Nonlinear Relaxation Dynamics in Elastic Networks and Design Principles of Molecular Machines

Analyzing nonlinear conformational relaxation dynamics in elastic networks corresponding to two classical motor proteins, we find that they respond by well-defined internal mechanical motions to various initial deformations and that these motions are robust against external perturbations. We show that this behavior is not characteristic for random elastic networks. However, special network architectures with such properties can be designed by evolutionary optimization methods. Using them, an example of an artificial elastic network, operating as a cyclic machine powered by ligand binding, is constructed.Comment: 12 pages, 9 figure

Stiction, Adhesion Energy and the Casimir Effect in Micromechanical Systems

We measure the adhesion energy of gold using a micromachined doubly-clamped beam. The stress and stiffness of the beam are characterized by measuring the spectrum of mechanical vibrations and the deflection due to an external force. To determine the adhesion energy we induce stiction between the beam and a nearby surface by capillary forces. Subsequent analysis yields a value $\gamma =0.06$ J/m$^{2}$ that is a factor of approximately six smaller than predicted by idealized theory. This discrepancy may be resolved with revised models that include surface roughness and the effect of adsorbed monolayers intervening between the contacting surfaces in these mesoscopic structures.Comment: RevTex, 4 pages, 4 eps figure

Observation of Spin-Dependent Charge Symmetry Breaking in ΛN\Lambda N Interaction: Gamma-Ray Spectroscopy of Λ4^4_{\Lambda }He

The energy spacing between the ground-state spin doublet of $^4_\Lambda$He(1$^+$,0$^+$) was determined to be $1406 \pm 2 \pm 2$ keV, by measuring $\gamma$ rays for the $1^+ \to 0^+$ transition with a high efficiency germanium detector array in coincidence with the $^4$He$(K^-,\pi^-)$ $^4_\Lambda$He reaction at J-PARC. In comparison to the corresponding energy spacing in the mirror hypernucleus $^4_\Lambda$H, the present result clearly indicates the existence of charge symmetry breaking (CSB) in $\Lambda N$ interaction. It is also found that the CSB effect is large in the $0^+$ ground state but is by one order of magnitude smaller in the $1^+$ excited state, demonstrating that the $\Lambda N$ CSB interaction has spin dependence

2-Amino­anilinium 2-chloro­acetate

In the crystal structure of the title compound, C6H9N2 +·ClCH2COO−, prepared by the reaction of OPDA (orthophenelynediamine) with chloro­acetic ­acid, N—H⋯O hydrogen bonds generate ladder-like chains and very weak inter­molecular C—H⋯Cl hydrogen-bonding inter­actions between the anions and cations lead to a supra­molecular network. C—H⋯O inter­actions also occur

(R)-1-Phenyl­ethyl­ammonium trifluoro­acetate

In the crystal structure of the title salt, C8H12N+·C2F3O2 −, all of the ammonium H atoms serve as donors for hydrogen bonds to carboxyl­ate O atoms, forming an R 4 3(10) ring motif based on two cations and two anions. Since both cations and anions act as inter-ion bridging groups, R(10) rings aggregate in a one-dimensional supra­molecular network by sharing the strongest N—H⋯O bond. Edge-sharing motifs lie on the twofold screw axis parallel to [010], and anti­parallel packing of these 21-column structural units results in the crystal structure. This arrangement is one of the most commonly occurring in conglomerates of chiral 1-phenyl­ethyl­amine with achiral monocarboxylic acids, confirming that these ionic salts are particularly robust supra­molecular heterosynthons useful in crystal engineering

Stereospecific winding of polycyclic aromatic hydrocarbons into Trinacria propellers

The stereospecific trimerization of enantiomerically-pure binaphthols with hexakis(bromomethyl)benzene gives access in one step to enantiomerically-pure molecular propellers, in which three binaphthyl rings are held together through dioxecine rings. X-Ray diffraction analysis revealed that three out the six naphthyl moieties are folded in a (EF)3-type arrangement held by three intramolecular C-H…π interactions. This slips outward the three remaining naphthyl rings in a blade-like fashion, just like in three-folded propeller components. This peculiar conformation shows striking similarity to the mythological Sicilian symbol of Trinacria, from which the name "trinacria propeller" derives. The propeller conformation is also preserved in chlorinated solutions, as displayed by the presence of a peak at 4.7 ppm typical of an aromatic proton resonance engaged in a C-H…π interaction. The denaturation of the propeller-like conformation is obtained at high temperature, corresponding to activation energy for the ring inversion of ca. 18.2 kcal mol-1. Notably, halide-functionalized molecular propellers exposing I-atoms at the leading and trailing edges could be prepared stereo- and regiospecifically by choosing the relevant iodo-bearing BINOL derivative

