Effect of microcrystalline and microfibrillated cellulose on the evolution of hydration of cement pastes by thermogravimetry

Journal of Thermal Analysis and Calorimetry - The interest in the use of cellulose fibers of increasingly smaller sizes in cementitious materials has increased in recent years. This paper brings...     

Quantum Defects as a Toolbox for the Covalent Functionalization of Carbon Nanotubes with Peptides and Proteins

Single‐walled carbon nanotubes (SWCNTs) are a 1D nanomaterial that shows fluorescence in the near‐infrared (NIR, >800 nm). In the past, covalent chemistry was less explored to functionalize SWCNTs as it impairs NIR emission. However, certain sp³ defects (quantum defects) in the carbon lattice have emerged that preserve NIR fluorescence and even introduce a new, red‐shifted emission peak. Here, we report on quantum defects, introduced using light‐driven diazonium chemistry, that serve as anchor points for peptides and proteins. We show that maleimide anchors allow conjugation of cysteine‐containing proteins such as a GFP‐binding nanobody. In addition, an Fmoc‐protected phenylalanine defect serves as a starting point for conjugation of visible fluorophores to create multicolor SWCNTs and in situ peptide synthesis directly on the nanotube. Therefore, these quantum defects are a versatile platform to tailor both the nanotube's photophysical properties as well as their surface chemistry.     

Spiro-Carbon: A Metallic Carbon Allotrope Predicted from First Principles Calculations

A structurally stable microporous metallic carbon allotrope, poly(spiro[2.2]penta-1,4-diyne) or, for short, spiro-carbon, with I4₁/amd (D_4h) symmetry is predicted by first-principles calculations using density functional theory (DFT). The calculations of electronic, vibrational, and structural properties show that spiro-carbon has lower relative energy than other elusive carbon allotropes such as T-Carbon and 1-diamondyne (Y-Carbon). Its structure can be pictured as a set of trans-cisoid-polyacetylene chains tangled and interconnected together by sp³ carbon atoms. Calculations reveal a metallic electronic structure arising from an “intrinsic doping” of trans-cisoid-polyacetylene chains with sp³ carbon atoms. Possible synthetic routes and various simulated spectra (XRD, NMR, and IR absorption) are provided in order to guide future efforts to synthesize this novel material.     

CO2 Capture by Hydroxylated Azine-Based Covalent Organic Frameworks

Covalent organic frameworks (COFs) RIO-13, RIO-12, RIO-11, and RIO-11m were investigated towards their CO₂ capture properties by thermogravimetric analysis at 1 atm and 40 °C. These microporous COFs bear in common the azine backbone composed of hydroxy-benzene moieties but differ in the relative number of hydroxyl groups present in each material. Thus, their sorption capacities were studied as a function of their textural and chemical properties. Their maximum CO₂ uptake values showed a strong correlation with an increasing specific surface area, but that property alone could not fully explain the CO₂ uptake data. Hence, the specific CO₂ uptake, combined with DFT calculations, indicated that the relative number of hydroxyl groups in the COF backbone acts as an adsorption threshold, as the hydroxyl groups were indeed identified as relevant adsorption sites in all the studied COFs. Additionally, the best performing COF was thoroughly investigated, experimentally and theoretically, for its CO₂ capture properties in a variety of CO₂ concentrations and temperatures, and showed excellent isothermal recyclability up to 3 cycles.     

Optimal static pricing for a tree network

We study the static pricing problem for a network service provider in a loss system with a tree structure. In the network, multiple classes share a common inbound link and then have dedicated outbound links. The motivation is from a company that sells phone cards and needs to price calls to different destinations. We characterize the optimal static prices in order to maximize the steady-state revenue. We report new structural findings as well as alternative proofs for some known results. We compare the optimal static prices versus prices that are asymptotically optimal, and through a set of illustrative numerical examples we show that in certain cases the loss in revenue can be significant. Finally, we show that static prices obtained using the reduced load approximation of the blocking probabilities can be easily obtained and have near-optimal performance, which makes them more attractive for applications.     

