectivity. The reaction proceeded smoothly in the presence of various primary, secondary, and tertiary alcohol nucleophiles, affording corresponding benzyl ethers. Combined experimental studies provided mechanistic insights into the possible radical pathways. Furthermore, a possible mechanism was proposed for this method.

Copper-Catalyzed Asymmetric Cyanation of Propargylic Radicals via Direct Decarboxylation of Propargylic Carboxylic Acids.

Chiral propargylic cyanides are often used as small-molecule feedstocks for the introduction of chiral centers into various valuable products and complex molecules. Here, we have developed a highly atom-economical strategy for the chiral copper complex-catalyzed synthesis of chiral propargylic cyanides. Propargylic radicals can be smoothly obtained by direct decarboxylation of the propargylic carboxylic acids without preactivation. The reactions show excellent selectivity and functional group compatibility. Gram-scale reaction and several conversion reactions from chiral propargylic cyanide have demonstrated the synthetic value of this strategy.

Dual Photoredox/Nickel-Catalyzed Dehydrative Difluoroalkylation of Benzyl Alcohols for the Synthesis of Allylic gem-Difluorides.

A photoredox/Lewis acid cooperative catalytic system has been developed for the construction of Cvinyl-CRf bonds through the dehydrative difluoroalkylation of benzyl alcohols. A variety of allylic gem-difluorides could be obtained in moderate yields with good to excellent E/Z selectivity. In addition, several control experiments have been explored, and a possible mechanism was proposed for this process.

Copper-Catalyzed Enantioselective Decarboxylative Cyanation of Benzylic Acids Promoted by Hypervalent Iodine(III) Reagents.

Copper-catalyzed asymmetric radical cyanation reactions have emerged as a powerful strategy for rapid construction of α-chiral nitriles. However, the directly decarboxylative cyanation reactions of common alkyl carboxylic acids remain largely elusive. Herein, we report a protocol for copper-catalyzed direct and enantioselective decarboxylative cyanation of benzylic acids. The in situ activation of acid substrates by a commercially inexpensive hypervalent iodine(III) reagent promoted the yield of the alkyl radicals under mild reaction conditions without prefunctionalization. The structurally diverse chiral alkyl nitriles were produced in good yields with high enantioselectivities. In addition, the chiral products can be readily converted to other useful chiral compounds via further transformations.

Wear Estimation of DLC Films Based on Energy-Dissipation Analysis: A Molecular Dynamics Study.

This study employs the energy-dissipation method to analyze the tribological behaviors of diamond-like carbon (DLC) films through molecular dynamics simulation. It is found that at small load and sliding velocity, the variation trend of average friction force is only dependent on the number of interface bonds (or contact area). However, at large load and sliding velocity, the friction mechanism is not only related to the number of interface bonds but also related to the presence of the transfer layer. The elastic-plastic deformation mainly occurs in the early sliding stage, and a part of the stored elastic potential energy is dissipated by plastic potential energy or internal frictional heat. After the sliding stabilization, over 95% of the total frictional energy is dissipated by thermal conduction, and the rest is mostly dissipated by wear. The increase in load, velocity, and temperature cause more frictional energy dissipated by elastic-plastic deformation, atomic motion, and elastic deformation instead of thermal conduction, respectively. Finally, the wear rate obtained in this work is the same order of magnitude as the experiment. Generally, this work provides an effective atomic-scale method to comprehensively analyze the microscopic wear mechanism of materials.

Bio-Tribology and Corrosion Behaviors of a Si- and N-Incorporated Diamond-like Carbon Film: A New Class of Protective Film for Ti6Al4V Artificial Implants.

Ti6Al4V artificial implants are increasingly demanded for addressing human dysfunction caused by an aging population and major diseases. However, they are restricted due to the release of vanadium and aluminum ions in the process of corrosion and wear. This work is aimed to provide a protective film for Ti6Al4V artificial implants, and then, a Si-incorporated diamond-like carbon (Si-DLC) film and Si- and N-incorporated DLC (SiN-DLC) film were deposited on the surface of Ti6Al4V by plasma-enhanced chemical vapor deposition. Results suggest that the thickness of the as-deposited DLC film is approximately 2 µm, and the SiN-DLC film shows the lowest surface roughness (53.0 ± 3.6 nm) compared with the Ti6Al4V and DLC films. The above DLC film possesses high mechanical properties compared with Ti6Al4V, and the SiN-DLC film shows the best resistance to plastic deformation. In addition, the DLC film exhibits high adhesive strength (>13 N) with Ti6Al4V, which is a prerequisite for service in liquid environments. Whether in SBF solution or SBF + BSA solution, the friction coefficient and wear rate of the above DLC film are much lower than those of Ti6Al4V, and the SiN-DLC film displays the optimal tribological properties (0.072 and 1.82 × 10-7 mm3·N-1·m-1, respectively). Moreover, Si-DLC and SiN-DLC films possess similar corrosion resistance but are far better than Ti6Al4V. Cytotoxicity test results show that the SiN-DLC film can significantly improve cell viability and promote cell proliferation to a certain extent. Consequently, the SiN-DLC film is a protective film with more potential for artificial implants.

