Synthesis,self-assembly,and photomechanical actuator performance of a sequence-defined polyviologen crosslinker

ABSTRACT

Although it is well known that viologen radical cations can self-assemble into stacks or complexes on account of radical-radical pairing interactions, it has only recently been demonstrated that reduction of main-chain polyviologens integrated into hydrogel networks can trigger actuation. In these earlier examples, hydrogels comprising oligoethylene glycol-based polyviologens and poly(ethylene glycol) were functionalized with terminal azide groups to prepare ‘click’-based gels. Here, we report a new structural design for the functional polyviologen that consists of main-chain viologen subunits separated by hexamethylene groups instead of glycols and is capped at each end with styrene groups. Activation of this viologen-based macrocrosslinker was achieved using chemical- and photoreduction methods and its ability to undergo intramolecular chain-folding was monitored by absorption spectroscopy. Acrylate-based organogels and hydrogels were also prepared and a comparison was carried out to assess the actuator performance in each gel in terms of the rate of contraction and changes in stiffness.     

A linearized two-stream radiative transfer code for fast approximation of multiple-scatter fields

Performance is an issue for radiative transfer simulations in hyper-spectral remote sensing backscatter retrieval algorithms. 2-Stream models are often used to speed up flux and radiance calculations. Here we present a linearized 2-stream multiple-scatter code, with the ability to generate analytic weighting functions with respect to any atmospheric or surface property. We examine 2-stream accuracy for the satellite intensity diffuse field, and the corresponding Jacobians for total ozone column and surface albedo, for an application in the ozone UV Huggins bands.     

A fast linearized pseudo-spherical two orders of scattering model to account for polarization in vertically inhomogeneous scattering-absorbing media

We calculate the reflection matrix for the first two orders of scattering in a vertically inhomogeneous, scattering-absorbing medium. We take full account of polarization and perform a complete linearization (analytic differentiation) of the reflection matrix with respect to both the inherent optical properties of the medium and the surface reflection condition. Further, we compute a scalar-vector correction to the total intensity due to the effect of polarization; this correction is also fully linearized. The solar beam attenuation has been computed for a pseudo-spherical atmosphere.Results from the two orders of scattering (2OS) model have been tested against scalar intensities for an inhomogeneous atmosphere, and against Stokes vector results for a homogeneous atmosphere. We have also performed backscatter simulations of reflected sunlight in the O₂A band for a variety of geometries, and compared our results with those from a full vector multiple scattering code. Our results are exact in the center of strong lines and most inaccurate in the continuum, where polarization is least significant. The s- and p-polarized radiances are always computed very accurately. The effect of gas absorption optical depth, solar zenith angle, viewing geometry, surface albedo and wind speed (in the case of ocean glint) on the intensity, polarization and corresponding weighting functions have been investigated. It is shown that the 2OS model provides fast and reliably accurate polarization corrections to the scalar-model radiance and weighting function fields. The model can be implemented in operational retrieval algorithms as an adjunct radiative transfer code to deal with polarization effects.     

Solvothermal depolymerization and recrystallization of imine-linked two-dimensional covalent organic frameworks

Mechanistic understanding into the formation and growth of imine-linked two-dimensional (2D) covalent organic frameworks (COFs) is needed to improve their materials quality and access larger crystallite sizes, both of which limit the promise of 2D COFs and 2D polymerization techniques. Here we report a previously unknown temperature-dependent depolymerization of colloidal 2D imine-linked COFs, which offers a new means to improve their crystallinity. 2D COF colloids form at room temperature but then depolymerize when their reaction mixtures are heated to 90 °C. As the solutions are cooled back to room temperature, the 2D COFs repolymerize and crystallize with improved crystallinity and porosity, as characterized by X-ray diffraction, infrared spectroscopy and N₂ porosimetry. The evolution of COF crystallinity during the solvothermal depolymerization and repolymerization processes was characterized by in situ wide angle X-ray scattering, and the concentrations of free COF monomers as a function of temperature were quantified by variable temperature ¹H NMR spectroscopy. The ability of a 2D COF to depolymerize under these conditions depends on both the identity of the COF and its initial materials quality. For one network formed at room temperature (TAPB-PDA COF), a first depolymerization process is nearly complete, and the repolymerization yields materials with dramatically enhanced crystallinity and surface area. Already recrystallized materials partially depolymerize upon heating their reaction mixtures a second time. A related 2D COF (TAPB-DMTA COF) forms initially with improved crystallinity compared to TAPB-PDA COF and then partially depolymerizes upon heating. These results suggest that both high materials quality and network-dependent properties, such as interlayer interaction strength, influence the extent to which 2D COFs resist depolymerization. These findings offer a new means to recrystallize or solvent anneal 2D COFs and may ultimately inform crystallization conditions for obtaining large-area imine-linked two-dimensional polymers from solution.

