pH‐Sensitive Mechanical Properties of Elastin‐Based Hydrogels

Ionizable amino acids in protein‐based hydrogels can confer pH‐responsive behavior. Because elastin‐like polypeptides (ELPs) have an established sequence and can crosslink to form hydrogels, they are an ideal system for creating pH‐sensitive materials. This study examines different parameters that might affect pH‐sensitive behavior and characterizes the mechanical and physical properties between pH 3 and 11 of three ELP‐based crosslinked hydrogels. The first finding is that varying the amount of crosslinker affects the overall stiffness and resilience of the hydrogels but does not strongly affect water content, swelling ratio, or pH sensitivity. Second, the choice of two popular tag sequences, which vary in histidine and aspartic acid content, does not have a strong effect on pH‐sensitive properties. Last, selectively blocking lysine and tyrosine residues through acetylation significantly decreases the pH‐sensitive zeta potential. Acetylated hydrogels also demonstrate different behavior at low pH values with reduced swelling, reduced water content, and higher stiffness. Overall, this work demonstrates that ELP hydrogels with ionizable groups are promising materials for environmentally‐responsive applications such as drug delivery, tissue engineering, and microfluidics.     

A Sustainable Solid Electrolyte Interphase for High‐Energy‐Density Lithium Metal Batteries Under Practical Conditions

High‐energy‐density Li metal batteries suffer from a short lifespan under practical conditions, such as limited lithium, high loading cathode, and lean electrolytes, owing to the absence of appropriate solid electrolyte interphase (SEI). Herein, a sustainable SEI was designed rationally by combining fluorinated co‐solvents with sustained‐release additives for practical challenges. The intrinsic uniformity of SEI and the constant supplements of building blocks of SEI jointly afford to sustainable SEI. Specific spatial distributions and abundant heterogeneous grain boundaries of LiF, LiN_xO_y, and Li₂O effectively regulate uniformity of Li deposition. In a Li metal battery with an ultrathin Li anode (33 μm), a high‐loading LiNi_0.5Co_0.2Mn_0.3O₂ cathode (4.4 mAh cm^?2), and lean electrolytes (6.1 g Ah^?1), 83 % of initial capacity retains after 150 cycles. A pouch cell (3.5 Ah) demonstrated a specific energy of 340 Wh kg^?1 for 60 cycles with lean electrolytes (2.3 g Ah^?1).     

Trimethoxymethylsilane as a solid-electrolyte interphases improver for graphite anode

To improve the cycling performance of graphite anode materials, we propose a functional electrolyte additive, trimethoxymethylsilane (TMSi), which contains a silyl ether functional group as part of its molecular structure. First principal calculation studies, in addition to ex situ analyses, demonstrated that electrochemical reduction of ethylene carbonate (EC) gives an anionic reduced EC product. Subsequent chemical reaction with TMSi then generates solid-electrolyte interphase (SEI) layers of Si–O and Si–C functionalized carbonate on the surface of the graphite anode, which prolongs and stabilizes the cycling performance of the cells. As a result, the cell cycled with TMSi-controlled electrolyte exhibits a cycling retention of 89.5%, whereas the cell cycled with standard electrolyte suffers from poor cycling retention (84.3%) after 100 cycles.     

Simultaneous Stabilization of Potassium Metal and Superoxide in K–O2 Batteries on the Basis of Electrolyte Reactivity

In superoxide batteries based on O₂/O₂^? redox chemistry, identifying an electrolyte to stabilize both the alkali metal and its superoxide remains challenging owing to their reactivity towards the electrolyte components. Bis(fluorosulfonyl)imide (FSI^?) has been recognized as a “magic anion” for passivating alkali metals. The KFSI–dimethoxyethane electrolyte passivates the potassium metal anode by cleavage of S?F bonds and the formation of a KF‐rich solid–electrolyte interphase (SEI). However, the KFSI salt is chemically unstable owing to nucleophilic attack by superoxide and/or hydroxide species. On the other hand, potassium bis(trifluorosulfonyl)imide (KTFSI) is stable to KO₂, but results in mossy potassium deposits and irreversible plating and stripping. To circumvent this dilemma, we developed an artificial SEI for the metal anode and thus long‐cycle‐life K–O₂ batteries. This study will guide the development of stable electrolytes and artificial SEIs for metal–O₂ batteries.     

Analysis of elastomeric composites based on fiber-reinforced systems 3. Two-directional composites

Results of investigation of deformation of elastomeric composite materials with a two-directional reinforcement scheme are presented. The study is performed on the basis of a structural macroscopic theory. The matrix of the composites analyzed is of a poorly compressible material. The fibers of both reinforcing systems are simulated as compressible bodies. Dependences of the parameters of tensile and shear strains on the strain values for different geometries of fiber arrangement are obtained.State Metallurgical Academy of Ukraine, Dnepropetrovsk, Ukraine. Translated from Mekhanika Kompozitnykh Materialov, Vol. 35, No. 4, pp. 479–492, May–June, 1999.     

