Magnetization reversal of CuyCr2Se4−zBrx single crystals

Due to a partially inhomogeneous Cu concentration, Cu_yCr₂Se_4?zBr_x single crystal can show a complicated temperature dependence of the wall motion threshold field which is about 0.5 kA/m near the Curie temperature. The crystals can be homogenized by means of a NH₄OH treatment.     

Microwave spectrum,structure, and chemical bonding of trimethylbromosilane

The microwave spectrum of trimethylbromosilane (trimethylsilylbromide) has been investigated in the 26.5–40.0-GHz region. Spectra of several isotopic species have been observed, including the previously unreported spectrum of the ¹H¹²C³⁰Si⁸¹Br species, which yielded a B rotational constant of 1440.92 ± 0.02 MHz. From the experimental data it has been possible to derive the following structural parameters: SiBr = 2.235 ± 0.002 Å, SiC = 1.856 ± 0.010 Å, and ∠CSiBr = 107.5 ± 0.1°. The results have been compared to other relevant data and discussed in terms of prevailing chemical bonding principles.     

Efficient syntheses of new chiral peptidomimetic macrocycles through a configurationally driven preorganization

A new family of 32-membered ring peptidomimetic macrocycles has been efficiently obtained in a simple one-pot two-step reductive amination reaction, from easily prepared precursors. The structural and stereochemical variables have been explored in order to rationalize the obtained selectivity. The formation of the [2A+2B] tetraimine intermediate has been explained in terms of a very favorable configurationally driven preorganization as detected by NMR, CD and molecular modeling.     

Raman and infrared spectra of CdIn2S4 and ZnIn2S4

Four one-phonon Raman lines have been found in CdIn₂S₄ (ZnIn₂S₄) spinels at 92 (72) cm^-1, 186 (184) cm^-1, 246 (253) cm^-1, and 367 (372) cm^-1 for incident photon energies well below the energy gap E_G ～ 2.4 (2.2) eV at 300 K. For photon energies close to E_G, the 367 cm^-1 mode underwent a resonant enhancement in CdIn₂S₄ and four infrared active but Raman forbidden F_1u modes appeared in the CdIn₂S₄ and ZnIn₂S₄ Raman spectra: TO modes at 226 (221) cm^-1 and 309 (312) cm^-1, and LO modes at 274 (272) cm^-1 and 340 (342) cm^-1.     

Inverse error propagation and model identification for coupled dynamic problems with application to electromagnetic metal forming

The purpose of this work is the development and application of strategies to identify material model parameters for metals at high strain-rates using data obtained from high-speed electromagnetic metal forming. To this end, a staggered algorithm for the finite-element-based numerical solution of the coupled electromagnetic-mechanical boundary-value problem has been developed based on mixed Eulerian–Lagrangian multigrid methods. On this basis, the parameter determination together with a sensitivity analysis and error estimation are carried out. After verifying the validity of this approach using synthetic data sets, it is applied to the identification of material parameters using experimental results from electromagnetic tube forming.     

Capture of toxic gases in MOFs: SO2, H2S,NH3 and NOx

MOFs are promising candidates for the capture of toxic gases since their adsorption properties can be tuned as a function of the topology and chemical composition of the pores. Although the main drawback of MOFs is their vulnerability to these highly corrosive gases which can compromise their chemical stability, remarkable examples have demonstrated high chemical stability to SO₂, H₂S, NH₃ and NO_x. Understanding the role of different chemical functionalities, within the pores of MOFs, is the key for accomplishing superior captures of these toxic gases. Thus, the interactions of such functional groups (coordinatively unsaturated metal sites, μ-OH groups, defective sites and halogen groups) with these toxic molecules, not only determines the capture properties of MOFs, but also can provide a guideline for the desigh of new multi-functionalised MOF materials. Thus, this perspective aims to provide valuable information on the significant progress on this environmental-remediation field, which could inspire more investigators to provide more and novel research on such challenging task.

MOFs are promising candidates for the capture of toxic gases such as SO₂, H₂S, NH₃ and NOx. Understanding the role of different chemical functionalities, within the pores of MOFs, is the key for accomplishing superior captures of these toxic gases.     

