Ambient-curable polysiloxane coatings: structure and mechanical properties

Ambient-curable polysiloxane coatings were prepared by hydrolysis and condensation of 3-methacryloxypropylmethyldimethoxysilane (MPDS) and methyltriethoxysilane (MTES) and subsequently mixing with 3-aminopropyltriethoxysilane (APS). The structures of the as-obtained polysiloxane oligomers as well as the dried polysiloxane coatings on tinplate substrates were analyzed by FTIR and ²⁹Si NMR. The mechanical properties of the coatings were thoroughly examined at both macro-level and micro-level using a pendulum hardness rocker, an impact tester, and a nanoindentation/nanoscratch instrument. Effects of the molar ratio of MPDS/MTES, the dosage of aqueous ammonia solution, and the catalytic condition on the structure of polysiloxane oligomers as well as the structure and mechanical properties of the polysiloxane coatings were investigated. The dried coatings with thickness of 15–26 μm are highly elastic. The hardness (Koenig hardness and microhardness), impact resistance and scratch resistance are mainly dependent on the condensation degree of polysiloxane coatings rather than on the organic component of the coatings. A proper pre-hydrolysis process or more APS is benefit for enhancing the mechanical strength of the polysiloxane coatings. Polysiloxane coatings with high hardness and excellent scratch resistance can be prepared preferentially at low molar ratio of MPDS/MTES.     

Studies on regioselective acylation of cellulose with bulky acid chlorides

The regioselective esterification of cellulose by reaction with bulky acyl halides including pivaloyl chloride, adamantoyl chloride and 2,4,6-trimethylbenzoyl chloride was studied. Functionalization conditions to achieve a given degree of substitution (DS) and the resulting ester substitution pattern were described in detail. One- and two-dimensional NMR spectroscopy techniques were used to confirm the structure of the esters obtained. We compared the effects on substitution of using different esterifying reagents and solvent systems including DMAc/LiCl, DMSO/TBAF, and ionic liquids (ILs).     

Study on radiative heat transfer property of fiber assemblies using FTIR

Radiative heat transfer could be a significant contribution to the total heat transfer within the highly porous materials. This article reports on the use of a conventional instrument, viz. Fourier transform infrared (FTIR) spectroscopy, for the characterization of radiative heat properties of fiber assemblies with low bulk densities. Experimental measurements on spectral transmission with FTIR were performed on five types of fiber assemblies commonly used for insulating materials. From the measurements, radiative heat conductivity was determined by calculating extinction coefficient using Beer’s Law and applying the diffusion approximation approach. Bulk density, fiber arrangement, and temperature influences to radiative heat transfer were discussed. Results show that radiative heat conductivity decreases with bulk density and that of the random arranged fiber assemblies shows lower radiative heat conductivity than the random ball and parallel arranged fiber assemblies. Radiative heat conductivity is proportional to the cubic temperature. The existing theoretical model was modified by comparing theoretical and experimental radiative heat conductivity results.     

Preparation and methane adsorption of two-dimensional carbide Ti<Subscript>2</Subscript>C

Here a novel material for methane adsorption was synthesized and studied, which is a graphene-like two-dimensional (2D) carbide (Ti₂C, a member of MXenes), formed by exfoliating Ti₂AlC powders in a solution of lithium fluoride (LiF) and hydrochloric acid (HCl) at 40 °C for 48 h. Based on first-principles calculation, theoretically perfect Ti₂C with O termination has a specific surface area (SSA) of 671 m² g^?1 and methane storage capacity is 22.9 wt%. Experimentally, 2.85 % exfoliated Ti₂C with mesopores shown methane capacity of 11.58 cm³ (STP: 0 °C, 1 bar) g^?1 (0.82 wt%) under 5 MPa and the SSA was 19.1 m² g^?1. For Ti₂C sample intercalated with NH₃·H₂O, the adsorbed amount was increased to 16.81 cm³ (STP) g^?1 at same temperature. At the temperature of 323 K, the adsorbed amount of as-prepared Ti₂C was increased to 52.76 cm³ (STP) g^?1. For fully exfoliated Ti₂C, the methane capacity was supposed to be 28.8 wt% or 1148 V (STP)v^?1. Ti₂C theoretically has much larger volume methane capacity than current methane storage materials, though its SSA is not very high.     

Extensional rheology of cellulose/NaOH/urea/H<Subscript>2</Subscript>O solutions

The extensional flow behaviors of cellulose/NaOH/urea/H₂O solution were investigated by using capillary breakup extensional rheometry (CaBER). The effects of temperature, storage time and cellulose concentrations on both the storage modulus G′ and the loss modulus G″ were also analyzed. For 2 wt% cellulose solution, the G′, G″ and filament lifetime remained unchanged after long storage time. While, for 4 wt% cellulose solution, physical gels could form at either higher temperature or for longer storage time, and the filament lifetime, the relaxation time (λ _e ) and the initial extensional viscosity (η _e0) first increased and then decreased with increase of the storage time. The transition points of the filament lifetime shifted to lower storage time with the increase of the temperature. The η _e0 is proportional to λ _e . The results presented suggest that the extensional properties of the cellulose/NaOH/urea/H₂O solution first increase and then decrease during the gelation process, and the spinning time, which decreases linearly with the increase in the storage temperature, must be controlled below the time that η _e0 starts to decrease.     