Octahedral Complexes in the Polymerization of α-Olefins

Summary : A series of dimethyl titanium benzamidinate complexes has been prepared containing various functional groups at the aromatic ring. These functional groups were selected to study their electronic or steric effects at the cationic metal center in the polymerization of propylene. Quantitative structure activity relationship (QSAR) studies showed that a linear relationship is observed only for the Taft Parameter (Es). Mono- and bis-benzamidinate complexes were found to produce similar polymers indicating that alike active species are obtained regardless of the starting complex. Deuterium labeled 2-D-propene showed that a new epimerization mechanism for this type of complexes is operative.     

Stationary interphases with extended alkyl chains: A comparative study on chain order by solid-state NMR spectroscopy

Stationary interphases with long n-alkyl chains (n = 18, 22, 30, 34) have been examined by solid-state NMR spectroscopy. The determination of the silane functionality and the degree of cross-linking of silane ligands on the silica surface was performed by ²⁹Si CP/MAS NMR spectroscopy. High-speed ¹H MAS and ¹³C CP/MAS NMR spectroscopy were utilized to assess alkyl chain order and mobility of the different bonded phases. For this purpose, ¹H NMR line widths and ¹³C chemical shifts have been evaluated. It is shown that stationary phase order and rigidity increase with alkyl chain length. In addition, the temperature-dependent trans/gauche conformational change occurs at higher temperatures for a polymeric C₃₄ phase compared with a C₃₀ sorbent. This behaviour is discussed in the context of previously reported Chromatographic (HPLC) shape selectivity differences.     

Molecular modeling of cellulose in amorphous state. III. An innovative elastomeric crosslink system

The flexibility of molecular structures of rubber materials was evaluated using molecular modeling techniques to develop new crosslink agents which improve deformation recovery of cellulose without significant loss of the mechanical strength. Among the studied structures Poly(propylene oxide) (PPO) pentamer appears to be the most flexible and coiled one. Our calculation results showed that, cellulose crosslinked with PPO pentamers had similar deformation recovery to that crosslinked with DMDHEU. No conformation transitions were observed in these crosslinks when cellulose models were extended to 15% strain, which is consistent with the previous result that conformation transitions in crosslinks should be avoided upon extension to achieve a good recovery on crosslinked cellulose. In addition, PPO crosslinks did not significantly affect the breaking strain of cellulose based upon the cavity volume calculations, and they helped to remove the stress concentration among cellulose chains as suggested by the results of hydrogen bonding analysis. Thus, breaking strength of cellulose might not be significantly affected by PPO crosslinks as well. The preliminary experimental results confirmed above observations. Therefore, PPO pentamer appears to be a promising elastomeric backbone structure of crosslinking agents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1821–1833, 2007     

Anisotropic Lattice Gases

We have studied lattice gases with a particle-conserving dynamic rule that involves two principal parameters. One of them has two limiting values that correspond, respectively, to a large, saturating constant field, which induces a positive particle current, and to a random field (zero net current). Varying the other parameter, either particle attractions or repulsions perpendicular to the field are simulated. The nature of ordering is shown to be independent of the value for the field parameter. In particular, the two indicated limiting cases of the latter lead to the same order-parameter critical behavior, consistent with 1/3, in the presence of a linear interface for attractions in two dimensions. Some qualitative features of the time relaxation are briefly described.     

On the macro- and microphase separation of compatibilizers in immiscible polymer blends

Macro- and microphase separation of compatibilizing graft copolymers in melt-mixed polystyrene/polyamide-6 blends was studied by transmission electron microscopy and thermal analysis. Three different graft copolymers with main chains of polystyrene and side chains of poly(ethylene oxide) were used as additives at various concentrations. The polyamide-6 domain sizes decreased with increasing amounts of compatibilizing graft copolymers in the blends up to a saturation concentration, after which no further reduction was noted. Macrophase separation of the graft copolymers into discrete macrodomains 20–200 nm in size occurred at concentrations equal to or slightly lower than the saturation concentration. The macrodomains of the graft copolymers were microphase separated, and the sizes and shapes of the microdomains were found to largely depend on the graft copolymer structure and composition. As a consequence of microphase separation, poly(ethylene oxide) crystallinity was noted in blends with sufficiently high macrophase contents. Observations of a graft copolymer interphase between the polystyrene matrix and the polyamide-6 domains confirmed that the graft copolymer was present at the blend interfaces in some of the compatibilized blends. © 1996 John Wiley & Sons, Inc.