The success of multi-armed, peptide-based receptors in supramolecular chemistry traditionally is not only based on the sequence but equally on an appropriate positioning of various peptidic chains to create a multivalent array of binding elements. As a faster, more versatile and alternative access toward (pseudo)peptidic receptors, a new approach based on multiple Ugi four-component reactions (Ugi-4CR) is proposed as a means of simultaneously incorporating several binding and catalytic elements into organizing scaffolds. By employing α-amino acids either as the amino or acid components of the Ugi-4CRs, this multiple multicomponent process allows for the one-pot assembly of podands bearing chimeric peptide-peptoid chains as appended arms. Tripodal, bowl-shaped, and concave polyfunctional skeletons are employed as topologically varied platforms for positioning the multiple peptidic chains formed by Ugi-4CRs. In a similar approach, steroidal building blocks with several axially-oriented isocyano groups are synthesized and utilized to align the chimeric chains with conformational constrains, thus providing an alternative to the classical peptido-steroidal receptors. The branched and hybrid peptide-peptoid appendages allow new possibilities for both rational design and combinatorial production of synthetic receptors. The concept is also expandable to other multicomponent reactions.
Herein, we reported the imino phosphonate compounds: (4‐methoxy‐benzylidene‐amino‐phenyl‐methyl‐phosphonic acid diethyl ester (MBPDE), 4‐hydroxy‐benzylidene‐amino‐phenyl‐methyl‐phosphonic acid diethyl ester (HBPDE) and 4‐hydroxy‐3‐methoxy‐benzylidene‐amino‐phenyl‐methyl‐phosphonic acid diethyl ester (HMBPD) form the chemical reaction of diethyl (α‐amino benzyl)phosphonate hydrochloride and substituted benzaldehyde. These compounds were characterized by various spectroscopic techniques: FT‐IR, Mass, UV–VIS, 1H NMR and 13 C NMR. Additionally, the optimized molecular structures, FT‐IR, natural bond orbitals (NBOs), frontier molecular orbitals (FMOs), non‐linear optical (NLO) properties were calculated by the density functional theory (DFT) using the B3LYP functional with the 6–311+G(d,p) basis set. Moreover, UV–Visible spectrum of MBPDE, HBPDE and HMBPD were predicted in different solvents using the time dependent TD‐DFT [B3LYP/6‐311+G(d,p)] method using Polarizable Continuum Model (PCM). The non‐linear optical (NLO) properties were calculated by M06 functional with the 6–311+G(d,p) basis set. A synergistic relationship is observed between the experimental and theoretical findings. NBO analysis provided insights about the stability and charge delocalization of the entitled molecules. The global reactivity descriptors were achieved through HOMO‐LUMO energies. The efficiency of the entitled molecules concerning charge transfer and participation in diverse chemical reactivities were figured out perceptibly by applying the frontier molecular orbitals (FMOs) analysis. The average polarizability <α>
values: 277.184, 261.332 and 280.254 a.u. of the MBPDE, HBPDE and HMBPD were determined respectively. The total first hyperpolarizability (βtot) values of the MBPDE, HBPDE and HMBPD were also obtained to be 992.900, 781.527 and 1107.526 a.u. respectively. The compound HMBPD comprising of higher magnitude of average polarizability and the total first hyperpolarizability (βtot) values than MBPDE and HBPDE molecules. Moreover, NLO properties of urea molecule were found smaller in comparison to the MBPDE, HBPDE and HMBPD. The medicinal importances of these novel compounds as well as its contribution towards nonlinear optical field are our future targets.
The success of GeSn alloys as active material for infrared lasers could pave the way toward a monolithic technology that can be manufactured within mainstream silicon photonics. Nonetheless, for operation on chip, lasing should occur at room temperature or beyond. Unfortunately, despite the intense research in recent years, many hurdles have yet to be overcome. An approach exploiting strain engineering to induce large tensile strain in micro‐disk made of GeSn alloy with Sn content of 14 at% is presented here. This method enables robust multimode laser emission at room temperature. Furthermore, tensile strain enables proper valence band engineering; as a result, over a large range of operating temperatures, lower lasing thresholds are observed compared to high Sn content GeSn lasers operating at similar wavelength.
Constraining small peptides into specific secondary structures has been a major challenge in peptide ligand design. So far, the major solution for decreasing the conformational flexibility in small peptides has been cyclization. An alternative is the use of topological templates, which are able to induce and/or stabilize peptide secondary structures by means of covalent attachment to the peptide. Herein a multicomponent strategy and structural analysis of a new type of peptidosteroid architecture having the steroid as N-substituent of an internal amide bond is reported. The approach comprises the one-pot conjugation of two peptide chains (or amino acid derivatives) to aminosteroids by means of the Ugi reaction to give a unique family of N-steroidal peptides. The conjugation efficiency of a variety of peptide sequences and steroidal amines, as well as their consecutive head-to-tail cyclization to produce chimeric cyclopeptide-steroid conjugates, that is, macrocyclic lipopeptides, was assessed. Determination of the three-dimensional structure of an acyclic N-steroidal peptide in solution proved that the bulky, rigid steroidal template is capable of both increasing significantly the conformational rigidity, even in a peptide sequence as short as five amino acid residues, and inducing a β-turn secondary structure even in the all-s-trans isomer. This report provides the first evidence of the steroid skeleton as β-turn inducer in linear peptide sequences.
A novel procedure, based in a closed space vapor transport (CSVT) configuration, has been devised to grow films or flakes of pure MoO2 in a reductive atmosphere, at relatively low temperature and using MoO3 as the source. In contrast with conventional CSVT technique, in the proposed method a temperature gradient is not required for the growth to take place, which occurs through an intermediate volatile transport species that is produced in the complex reduction reaction of MoO3. An added value of this simple method is the possibility of transforming the MoO2 into MoTe2, one of the most interesting members of the transition metal dichalcogenide family. This is achieved in a sequential process that includes the growth of Mo oxide and its (in-situ) tellurization in two consecutive steps.
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