Reducing Space Charge Effects in a Linear Ion Trap by Rhombic Ion Excitation and Ejection

Space charge effects play important roles in ion trap operations, which typically limit the ion trapping capacity, dynamic range, mass accuracy, and resolving power of a quadrupole ion trap. In this study, a rhombic ion excitation and ejection method was proposed to minimize space charge effects in a linear ion trap. Instead of applying a single dipolar AC excitation signal, two dipolar AC excitation signals with the same frequency and amplitude but 90° phase difference were applied in the x- and y-directions of the linear ion trap, respectively. As a result, mass selective excited ions would circle around the ion cloud located at the center of the ion trap, rather than go through the ion cloud. In this work, excited ions were then axially ejected and detected, but this rhombic ion excitation method could also be applied to linear ion traps with ion radial ejection capabilities. Experiments show that space charge induced mass resolution degradation and mass shift could be alleviated with this method. For the experimental conditions in this work, space charge induced mass shift could be decreased by ~50%, and the mass resolving power could be improved by ~2 times at the same time.

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Computational Analysis of Quadrupole Mass Filters Employing Nontraditional Waveforms

Quadrupole mass filters using non-sinusoidal driving potentials present exciting opportunities for new functionality. Predicting figures of merit like resolving power and transmission efficiency helps characterize these emerging devices. To this end, matrix methods of solving the Hill equation of ion motion are employed to calculate stability diagrams and pseudopotential well depth maps in the a,q plane for arbitrary waveforms. The theoretical resolving power and well depth of digital, trapezoidal and sinusoidal mass filters are compared. Simplified expressions for digital mass filter operation are presented.

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“Wet” Versus “Dry” Folding of Polyproline

When the all-cis polyproline-I helix (PPI, favored in 1-propanol) of polyproline-13 is introduced into water, it folds into the all-trans polyproline-II (PPII) helix through at least six intermediates [Shi, L., Holliday, A.E., Shi, H., Zhu, F., Ewing, M.A., Russell, D.H., Clemmer, D.E.: Characterizing intermediates along the transition from PPI to PPII using ion mobility-mass spectrometry. J. Am. Chem. Soc. 136, 12702–12711 (2014)]. Here, we show that the solvent-free intermediates refold into the all-cis PPI helix with high (>90%) efficiency. Moreover, in the absence of solvent, each intermediate appears to utilize the same small set of pathways observed for the solution-phase PPII → PPI transition upon immersion of PPII_aq in 1-propanol. That folding in solution (under conditions where water is displaced by propanol) and folding in vacuo (where energy required for folding is provided by collisional activation) occur along the same pathway is remarkable. Implicit in this statement is that 1-propanol mimics a “dry” environment, similar to the gas phase. We note that intermediates with structures that are similar to PPII_aq can form PPII under the most gentle activation conditions—indicating that some transitions observed in water (i.e., “wet” folding, are accessible (albeit inefficient) in vacuo. Lastly, these “dry” folding experiments show that PPI (all cis) is favored under “dry” conditions, which underscores the role of water as the major factor promoting preference for trans proline.

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Cis→Trans Isomerization of Pro<Superscript>7</Superscript> in Oxytocin Regulates Zn<Superscript>2+</Superscript> Binding

Ion mobility/mass spectrometry techniques are employed to investigate the binding of Zn²⁺ to the nine-residue peptide hormone oxytocin (OT, Cys¹-Tyr²-Ile³-Gln⁴-Asn⁵-Cys⁶-Pro⁷-Leu⁸-Gly⁹-NH₂, having a disulfide bond between Cys¹ and Cys⁶ residues). Zn²⁺ binding to OT is known to increase the affinity of OT for its receptor [Pearlmutter, A. F., Soloff, M. S.: Characterization of the metal ion requirement for oxytocin-receptor interaction in rat mammary gland membranes. J. Biol. Chem. 254, 3899–3906 (1979)]. In the absence of Zn²⁺, we find evidence for two primary OT conformations, which arise because the Cys⁶–Pro⁷ peptide bond exists in both the trans- and cis-configurations. Upon addition of Zn²⁺, we determine binding constants in water of K_A = 1.43 ± 0.24 and 0.42 ± 0.12 μM^?1, for the trans- and cis-configured populations, respectively. The Zn²⁺ bound form of OT, having a cross section of Ω = 235 Ų, has Pro⁷ in the trans-configuration, which agrees with a prior report [Wyttenbach, T., Liu, D., Bowers, M. T.: Interactions of the hormone oxytocin with divalent metal ions. J. Am. Chem. Soc. 130, 5993–6000 (2008)], in which it was proposed that Zn²⁺ binds to the peptide ring and is further coordinated by interaction of the C-terminal, Pro⁷-Leu⁸-Gly⁹-NH₂, tail. The present work shows that the cis-configuration of OT isomerizes to the trans-configuration upon binding Zn²⁺. In this way, the proline residue regulates Zn²⁺ binding to OT and, hence, is important in receptor binding.

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Structural study of the stability of the captopril drug regarding the formation of its captopril disulphide dimer

Captopril disulphide is obtained under hydrothermal conditions. The IR and Raman spectra data are in agreement with the X-ray diffraction results. The disappearance of the band at 2566 cm^–1 (ν(SH)) in both spectra of captopril disulphide is consistent with the formation of the S–S bond. The degradation of the captopril drug is investigated by Raman spectroscopy and the results indicate that after 6 weeks of air exposure, a band at 512 cm^–1, assigned as ν(SS), is observed, suggesting the formation of captopril disulphide. DFT calculations in the solid state are performed for captopril and captopril disulphide. The results indicate that captopril disulphide is approximately 30 kcal?mol^–1 more stable than captopril. The analysis of the total density of states (DOS) reveals that the captopril valence band contains a significant contribution from the S atom, whereas for captopril disulphide, the O atom is the most important for the valence band.