An enzymatic continuous-flow reactor based on a pore-size matching nano- and isoporous block copolymer membrane.

Continuous-flow biocatalysis utilizing immobilized enzymes emerged as a sustainable route for chemical synthesis. However, inadequate biocatalytic efficiency from current flow reactors, caused by non-productive enzyme immobilization or enzyme-carrier mismatches in size, hampers its widespread application. Here, we demonstrate a general-applicable and robust approach for the fabrication of a high-performance enzymatic continuous-flow reactor via integrating well-designed scalable isoporous block copolymer (BCP) membranes as carriers with an oriented and productive immobilization employing material binding peptides (MBP). Densely packed uniform enzyme-matched nanochannels of well-designed BCP membranes endow the desired nanoconfined environments towards a productive immobilized phytase. Tuning nanochannel properties can further regulate the complex reaction process and fortify the catalytic performance. The synergistic design of enzyme-matched carriers and efficient enzyme immobilization empowers an excellent catalytic performance with >1 month operational stability, superior productivity, and a high space-time yield (1.05 × 105 g L-1 d-1) via a single-pass continuous-flow process. The obtained performance makes the designed nano- and isoporous block copolymer membrane reactor highly attractive for industrial applications.

Two-Dimensional Nanoporous Cross-linked Polymer Networks as Emerging Candidates for Gas Adsorption.

This paper illustrates the gas adsorption properties of newly synthesized nanoporous cross-linked polymer networks (CPNs). All synthesized CPNs possess N-rich functional groups and are used for the utilization of carbon dioxide and methane. Good gas adsorption and selectivities are obtained for all of the samples. Among the materials, HEREON2 outperforms better selectivity for methane separation from nitrogen rather than zeolites, activated carbons, molecular sieves, covalent organic frameworks, and metal-organic frameworks (MOFs). The accessibility of the N-rich functionalities makes these materials potential candidates for the separation of hydrocarbons via increased polarizabilities. High-pressure adsorption experiments showed that the synthesized two-dimensional nanoporous materials also have a high affinity toward carbon dioxide. HEREON2 powders showed an increased experimental CO2/N2 selectivity of ∼25,000 at 50 bar due to the presence of nitrogen groups in the structure. Fourier-transform infrared spectroscopy (FTIR), solid-state NMR, X-ray diffraction, thermogravimetric analysis, energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) were applied for the characterization of the synthesized nanoporous CPNs. The results show a potential new pathway for future CPN membrane development.

Structural and kinetic investigation of the hydride composite Ca(BH4)2 + MgH2 system doped with NbF5 for solid-state hydrogen storage.

Designing safe, compact and high capacity hydrogen storage systems is the key step towards introducing a pollutant free hydrogen technology into a broad field of applications. Due to the chemical bonds of hydrogen-metal atoms, metal hydrides provide high energy density in safe hydrogen storage media. Reactive hydride composites (RHCs) are a promising class of high capacity solid state hydrogen storage systems. Ca(BH4)2 + MgH2 with a hydrogen content of 8.4 wt% is one of the most promising members of the RHCs. However, its relatively high desorption temperature of ∼350 °C is a major drawback to meeting the requirements for practical application. In this work, by using NbF5 as an additive, the dehydrogenation temperature of this RHC was significantly decreased. To elucidate the role of NbF5 in enhancing the desorption properties of the Ca(BH4)2 + MgH2 (Ca-RHC), a comprehensive investigation was carried out via manometric measurements, mass spectrometry, Differential Scanning Calorimetry (DSC), in situ Synchrotron Radiation-Powder X-ray Diffraction (SR-PXD), X-ray Absorption Spectroscopy (XAS), Anomalous Small-Angle X-ray Scattering (ASAXS), Scanning and Transmission Electron Microscopy (SEM, TEM) and Nuclear Magnetic Resonance (NMR) techniques.

Free volume and gas permeation in anthracene maleimide-based polymers of intrinsic microporosity.

High free-volume copolymers were prepared via polycondensation with 2,3,5,6,-tetrafluoroterephthalonitrile (TFTPN) in which a portion of the 3,3,3',3'-tetramethyl-1,1'-spirobisindane (TTSBI) of PIM-1 was replaced with dibutyl anthracene maleimide (4bIII). An investigation of free volume using positron annihilation lifetime spectroscopy (PALS), and gas permeation measurements was carried out for the thin film composite copolymer membranes and compared to PIM-1. The average free volume hole size and the gas permeance of the copolymer membranes increased with decreasing TTSBI content in the copolymer.

Solid-state NMR studies of aminocarboxylic salt bridges in L-lysine modified cellulose.

