Lucasdale2763

Aspartic acid (Asp) to isoaspartic acid (isoAsp) isomerization in therapeutic monoclonal antibodies (mAbs) and other biotherapeutics is a critical quality attribute (CQA) that requires careful control and monitoring during the drug discovery and production processes. The unwanted formation of isoAsp within biotherapeutics and resultant structural changes in the peptide backbone may negatively impact the efficacy, potency, and safety of the molecule or become immunogenic, especially if the isomerization occurs within the mAb complementarity determining region (CDR). Herein we describe a MALDI-TOF/TOF mass spectrometry method that affords unequivocal identification of the presence and the exact position of the isoAsp residue(s) in peptide standards ranging in size from a tripeptide to a docosapeptide (22 residues). In general, the peptide bond immediately N-terminal to the isoAsp residue is more susceptible to MALDI-TOF/TOF fragmentation than its unmodified counterpart. In some of the peptides evaluated in this study, fragmentation of the peptide bond C-terminal to the isoAsp residue (the aspartate effect) is also enhanced when compared to the control. Relative quantification by MALDI-TOF/TOF of this chemical modification is dependent upon a successful reversed-phase HPLC (rpHPLC) separation of the control and modified peptides. This method has also been validated on a therapeutic mAb that contains a well-documented isoAsp residue in the heavy chain CDR3 after forced degradation. Moreover, we also demonstrate that higher energy C-trap dissociation of only the singly charged species, and not the multiply charged form, of the isoAsp containing peptide, separated by rpHPLC, results in LC-MS/MS fragmentation that is highly consistent to that of MALDI-TOF/TOF.In this study, three different Ga-containing systems based on GaCl3, Ga2Cl6, or ionic [Ga(L)3][GaCl4]3 (L = methylidenemalonate) complex were screened to elucidate the mechanism, regioselectivity, chemoselectivity, and role of Ga mediator in the reaction between two types of acetylenes (phenylacetylene and but-1-yn-1-ylbenzene) and methylidenemalonates, i.e., the 1,2-zwitterionic precursors that are similar to intermediates derived from donor-acceptor cyclopropanes (DACs). Our DFT calculation results clearly show that the ionic gallium complex [Ga(L)3][GaCl4]3 represents the key mediator in the title reaction. After the formation of such a complex, the first reaction step is the nucleophilic addition of phenylacetylene or but-1-yn-1-ylbenzene to [Ga(L)3][GaCl4]3, generating an unstable vinyl cation intermediate. In the phenylacetylene system, this vinyl cation intermediate accepts a chlorine atom from [GaCl4]- to give E-configuration intermediate. Then, the above process occurs to other two ligands of the Ga(ize various Ga-mediated reactions, which might also be extrapolated to organic transformations undergoing in the presence of aluminum and indium complexes.The increasingly large stream of e-waste is seriously threatening the environment; meanwhile, global energy shortage is on the rise. Based on the principles of energy regeneration and waste utilization, we introduced a win-win approach to utilize waste capacitors for construction of magnetic and core-shell Z-scheme Nb-Pb-codoped BaTiO3/Ni-Pd@graphite-like carbon nitride (g-C3N4) photocatalysts for H2 evolution. Using simple ball-milling, waste capacitors were transformed to Nb-Pb-codoped BaTiO3/Ni-Pd-Ag-Sn nanoparticles and g-C3N4 was coated on the nanoparticles, forming a core-shell structure. The Ni-Pd acted as the electron mediator in the Z-scheme, and Ag-Sn also facilitated the electron transfer. Moreover, Ni made the Z-scheme magnetically separable. The Z-scheme showed a remarkably enhanced photocatalytic H2 evolution rate, which was 22.2 times higher than that of g-C3N4. Such an enhanced photocatalytic performance was attributed to the special Z-scheme and core-shell structure, improving the light adsorption, increasing the Brunauer-Emmett-Teller (BET) surface area, facilitating the efficient separation of electron-hole pairs, and maintaining the strong redox ability of charge carriers. Furthermore, the photoluminescence analysis combined with density functional theory (DFT) calculations provided the basis for the Z-scheme mechanism. This study adequately utilized the composition of e-waste to construct a highly efficient and magnetically separable Z-scheme for H2 generation, which realizes energy regeneration, waste recycling, and environmental protection.The naturally occurring (4R,5R)-4-hydroxy-γ-decalactone from the Japanese orange fly and the antipode of (4S,5R)-4-hydroxy-γ-dodecalactone from the harvestmen arachnid and their stereoisomers are synthesized from the chiral pool material d-glucono-δ-lactone in a few steps. The one-pot conversion of the latter to γ-vinyl-β-hydroxy-γ-lactone, cross-metathesis with requisite olefin, and hydrogenation enabled the synthesis of syn-lactones in just a two-pot operation. An additional efficient Pd-catalyzed allylic isomerization of γ-vinyl-β-hydroxy-γ-lactone led to the anti-lactones in high yields.Cephalopods use chromatophores distributed on their soft skin to change skin color and its pattern. Each chromatophore consists of a central sac containing pigment granules and radial muscles surrounding the sac. The contraction of the radial muscle causes the central sac to expand in area, making the color of the pigment more visible. With the chromatophores actuating individually, cephalopods can create extremely complex skin color patterns, which they utilize for exquisite functions