Helices are among the simplest shapes that are observed in the filamentary and molecular structures of nature. The local mechanical properties of such structures are often modeled by a uniform elastic potential energy dependent on bending and twist, which is what we term a rod model. Our first result is to complete the semi-inverse classification, initiated by Kirchhoff, of all infinite, helical equilibria of inextensible, unshearable uniform rods with elastic energies that are a general quadratic function of the flexures and twist. Specifically, we demonstrate that all uniform helical equilibria can be found by means of an explicit planar construction in terms of the intersections of certain circles and hyperbolas. Second, we demonstrate that the same helical centerlines persist as equilibria in the presence of realistic distributed forces modeling nonlocal interactions as those that arise, for example, for charged linear molecules and for filaments of finite thickness exhibiting self-contact. Third, in the absence of any external loading, we demonstrate how to construct explicitly two helical equilibria, precisely one of each handedness, that are the only local energy minimizers subject to a nonconvex constraint of self-avoidance.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1480419 | PMC |
http://dx.doi.org/10.1073/pnas.0508370103 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, Massachusetts Institute of Technology, 170 Albany Street, Cambridge, Massachusetts 02139, United States.
The tau protein misfolds in neurodegenerative diseases such as Alzheimer's disease (AD). These pathological tau aggregates are associated with neuronal membranes, but molecular structural information about how disease-like tau fibrils interact with the lipid membrane is scarce. Here, we use solid-state NMR to investigate the structure of a tau construct bearing four AD-relevant phospho-mimetic mutations (4E tau) with cholesterol-containing high-curvature lipid membranes, which mimic the membrane of synaptic vesicles in neurons.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, 75005, Paris, France.
Dalton Trans
November 2024
Department of Inorganic and Analytical Chemistry, University of Geneva, 30 quai E. Ansermet, CH-1211 Geneva 4, Switzerland.
Due to the primogenic effect, the valence shells of divalent iron Fe(II) ([Ar]3d) and trivalent lanthanides Ln(III) ([Xe]4f) are compact enough to induce spin-state equilibrium for the 3d-block metal and atom-like luminescence for the 4f-block partner in Fe(II)-Ln(III) dyads. In the specific case of homoleptic pseudo-octahedral [Fe(II)N] units, programming spin crossover (SCO) around room temperature at normal pressure requires the design of unsymmetrical didentate five-membered ring chelating NN' ligands, in which a five-membered (benz)imidazole heterocycle (N) is connected to a six-membered pyrimidine heterocycle (N'). Benefiting from the influence, the facial isomer -[Fe(II)(NN')] is suitable for inducing SCO properties at room temperature in solution.
View Article and Find Full Text PDFJ Inorg Biochem
January 2025
Department of Inorganic Chemistry, P. J. Šafárik University, Moyzesova 11, 041 54 Košice, Slovak Republic. Electronic address:
Two In(III) - pyridinecarboxylates ([In(Pic)(NO)(HO)] (InPic; HPic = picolinic acid), [In(HDpic)(Dpic)(HO)]·5HO (InDpic; HDpic = dipicolinic acid), have been synthesized by one-step procedure. The complexes composition was confirmed by physicochemical analyses and X-ray diffraction confirmed molecular structure of both complexes. Moreover, complex species speciation was described in both systems by potentiometry and H NMR spectroscopy and mononuclear complex species were determined; [In(Pic)] (logβ = 6.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
Department of Inorganic and Analytical Chemistry, University of Geneva, 30 Quai E. Ansermet, CH-1211 Geneva 4, Switzerland.
Compared with the ripple of visible Eu-based emission intensity induced by appended [FeN] spin crossover (SCO) units, as detected in the triple-stranded [EuFe()] helicate, the lanthanide-based luminescent detection of Fe spin-state equilibria could be improved significantly if the luminophore emission is shifted toward the near-infrared (NIR) domain. Replacing Eu with Nd in [NdFe()] (i) maintains the favorable SCO properties in acetonitrile [critical temperature = 322(2) K], (ii) saturates nonradiative vibrational relaxation processes in the 233-333 K range, and (iii) boosts the crucial intramolecular Nd → Fe energy transfer rate processes, which are sensitive to the spin state of the Fe metallic center. Consequently, the steady-state NIR Nd(F → I) emission of the luminophore is amplified and linearly correlated with the low-spin-[FeN] and high-spin-[FeN] mole fractions controlled by the SCO equilibrium.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!