Online hyphenation of size-exclusion chromatography and gas-phase electrophoresis facilitates the characterization of protein aggregates

Gas-phase electrophoresis yields size distributions of polydisperse, aerosolized analytes based on electrophoretic principles. Nanometer-sized, surface-dry, single-charged particles are separated in a high laminar sheath flow of particle-free air and an orthogonal tunable electric field. Additionally, nano Electrospray Gas-Phase Electrophoretic Mobility Molecular Analyzer (nES GEMMA) data are particle-number based. Therefore, small particles can be detected next to larger ones without a bias, for example, native proteins next to their aggregates. Analyte transition from the liquid to the gas phase is a method inherent prerequisite. In this context, nonvolatile sample buffers influence results. In the worst case, the (bio-)nanoparticle signal is lost due to an increased baseline and unspecific clustering of nonvolatile components. We present a novel online hyphenation of liquid chromatography and gas-phase electrophoresis, coupling a size-exclusion chromatography (SEC) column to an advanced nES GEMMA. Via this novel approach, it is possible to (i) separate analyte multimers already present in liquid phase from aggregates formed during the nES process, (ii) differentiate liquid phase and spray-induced multimers, and (iii) to remove nonvolatile buffer components online before SEC–nES GEMMA analysis. Due to these findings, SEC–nES GEMMA has the high potential to help to understand aggregation processes in biological buffers adding the benefit of actual size determination for noncovalent assemblies formed in solution. As detection and characterization of protein aggregation in large-scale pharmaceutical production or sizing of noncovalently bound proteins are findings directly related to technologically and biologically relevant situations, we proposed the presented method to be a valuable addition to LC-MS approaches.     

Shear modulus of single wood pulp fibers from torsion tests

Cellulose - The shear modulus of pulp fibers is difficult to measure and only very little literature is available on this topic. In this work we are introducing a method to measure this fiber...     

The potential energy surface of singlet cyclobutadiene and substituted analogs: a coupled-cluster study

Coupled-cluster investigations (CCSD/cc-pVDZ and CCSD/cc-pVQZ//CCSD/cc-pVDZ) of singlet cyclobutadiene and fifteen-substituted analogs were conducted. A local minimum with a square frame does not exist on their potential surfaces. The well-known rectangular D_2h minimum, the square D_4h transition state, and two additional stationary points were found on cyclobutadiene’s potential surface. This included a transition state with a rhombic carbon ring and C_2h symmetry, separating two equivalent puckered C_2v local minima. The predicted barriers were 19.7 and 19.8 kcal/mol at the CCSD/cc-pVDZ and CCSD/cc-pVQZ//CCSD/cc-pVDZ levels, respectively. The relative strain energies of rectangular D_2h cyclobutadiene and all fifteen-substituted analogs were obtained from isodesmic reactions. Progressive substitution with methyl or BH₂ groups continuously lowers ring strain while increasing substitution with fluorines or trifluoromethyl groups steadily increases ring strain. C₄(BH₂)₄ is 16.6 and 13.3 kcal/mol less strained than cyclobutadiene while C₄F₄ is 17.7 and 21.5 kcal/mol more strained at the levels above. Cyclobutadiene is more strained than both cyclopropene and cyclobutene by 12.2 and 37.0 kcal/mol, respectively. Electron density contours indicate that fluorine substitution raised the electron density especially in the short C=C ring bonds above/below the ring plane (π-electrons) but not in the ring plane (σ-electrons). BH₂-substitutions lower the ring π-electron density with little effect in the ring plane. Methyl substituents have little effect on electron densities. All rings retain a strong bond alternation tendency (rectangular) whether substituted with electron-donating or -attracting groups. One-bond coupling constants and the percent p-character in ring C-to-C and C-to-substituent bonds are described.     