including camouflage and communication. Inspired by this mechanism, we present an artificial chromatophore that can modulate its color pattern in response to light. Multimaterial projection microstereolithography is used to integrate three functional components including a photoactive hydrogel composite with polydopamine nanoparticles (PDA-NPs), acrylic acid hydrogel, and poly(ethylene glycol) diacrylate. In order to generate light-driven actuation of the artificial chromatophore, the photothermal effect of the PDA-NPs, light-responsive deformation of the photoactive hydrogel composite, and the produced mechanical stresses are studied. Mechanical properties and interfacial bonding strengths between different materials are also investigated to ensure structural integrity during actuation. We demonstrate pattern modulation of the light-responsive artificial chromatophores (LACs) with the projection of different light patterns. The LAC may suggest a new concept for various engineering applications such as the camouflage interface, biophotonic device, and flexible display.The three-component reaction of α,β-unsaturated N-arylaldimines, dialkyl but-2-ynedioates, and 2-arylidene Meldrum acids in DCM at room temperature gave mixtures of cis/trans-11-aryl-7-styryl-2,4-dioxa-8-azaspiro[5.5]undec-9-enes in satisfactory yields. The similar three-component reaction with 2-arylidene-N,N'-dimethylbarbituric acids afforded cis-11-phenyl-7-styryl-2,4,8-triazaspiro[5.5]undec-9-enes as major products. On the other hand, the three-component reaction of N-arylaldimines, dialkyl but-2-ynedioates, and 2-arylidene Meldrum acids or 2-arylidene-N,N'-dimethylbarbituric acids afforded cis/trans-isomeric spirocompounds in satisfactory yields with high diastereoselectivity. This domino [2+2+2] cycloaddition reaction proceeded with sequential nucleophilic addition of N-arylaldimine to an electron-deficient alkyne, Michael addition, and annulation process. The stereochemistry of all cis/trans isomeric spirocompounds was clearly elucidated by the determination of 33 single-crystal structures. The diastereoselectivity of the three-component reaction was correlated by DFT calculations.During the past years, much research work has been focused on efficiently harvesting solar energy with black silicon (b-Si). However, semiconductor Si can only utilize solar energy with wavelength smaller than λ = 1110 nm (bandgap Eg = 1.12 eV) for photovoltaic applications or photoelectrochemical conversions. Light with wavelength beyond the band edge (above λ = 1110 nm) cannot be used. Here, we prepared highly conductive b-Si without an apparent optical bandgap by a reactive ion etching process, which can largely absorb light with a wide range wavelength and even far into the near-infrared region (∼2500 nm). The optimized b-Si with surface texture shows the specular reflection rate lower than 0.1% and the average total reflection (specular reflectance + diffuse reflectance) is about 1.1%. Additionally, we briefly introduce the mechanism and reflection principle of surface nanostructured b-Si. By using b-Si structured material, we successfully convert the solar energy to electric power via photo-thermoelectric conversion, especially solar energy exceeding 1110 nm wavelength can also be efficiently used. The excellent light trapping of sunlight shows great potential for photothermal applications, such as photothermal imaging, seawater desalination, and further applications.Structural coloration with artificially nanostructured materials is emerging as a prospective alternative to traditional pigments for the high resolution, sustainable recycling, and long-time durability. However, achieving bright field structural colors with dielectric nanostructures remains a great challenge due to the weak scattering in an asymmetric environment. Here, we demonstrate all-dielectric bright field structural colors with diffraction-limited resolution on the silicon-on-insulator platform. The backscattering is strongly enhanced from the constructive interference between Mie resonances of individual Si antennas and Fabry-Perot resonances supported by the SiO2 layer. The fabricated colors with varying hues and saturations show strong insensitivity with respect to the interparticle spacing and, remarkably, the viewing angle under resonant conditions. Compared with creating a quasi-homogeneous environment, our strategy is solid and complementary metal-oxide semiconductor integrable, paving the way for practical applications of structural colors in nanoscale color printing, microdisplays, and imaging.Guided by the self-assembled process and mechanism, the strategy of in situ Schiff base reaction would be capable of bringing a feasible method to construct and synthesize lanthanide compounds with distinct structures and magnetic properties. A mononuclear Dy(III) compound was synthesized through a multidentate Schiff base ligand and a chelating β-diketonate ligand, which was named as [Dy(L)(bppd)]·CH3OH [1; H2L = N,N'-bis(2-hydroxy-5-methyl-3-formylbenzyl)-N,N'-bis(pyridin-2-ylmethyl)ethylenediamine and bppd = 3-bis(pyridin-2-yl)propane-1,3-dione]. selleck chemicals Furthermore, a new binuclear Dy(III) compound, [Dy2(H2Lox)(bppd)3]·8CH3OH [2; H4Lox = N,N'-bis[2-hydroxy-5-methyl-3-(hydroxyiminomethyl)benzyl]-N,N'-bis(pyridin-2-ylmethyl)ethylenediamine], was obtained via an in situ synthetic process. Under similar synthetic conditions, [Dy(L)(ctbd)] [3; ctbd = 1-(4-chlorophenyl)-4,4,4-trifluoro-1,3-butanedione] and [Dy2(H2Lox)(ctbd)3]·CH3OH·C4H10O (4) were synthesized by modifying the β-diketonate ligand and in situ Schiff base reaction.