Correction: The corrosion behaviors of multilayer diamond-like carbon coatings: influence of deposition periods and corrosive medium.

[This corrects the article DOI: 10.1039/C6RA05527C.].

Correction: Corrosion and tribocorrosion performance of multilayer diamond-like carbon film in NaCl solution.

[This corrects the article DOI: 10.1039/C5RA21207C.].

Cu-Catalyzed Dehydrogenative Olefinsulfonation of Alkyl Arenes.

A copper-catalyzed reaction protocol for the dehydrogenation of ethylbenzenes into styrene derivatives has been developed. This reaction procedure proceeded well under mild reaction conditions, providing a practical and efficient strategy for the rapid assembly of biologically and pharmaceutically significant molecules, such as vinyl sulfone. Simple alkyl arenes were functionalized via consecutive ß-elimination in the presence of N-sulfonylbenzo[d]imidazole with broad substrate scope and good functional group tolerance.

Strain Effects of Vertical Separation and Horizontal Sliding in Commensurate Two-Dimensional Homojunctions.

Strain, as an economic yet controllable approach for structural modulation, frequently plays a vital role in the preparation and performance optimization of two-dimensional nanomaterials (TNMs). Here, utilizing first-principles simulations, the analysis of energetics shows that the biaxial stretching and compressing could facilitate the vertical separation and horizontal sliding in graphene (Gr/Gr), hexagonal boron nitride (h-BN/h-BN), and molybdenum disulfide (MoS2/MoS2) bilayers. The quantification of electron redistribution between layers confirmed that the shifts of interlayer charge density (ρinter-) and its relative values (Δρinter-) are responsible for the vertical separation and horizontal sliding facilitated by biaxial strain. More effortless horizontal sliding was enabled by a smoother potential energy surface because a smaller Δρinter- can be acquired under compression, whereas more effortless vertical separation followed a more vulnerable surface energy because a lower ρinter- occurs under tensile strain. The vertical and horizontal division of strain effect provides a novel idea for further understanding its pivotal roles in strain engineering of commensurate-contact TNMs, such as mechanical exfoliation and solid lubrication.

Tribochemistry of adaptive integrated interfaces at boundary lubricated contacts.

Understanding how an adaptive integrated interface between lubricant additives and solid contacts works will enable improving the wear and friction of moving engine components. This work represents the comprehensive characterization of compositional and structural orientation at the sliding interface from the perspective of surface/interface tribochemistry. The integrated interface of a lubricant additive-solid resulting from the friction testing of Graphite-like carbon (GLC) and PVD-CrN coated rings sliding against cast iron under boundary lubrication was studied. The results indicate that in the case of the CrN/cast iron pair the antiwear and friction behavior were very strongly dependent upon lubricant. In contrast, the tribology of the GLC surface showed a much lower dependence on lubrication. In order to identify the compounds and their distribution across the interface, x-ray microanalysis phase mapping was innovatively applied and the principle of hard and soft acids and bases (HSAB) to understand the behaviour. Phase mapping clearly showed the hierarchical interface of the zinc-iron polyphosphate tribofilm for various sliding pairs and different sliding durations. This interface structure formed between lubricant additives and the sliding surfaces adapts to the sliding conditions - the term adaptive interface. The current results help explain the tribology of these sliding components in engine.

Interface architecture for superthick carbon-based films toward low internal stress and ultrahigh load-bearing capacity.

Superthick diamond-like carbon (DLC) films [(Six-DLC/Siy-DLC)n/DLC] were deposited on 304 stainless steel substrates by using a plane hollow cathode plasma-enhanced chemical vapor deposition method. The structure was investigated by scanning electron microscopy and transmission electron microscopy. Chemical bonding was examined by Raman, Auger electron, and X-ray photoelectron spectroscopy techniques. Mechanical and tribological properties were evaluated using nanoindentation, scratch, interferometry, and reciprocating-sliding friction testing. The results showed that implantation of a silicon ion into the substrate and the architecture of the tensile stress/compressive stress structure decreased the residual stress to almost 0, resulting in deposition of (Six-DLC/Siy-DLC)n/DLC films with a thickness of more than 50 µm. The hardness of the film ranged from 9 to 23 GPa, and the adhesion strength ranged from 4.6 to 57 N depending on the thickness of the film. Friction coefficients were determined in three tested environments, namely, air, water, and oil. Friction coefficients were typically below 0.24 and as low as 0.02 in a water environment. The as-prepared superthick films also showed an ultrahigh load-bearing capacity, and no failure was detected in the reciprocating wear test with contact pressure higher than 3.2 GPa. Reasons for the ultrahigh load-bearing capacity are proposed in combination with the finite-element method.