Microbial Leaching of Waste Solder for Recovery of Metal

This study proposes an environment-friendly bioleaching process for recovery of metals from solders. Tin-copper (Sn-Cu), tin-copper-silver (Sn-Cu-Ag), and tin-lead (Sn-Pb) solders were used in the current study. The culture supernatant of Aspergillus niger removed metals faster than the culture supernatant of Acidithiobacillus ferrooxidans. Also, the metal removal by A. niger culture supernatant is faster for Sn-Cu-Ag solder as compared to other solder types. The effect of various process parameters such as shaking speed, temperature, volume of culture supernatant, and increased solder weight on bioleaching of metals was studied. About 99 (±1.75)?% metal dissolution was achieved in 60 h, at 200-rpm shaking speed, 30 °C temperature, and by using 100-ml A. niger culture supernatant. An optimum solder weight for bioleaching was found to be 5 g/l. Addition of sodium hydroxide (NaOH) and sodium chloride (NaCl) in the bioleached solution from Sn-Cu-Ag precipitated tin (85?±?0.35 %) and silver (80?±?0.08 %), respectively. Passing of hydrogen sulfide (H₂S) gas at pH 8.1 selectively precipitated lead (57.18?±?0.13 %) from the Sn-Pb bioleached solution. The proposed innovative bioleaching process provides an alternative technology for recycling waste solders to conserve resources and protect environment.     

Base Metal Catalyzed Isocyanide Insertions

Isocyanides are diverse C₁ building blocks considering their potential to react with nucleophiles, electrophiles, and radicals. Therefore, perhaps not surprisingly, isocyanides are highly valuable as inputs for multicomponent reactions (MCRs) and other one‐pot cascade processes. In the field of organometallic chemistry, isocyanides typically serve as ligands for transition metals. The coordination of isocyanides to metal centers alters the electronic distribution of the isocyano moiety, and reaction pathways can therefore be accessed that are not possible in the absence of the metal. The tunable reactivity of the isocyanide functional group by transition metals has evolved into numerous useful applications. Especially palladium‐catalyzed isocyanide insertion processes have emerged as powerful reactions in the past decade. However, reports on the use of earth‐abundant and cheap base metals in these types of transformations are scarce and have received far less attention. In this Minireview, we focus on these emerging base metal catalyzed reactions and highlight their potential in synthetic organic chemistry. Although mechanistic studies are still scarce, we discuss distinct proposed catalytic cycles and categorize the literature according to 1) the (hetero)atom bound to and 2) the type of bonding with the transition metal in which the (formal) insertion occurs.     

Interlaboratory Study to Improve the Quality Control of Methylmercury Determination in Sediment

The results are presented of an interlaboratory study on methylmercury (MeHg) in sediment carried out by a group of European laboratories within the framework of a project managed by the EC Standards, Measurements and Testing Programme (formerly BCR). The aim of this exercise was to evaluate the performance of current methods used for MeHg determination in sediment in order to improve the state-of-the-art prior to the certification of a candidate reference material. The paper describes the organization of the interlaboratory study, the preparation of the sediment material used, the techniques evaluated and the results obtained by the participating laboratories. The outcome of the collaborative project showed that certification could be contemplated, providing that certain analytical techniques were optimized, especially with regard to extraction methods.     

Crystallization Kinetics of Silicalite-1: Use of Tetrapropylammonium Bromide and Chloride as Templates

Silicalite-1, the aluminum-free end number of the ZSM-5 zeolites, was synthesized from a batch composition of 3.25 Na₂O · 40.0 SiO₂ · 552 H₂O · 2.00 TPA by using tetrapropylammonium bromide (TPA-Br) or chloride (TPA-Cl) as templates in the temperature range of 100 to 175 °C in a batch system. Conversion of silica in the starting batch composition into silicalite-1 in the product was followed quantitatively. The activation energies of nucleation and crystallization were determined as 37.2 and 66.5 kJ/mol, respectively. The use of TPA-Cl as the template instead of TPA-Br results in longer induction period for crystallization to start and a larger crystal size in product.