Metal-ion permeation in congested nanochannels: the exposure effect of Ag plus ions on the phosphorescent properties of a gold(I)-pyrazolate complex that is confined in the nanoscopic channels of mesoporous silica

An organometallic/silica nanocomposite of a 1D cylindrical assembly of a trinuclear gold(I)pyrazolate complex ([Au3Pz3]) that was confined inside the nanoscopic channels of hexagonal mesoporous silica ([Au3Pz3]/silicahex), emitted red light with a luminescence center at 693 nm upon photoexcitation at 276 nm owing to a AuI?AuI metallophilic interaction. When a film of [Au3Pz3]/silicahex was dipped into a solution of Ag+ in tetrahydrofuran (THF), the resulting nanocomposite material (Ag@[Au3Pz3]/silicahex) emitted green light with a new luminescence center at 486 nm, which was characteristic of a AuI?AgI heterometallic interaction. Changes in the emission/excitation and XPS spectra of Ag@[Au3Pz3]/silicahex revealed that Ag+ ions permeated into the congested nanochannels of [Au3Pz3]/silicahex, which were filled with the cylindrical assembly of [Au3Pz3]

Connective Tissue Growth Factor Causes Persistent Proα2(I) Collagen Gene Expression Induced by Transforming Growth Factor-β in a Mouse Fibrosis Model

Skin fibrotic disorders such as systemic sclerosis (SSc) are characterized by an excessive production of extracellular matrix (ECM) and understood to develop under the influence of certain growth factors. Connective tissue growth factor (CTGF) is a cysteine-rich mitogenic peptide that is implicated in various fibrotic disorders and induced in fibroblasts after activation with transforming growth factor-beta (TGF-beta). To better understand the mechanisms of persistent fibrosis seen in SSc, we previously established an animal model of skin fibrosis induced by exogenous application of growth factors. In this model, TGF-beta transiently induced subcutaneous fibrosis and serial injections of CTGF after TGF-beta caused persistent fibrosis. To further define the mechanisms of skin fibrosis induced by TGF-beta and CTGF in vivo, we investigated in this study, the effects of growth factors on the promoter activity of the pro alpha 2 (1) collagen (COL1A2) gene in skin fibrosis. For this purpose, we utilized transgenic reporter mice harboring the -17 kb promoter sequence of the mouse COL1A2 linked to either a firefly luciferase gene or a bacterial P-galactosidase gene. Serial injections of CTGF after TGF-beta resulted in a sustained elevation of COL1A2 mRNA expression and promoter activity compared with consecutive injection of TGF-beta alone on day 8. We also demonstrated that the number of fibroblasts with activated COL1A2 transcription was increased by serial injections of CTGF after TGF-beta in comparison with the injection of TGF-beta alone. Furthermore, the serial injections recruited mast cells and macrophages. The number of mast cells reached a maximum on day 4 and remained relatively high up to day 8. In contrast to the kinetics of mast cells, the number of macrophages was increased on day 4 and continued to rise during the subsequent consecutive CTGF injections until day 8. These results suggested that CTGF maintains TGF-beta-induced skin fibrosis by sustaining COL1A2 promoter activation and increasing the number of activated fibroblasts. The infiltrated mast cells and macrophages may also contribute to the maintenance of fibrosis

Supramolecularly directed rotary motion in a photoresponsive receptor

Stimuli-controlled motion at the molecular level has fascinated chemists already for several decades. Taking inspiration from the myriad of dynamic and machine-like functions in nature, a number of strategies have been developed to control motion in purely synthetic systems. Unidirectional rotary motion, such as is observed in ATP synthase and other motor proteins, remains highly challenging to achieve. Current artificial molecular motor systems rely on intrinsic asymmetry or a specific sequence of chemical transformations. Here, we present an alternative design in which the rotation is directed by a chiral guest molecule, which is able to bind non-covalently to a light-responsive receptor. It is demonstrated that the rotary direction is governed by the guest chirality and hence, can be selected and changed at will. This feature offers unique control of directional rotation and will prove highly important in the further development of molecular machinery