Four amphiphilic peptides were synthesized, characterized, and evaluated regarding their efficiency in the catalysis of direct aldol reactions in water. The lipopeptides differ by having a double ...lipid chain and a guanidinium pyrrole group functionalizing one Lys side chain. All the samples are composed of the amino acids
l
-proline (P),
l
-arginine (R), or
l
-lysine (K) functionalized with the cationic guanidiniocarbonyl pyrrole unit (GCP),
l
-tryptophan (W), and
l
-glycine (G), covalently linked to one or two long aliphatic chains, leading to surfactant-like designs with controlled proline protonation state and different stereoselectivity. Critical aggregation concentrations (cac) were higher in the presence of the GCP group, suggesting that self-assembly depends on charge distribution along the peptide backbone. Cryogenic Transmission Electron Microscopy (Cryo-TEM) and Small Angle X-ray Scattering (SAXS) showed a rich polymorphism including spherical, cylindrical, and bilayer structures. Molecular dynamics simulations performed to assess the lipopeptide polymorphs revealed an excellent agreement with core-shell arrangements derived from SAXS data and provided an atomistic view of the changes incurred by modifying head groups and lipid chains. The resulting nanostructures behaved as excellent catalysts for aldol condensation reactions, in which superior conversions (>99%), high diastereoselectivities (ds = 94 : 6), and enantioselectivities (ee = 92%) were obtained. Our findings contribute to elucidate the effect of nanoscale organization of lipopeptide assemblies in the catalysis of aldol reactions in an aqueous environment.
Guanidiniocarbonyl pyrrole (GCP) conjugated lipopeptides improve aldol reaction catalysis by enhanced the molecules packing parameter, as shown by SAXS data and molecular dynamics simulations.
The large-scale use of glyphosate pesticides in food production has attracted attention due to environmental damage and toxicity risks. Several regulatory authorities have established safe limits or ...concentrations of these pesticides in water and various food products consumed daily. The irreversible inhibition of acetylcholinesterase (AChE) activity is one of the strategies used for pesticide detection. Herein, we found that lipopeptide sequences can act as biomimetic microenvironments of AChE, showing higher catalytic activities than natural enzymes in an aqueous solution, based on IC
50
values. These biomolecules contain in the hydrophilic part the amino acids
l
-proline (P),
l
-arginine (R),
l
-tryptophan (W), and
l
-glycine (G), covalently linked to a hydrophobic part formed by one or two long aliphatic chains. The obtained materials are referred to as compounds
1
and
2
, respectively. According to fluorescence assays,
2
is more hydrophobic than
1
. The circular dichroism (CD) data present a significant difference in the molar ellipticity values, likely related to distinct conformations assumed by the proline residue in the lipopeptide supramolecular structure in solution. The morphological aspect was further characterized using small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM), which showed that compounds
1
and
2
self-assembly into cylindrical and planar core-shell structures, respectively. The mimetic AchE behaviour of lipopeptides was confirmed by Ellman's hydrolysis reaction, where the proline residue in the peptides act as a nucleophilic scavenger of organophosphate pesticides. Moreover, the isothermal titration calorimetry (ITC) experiments revealed that host-guest interactions in both systems were dominated by enthalpically-driven thermodynamics. UV-vis kinetic experiments were performed to assess the inhibition of the lipopeptide catalytic activity and the IC
50
values were obtained, and we found that the detection limit correlated with the increase in hydrophobicity of the lipopeptides, implying the micellization process is more favorable.
Self-assembled lipopeptides act function like the active site of acetylcholinesterase to detect organophosphorus pesticides.
We present azimuthal angular correlations between charged hadrons and energy deposited in calorimeter towers in central d+Au and minimum bias p+p collisions at sNN=200 GeV. The charged hadron is ...measured at midrapidity |eta|<0.35, and the energy is measured at large rapidity (-3.7<eta< -3.1, Au-going direction). An enhanced near-side angular correlation across | Delta eta|>2.75 is observed in d+Au collisions. Using the event plane method applied to the Au-going energy distribution, we extract the anisotropy strength v2 for inclusive charged hadrons at midrapidity up to pT=4.5 GeV/c. We also present the measurement of v2 for identified pi+ or - and (anti)protons in central d+Au collisions, and observe a mass-ordering pattern similar to that seen in heavy-ion collisions. These results are compared with viscous hydrodynamic calculations and measurements from p+Pb at sNN=5.02 TeV. The magnitude of the mass ordering in d+Au is found to be smaller than that in p+Pb collisions, which may indicate smaller radial flow in lower energy d+Au collisions.
In this paper, we present the first measurement of elliptic (v2) and triangular (v3) flow in high-multiplicity 3He+Aucollisions at √sNN=200 GeV. Two-particle correlations, where the particles have a ...large separation in pseudorapidity, are compared in 3He+Au and in p+p collisions and indicate that collective effects dominate the second and third Fourier components for the correlations observed in the 3He+Ausystem. The collective behavior is quantified in terms of elliptic v2 and triangular v3 anisotropy coefficients measured with respect to their corresponding event planes. The v2 values are comparable to those previously measured in d+Au collisions at the same nucleon-nucleon center-of-mass energy. Comparisons with various theoretical predictions are made, including to models where the hot spots created by the impact of the three 3He nucleons on the Au nucleus expand hydrodynamically to generate the triangular flow. Finally, the agreement of these models with data may indicate the formation of low-viscosity quark-gluon plasma even in these small collision systems.
The PHENIX experiment at the Relativistic Heavy Ion Collider has measured φ meson production and its nuclear modification in asymmetric Cu + Au heavy-ion collisions at √sNN = 200 GeV at both forward ...Cu-going direction (1.2 < y < 2.2) and backward Au-going direction (-2.2 < y < -1.2) rapidities. The measurements are performed via the dimuon decay channel and reported as a function of the number of participating nucleons, rapidity, and transverse momentum. In the most central events, 0%–20% centrality, the φ meson yield integrated over 1 < pT < 5 GeV/c prefers a smaller value, which means a larger nuclear modification, in the Cu-going direction compared to the Au-going direction. Finally and additionally, the nuclear-modification factor in Cu + Au collisions averaged over all centrality is measured to be similar to the previous PHENIX result in d + Au collisions for these rapidities.
PDF