LysCel is a cellulose-based material in which l-lysine molecules are grafted with their amino side chains to the cellulose hydroxyl groups. This modification increases considerably the mechanical strength and resistance of cellulosic structures toward water. It has been attributed to the formation of double salt bridges between lysine aminocarboxyl groups in the zwitterionic state. In order to characterize this unusual structure, we have performed high-resolution solid-state (15)N and (13)C CPMAS NMR experiments on LysCel samples labeled with (15)N in the alpha-position or epsilon-position. Furthermore, (13)C-(15)N REDOR experiments were performed on LysCel where half of the aminocarboxyl groups were labeled in 1-position with 13C and the other half in alpha-position with (15)N. The comparison with the 13C and 15N chemical shifts of l-leucine lyophilized at different pH shows that the aminocarboxyl groups of LysCel are indeed zwitterionic. The REDOR experiments indicate distances of about 3.5 A between the carboxyl carbon and the nitrogen atoms of different aminocarboxyl groups, indicating that the latter are in close contact with each other. However, the data are not compatible with isolated aminocarboxyl dimers but indicate the assembly of zwitterionic aminocarboxyl dimers either in a flat ribbon or as tetramers, exhibiting similar intra- and interdimer (13)C...(15)N distances. This interaction of several aminocarboxyl groups is responsible for the zwitterionic state, in contrast to the gas phase, where amino acid dimers exhibiting two OHN hydrogen bonds are neutral.

A novel green template for the synthesis of mesoporous silica.

Mesoporous pure silicas and functionalized silica with a narrow pore size distribution centered at 3.8 nm were prepared by a novel template, amphiphilic dendritic polyglycerol. The resulting silica materials were characterized by electron microscopy; nitrogen adsorption; (1)H, (13)C, and (29)Si solid-state cross-polarization magic-angle spinning NMR spectroscopy. It was shown that the template could be completely removed from the pure and functionalized silica in an environmentally friendly way by means of a simple water extraction procedure. Furthermore, it was shown that these materials could be easily functionalized, for example, by employing aminopropyl groups. Thus, a new environmentally friendly pathway to this fascinating class of silica material has been opened.

Structural and dynamical properties of guest molecules confined in mesoporous silica materials revealed by NMR.

In the last fifteen years several novel porous silica materials, which are periodically structured on the mesoscopic length scale, have been synthesized. They are of broad interest for fundamental studies of surface-substrate interactions, for studies of the dynamics of guest molecules in confinement and for studies of the effect of confinement on the structural and thermophysical properties of fluids. Examples of such confinement effects include the change of the freezing and melting points or glass transitions of the confined liquids. These effects are studied by combinations of several NMR techniques, such as (15)N- and (2)H-solid-state NMR line shape analysis, MAS NMR and NMR diffusometry with physico-chemical characterization techniques such as nitrogen adsorption and small angle diffraction of neutrons or X-rays. This combination does not require crystalline samples or special clean and well defined surfaces such as conventional surface science techniques, but can work with typical ill-defined real world systems. The review discusses, after a short introduction, the salient features of these materials and the applied NMR experiments to give the reader a basic knowledge of the systems and the experiments. The rest of the review then focuses on the structural and dynamical properties of guest molecules confined in the mesoporous silica. It is shown that the confinement into the pores leads to fascinating new features of the guests, which are often not known for their bulk phases. These features depend strongly on the interplay of the their interactions with the silica surface and their mutual interactions.

Counting of labelled tyrosine molecules in hydrophobic yoctolitre wells filled with water.

Time-dependent radioactivity and solid-state 13C-NMR measurements of tyrosine entrapped in water-filled yoctolitre (10(-24) L) wells with hydrophobic walls are reported; the results indicate that such wells induce the formation of quasi solid tyrosine if they are brought in contact with 0.1 M solutions of this edge amphiphile.

Hydrogen bonding of water confined in mesoporous silica MCM-41 and SBA-15 studied by 1H solid-state NMR.

The adsorption of water in two mesoporous silica materials with cylindrical pores of uniform diameter, MCM-41 and SBA-15, was studied by 1H MAS (MAS=magic angle spinning) and static solid-state NMR spectroscopy. All observed hydrogen atoms are either surface -SiOH groups or hydrogen-bonded water molecules. Unlike MCM-41, some strongly bound water molecules exist at the inner surfaces of SBA-15 that are assigned to surface defects. At higher filling levels, a further difference between MCM-41 and SBA-15 is observed. Water molecules in MCM-41 exhibit a bimodal line distribution of chemical shifts, with one peak at the position of inner-bulk water, and the second peak at the position of water molecules in fast exchange with surface -SiOH groups. In SBA-15, a single line is observed that shifts continuously as the pore filling is increased. This result is attributed to a different pore-filling mechanism for the two silica materials. In MCM-41, due to its small pore diameter (3.3 nm), pore filling by pore condensation (axial-pore-filling mode) occurs at a low relative pressure, corresponding roughly to a single adsorbed monolayer. For SBA-15, owing to its larger pore diameter (8 nm), a gradual increase in the thickness of the adsorbed layer (radial-pore-filling mode) prevails until pore condensation takes place at a higher level of pore filling.