Sequestration within biomolecular condensates inhibits Aβ-42 amyloid formation

Biomolecular condensates are emerging as an efficient strategy developed by cells to control biochemical reactions in space and time by locally modifying composition and environment. Yet, local increase in protein concentration within these compartments could promote aberrant aggregation events, including the nucleation and growth of amyloid fibrils. Understanding protein stability within the crowded and heterogeneous environment of biological condensates is therefore crucial, not only when the aggregation-prone protein is the scaffold element of the condensates but also when proteins are recruited as client molecules within the compartments. Here, we investigate the partitioning and aggregation kinetics of the amyloidogenic peptide Abeta42 (Aβ-42), the peptide strongly associated with Alzheimer''s disease, recruited into condensates based on low complexity domains (LCDs) derived from the DEAD-box proteins Laf1, Dbp1 and Ddx4, which are associated with biological membraneless organelles. We show that interactions between Aβ-42 and the scaffold proteins promote sequestration and local increase of the peptide concentration within the condensates. Yet, heterotypic interactions within the condensates inhibit the formation of amyloid fibrils. These results demonstrate that biomolecular condensates could sequester aggregation-prone proteins and prevent aberrant aggregation events, despite the local increase in their concentration. Biomolecular condensates could therefore work not only as hot-spots of protein aggregation but also as protective reservoirs, since the heterogenous composition of the condensates could prevent the formation of ordered fibrillar aggregates.

Biomolecular condensates sequester an aggregation-prone peptide and prevent its aggregation, showing that heterotypic interactions within the condensates can prevent the formation of amyloid fibrils, despite the local increase in concentration.     

The Photodecomposition of 1,l-Dichloro-2,2-bis(5′-chloro-2′-methoxyphenyl)ethylene (MPE), an Analogue of DDE

The solution-phase photodecomposition of l, l-dichloro-2,2-bis(5′-chloro-2′-methoxy-phenyl)ethylene (MPE) has been studied at an excitation wavelength of 313 nm in the presence of O₂ as well as in vacuum-degassed solutions. Only two non-volatile compounds are produced: 2,5-dichloro-3-(5′-chloro-2′-methoxyphenyl)benzofuran (BFD) and a minor product which was not identified. The BFD represents approximately 90% of the total non-volatiles. The volatile products were identified as CH₃Cl, CH₄ and HC1, with CH₃C1 being approximately 99.9 % of the total volatiles. Photolyses were carried out in C₆H₁₂ and CCI₄ solvents, the same products being observed in both solvents. Variation of MPE concentration has little or no effect on the relative quantum yield of decomposition. The photodecomposition of MPE does not follow the same pathway as the photodecomposition of DDE.     

On the nature of ion-stabilized cytosine pairs in DNA i-motifs: The importance of charge transfer processes

Recent experimental results indicate that the stability of non-Watson-Crick DNA i-motif structures can be influenced by the presence of various metal cations. Whereas Au⁺, Cu⁺, and Ag⁺ are stabilizing agents, alkali metal ions like Na⁺ or Li⁺ are known to destabilize the i-motif. In terms of reduced ion-cytosine complexes, we rationalize the experimental observations with the help of standard and conceptual density functional theory (DFT) calculations. Our results highlight the importance of coordinating electrostatic bonds with partially covalent character for the stability of the ion-cytosine complex. The occurrence of these bonds can be mainly attributed to charge transfer processes between two cytosines and the transition metal ions, which can be either explained by frontier molecular orbital theory in combination with a bond critical point analysis, or by the concept of chemical reactivity indices within a conceptual DFT approach. The results of our calculations establish a consistent theoretical framework to understand the experimentally observed behavior, and are also important in order to achieve more detailed insights into nucleobase pairing mechanisms in general.     

Site-specific conjugation of ScFvs antibodies to nanoparticles by bioorthogonal strain-promoted alkyne-nitrone cycloaddition

Particularly suitable: An N-terminal serine mutant of anti-HER2 scFv antibody was conjugated to polymer-coated magnetofluorescent nanoparticles by strain-promoted alkyne-nitrone cycloaddition. The resulting nanoparticles (see scheme) proved effective in targeting and labeling HER2-positive breast cancer cells.