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1.
Adv Mater ; 36(11): e2303891, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-37726008

RESUMO

Symmetries and tunability are of fundamental importance in wave scattering control, but symmetries are often obvious upon visual inspection, which constitutes a significant vulnerability of metamaterial wave devices to reverse-engineering risks. Here, it is theoretically and experimentally shown that a symmetry in the reduced basis of the "primary meta-atoms" that are directly connected to the outside world is sufficient; meanwhile, a suitable topology of non-local interactions between them, mediated by the internal "secondary" meta-atoms, can hide the symmetry from sight in the canonical basis. Covert symmetry-based scattering control in a cable-network metamaterial featuring a hidden parity ( P $\mathcal {P}$ ) symmetry in combination with hidden- P $\mathcal {P}$ -symmetry-preserving and hidden- P $\mathcal {P}$ -symmetry-breaking tuning mechanisms is experimentally demonstrated. Physical-layer security in wired communications is achieved using the domain-wise hidden P $\mathcal {P}$ -symmetry as a shared secret between the sender and the legitimate receiver. Within the approximation of negligible absorption, the first tuning of a complex scattering metamaterial without mirror symmetry to feature exceptional points (EPs) of PT $\mathcal {PT}$ -symmetric reflectionless states, as well as quasi-bound states in the continuum, is reported. These results are reproduced in metamaterials involving non-reciprocal interactions between meta-atoms, including the first observation of reflectionless EPs in a non-reciprocal system.

2.
Bioorg Med Chem Lett ; 51: 128341, 2021 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-34454062

RESUMO

A novel engineering strategy to improve autoantibody detection with peptide fragments derived from the parent antigen is presented. The model system studied was the binding of the putative p53 TAD peptide antigen (residues 46-55) to its cognate anti-p53 antibody, ab28. Each engineered peptide contained the full decapeptide epitope and differed only in the flanking regions. Since minimal structural information was available to guide the design, a simple epitope:paratope binding model was applied. The Hidden Symmetry Model, which we recently reported, was used to guide peptide design and estimate per-residue contributions to interaction free energy as a function of added C- and N-terminal flanking peptides. Twenty-four peptide constructs were designed, synthesized, and assessed for binding affinity to ab28 by surface plasmon resonance, and a subset of these peptides were evaluated in a simulated immunoassay for limit of detection. Many peptides exhibited over 200-fold enhancements in binding affinity and improved limits of detection. The epitope was reevaluated and is proposed to be the undecapeptide corresponding to residues 45-55. HSymM calculated binding free energy and experimental data were found to be in good agreement (R2 > 0.75).


Assuntos
Anticorpos Monoclonais/imunologia , Antígenos/imunologia , Fragmentos de Peptídeos/imunologia , Engenharia de Proteínas , Proteína Supressora de Tumor p53/imunologia , Anticorpos Monoclonais/química , Antígenos/química , Humanos , Epitopos Imunodominantes , Fragmentos de Peptídeos/química , Conformação Proteica , Proteína Supressora de Tumor p53/química
3.
Angew Chem Int Ed Engl ; 60(27): 14869-14874, 2021 06 25.
Artigo em Inglês | MEDLINE | ID: mdl-33856105

RESUMO

Herein we report the first enantioselective total synthesis of 3,5-dimethylorsellinic acid-derived meroterpenoids (-)-berkeleyone A and its five congeners ((-)-preaustinoids A, A1, B, B1, and B2) in 12-15 steps, starting from commercially available 2,4,6-trihydroxybenzoic acid hydrate. Based upon the recognition of latent symmetry within D-ring, our convergent synthesis features two critical reactions: 1) a symmetry-breaking, diastereoselective dearomative alkylation to assemble the entire carbon core, and 2) a Sc(OTf)3 -mediated sequential Krapcho dealkoxycarbonylation/carbonyl α-tert-alkylation to forge the intricate bicyclo[3.3.1]nonane framework. We also conducted our preliminary biomimetic investigations and uncovered a series of rearrangements (α-ketol, α-hydroxyl-ß-diketone, etc.) responsible for the biomimetic diversification of (-)-berkeleyone A into its five preaustinoid congeners.

4.
J Neurosci Res ; 94(5): 351-65, 2016 May.
Artigo em Inglês | MEDLINE | ID: mdl-26887842

RESUMO

Symmetries are widespread invariances underscoring countless systems, including the brain. A symmetry break occurs when the symmetry is present at one level of observation but is hidden at another level. In such a general framework, a concept from algebraic topology, namely, the Borsuk-Ulam theorem (BUT), comes into play and sheds new light on the general mechanisms of nervous symmetries. The BUT tells us that we can find, on an n-dimensional sphere, a pair of opposite points that have the same encoding on an n - 1 sphere. This mapping makes it possible to describe both antipodal points with a single real-valued vector on a lower dimensional sphere. Here we argue that this topological approach is useful for the evaluation of hidden nervous symmetries. This means that symmetries can be found when evaluating the brain in a proper dimension, although they disappear (are hidden or broken) when we evaluate the same brain only one dimension lower. In conclusion, we provide a topological methodology for the evaluation of the most general features of brain activity, i.e., the symmetries, cast in a physical/biological fashion that has the potential to be operationalized. © 2016 Wiley Periodicals, Inc.


Assuntos
Mapeamento Encefálico/métodos , Encéfalo/fisiologia , Rede Nervosa/fisiologia , Animais , Humanos , Imageamento por Ressonância Magnética/métodos , Vias Neurais/fisiologia
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