Influence of metal ions on antioxidant behaviour in polypropylene

The effect of Cr(III), Fe(III) and Cu(II) ions, at trace levels, on the effectiveness of four commercial antioxidant systems, viz. Topanol, Santowhite, Hostanox 03 and Irganox 1425, in polypropylene (PP) films is examined using infra-red and second-order derivative uv spectroscopy. The results show that at these levels the metal ions have a minor effect on the unstabilised polymer. However, the ions can have a beneficial or adverse effect on antioxidant activity, particularly under oven ageing conditions. The observed effect depends on the metal/antioxidant system, and is attributed to an indirect interaction between the components which can delay or accelerate antioxidant decomposition in the polymer. An exception to this behaviour is the metal complex Irganox 1425, which interacts strongly with copper ions in the polymer matrix. The antioxidant is partially transformed by copper ions during the compression moulding stage. The beneficial effect present in some cases is in direct contrast with what has generally been observed in studies using unstabilised polymers.     

On Transfer Operators for Continued Fractions with Restricted Digits

For any non-empty subset I of the natural numbers, let _I denotethose numbers in the unit interval whose continued fractiondigits all lie in I. Define the corresponding transfer operator for , where Re (rß) = _I is the abscissa of convergence of the series . When acting on a certain Hilbert space H_I, rß, weshow that the operator L_I, rß is conjugate to an integraloperator K_I, rß. If furthermore rß is real,then K_I, rß is selfadjoint, so that L_I, rß: H_I, rß H_I, rß has purely real spectrum.It is proved that L_I, rß also has purely real spectrumwhen acting on various Hilbert or Banach spaces of holomorphicfunctions, on the nuclear space C [0, 1], and on the Fréchetspace C [0, 1]. The analytic properties of the map rß L_I, rßare investigated. For certain alphabets I of an arithmetic nature(for example, I = primes, I = squares, I an arithmetic progression,I the set of sums of two squares it is shown that rß L_I, rß admits an analytic continuation beyond thehalf-plane Re rß > _I. 2000 Mathematics SubjectClassification 37D35, 37D20, 30B70.     

Operator Splitting Multiscale Finite Volume Element Method for Two-Phase Flow with Capillary Pressure

A numerical method used for solving a two-phase flow problem as found in typical oil recovery is investigated in the setting of physics-based two-level operator splitting. The governing equations involve an elliptic differential equation coupled with a parabolic convection-dominated equation which poses a severe restriction for obtaining fully implicit numerical solutions. Furthermore, strong heterogeneity of the porous medium over many length scales adds to the complications for effectively solving the system. One viable approach is to split the system into three sub-systems: the elliptic, the hyperbolic, and the parabolic equation, respectively. In doing so, we allow for the use of appropriate numerical discretization for each type of equation and the careful exchange of information between them. We propose to use the multiscale finite volume element method (MsFVEM) for the elliptic and parabolic equations, and a nonoscillatory difference scheme for the hyperbolic equation. Performance of this procedure is confirmed through several numerical experiments.     

Mechanical properties of natural rubber nanocomposites reinforced with cellulosic nanoparticles obtained from combined mechanical shearing,and enzymatic and acid hydrolysis of sisal fibers

In a previous work (Siqueira et al. 2010b) the preparation of cellulosic nanoparticles from sisal fibers using different processing routes, viz. a combination of mechanical shearing, acid and enzymatic hydrolysis was reported. It was shown that the pre-enzymatic hydrolysis treatment of bleached sisal pulp helps the preparation of well individualized rod-like nanocrystals. An amorphous polymer (natural rubber—NR) was chosen as model matrix to investigate the effect of these nanoparticles on the thermo-mechanical properties of nanocomposites. Both tensile tests and dynamic mechanical analyses showed improved stiffness for all nanocomposites. The enzymatic treatment allowed production of a huge range of cellulosic nanoparticles which provided completely different mechanical properties to NR matrix.