Conditions for which imine-linked 2D COF polymerizations are temperature-sensitive are identified that enable a dissolution/repolymerization process akin to molecular recrystallization.     

Shape‐Selective Interception by Hydrocarbons of the O2‐Derived Oxidant of a Biomimetic Nonheme Iron Complex

Picky ferryl : The complex [Fe(Tp)(BF)] (Tp=hydrotris(3,5‐diphenylpyrazolyl)borate; BF=benzoylformate) reacts with O₂ to generate an oxidant (see picture; O red, pink; Fe yellow; N blue; C gray; H white) that oxidizes added hydrocarbons shape‐selectively. Discrimination derives from a cleft formed by two phenyl groups of the Tp ligand, favoring oblate spheroidal substrates.

     

Galactose Grafted Two-Dimensional Nanosheets as a Scaffold for the In Situ Synthesis of Silver Nanoparticles: A Potential Catalyst for the Reduction of Nitroaromatics

Two major hurdles in NP-based catalysis are the aggregation of the NPs and their recycling. Immobilization of NPs onto a 2D support is the most promising strategy to overcome these difficulties. Herein, amphiphilicity-driven self-assembly of galactose-hexaphenylbenzene-based amphiphiles into galactose-decorated 2D nanosheet is reported. The extremely dense decoration of reducing sugar on the surface of the sheets is used for the in situ synthesis and immobilization of ultrafine catalytically active AgNPs by using Tollens’ reaction. The potential of the system as a catalyst for the reduction of various nitroaromatics is demonstrated. Enhanced catalytic activity is observed for the immobilized AgNPs when compared to the corresponding discrete AgNPs. Recovery of the catalytic system from the reaction mixture by ultrafiltration and its subsequent recycling for several cycles without dropping its activity is shown. This is the first report demonstrating the in situ synthesis and immobilization of ultrafine AgNPs onto a 2D nanosheet that exhibits excellent catalytic performance for the reduction of nitroaromatics.     

A novel Zn(4)O-based triazolyl benzoate MOF: synthesis, crystal structure, adsorption properties and solid state 13C NMR investigations

The newly synthesized Zn(4)O-based MOF (3)(∞)[Zn(4)(μ(4)-O){(Metrz-pba)(2)mPh}(3)]·8 DMF (1·8 DMF) of rare tungsten carbide (acs) topology exhibits a porosity of 43% and remarkably high thermal stability up to 430 °C. Single crystal X-ray structure analyses could be performed using as-synthesized as well as desolvated crystals. Besides the solvothermal synthesis of single crystals a scalable synthesis of microcrystalline material of the MOF is reported. Combined TG-MS and solid state NMR measurements reveal the presence of mobile DMF molecules in the pore system of the framework. Adsorption measurements confirm that the pore structure is fully accessible for nitrogen molecules at 77 K. The adsorptive pore volume of 0.41 cm(3) g(-1) correlates well with the pore volume of 0.43 cm(3) g(-1) estimated from the single crystal structure.     

Retrieval of ozone profile from ground-based measurements with polarization: A synthetic study

We perform a retrieval based on optimal estimation theory to retrieve the vertical distribution of ozone from simulated spectra in the Huggins bands. The model atmosphere includes scattering by aerosol as well as Rayleigh scattering. The virtual instrument is ground-based and zenith-viewing. Using this algorithm, we show that it is possible to retrieve the ozone profile provided that the spectral resolution is at least 0.2 nm and the signal to noise ratio greater than 500. Our synthetic retrievals suggest that if we are able to measure the Stokes parameters Q, U and V with accuracy comparable to that of the intensity, the information contained in the measurements, and therefore the inversion, will improve. Furthermore, we find that the measurement of the full Stokes vector from the ground-based instrument will especially enhance the retrieval of tropospheric ozone. Utilizing concepts from information theory, our arguments are confirmed by increases in the degrees of freedom and the Shannon information content in the simulated measurements.     

Consolidating Maintenance Spares

The inventory of spare parts that a firm holds depends on the number of working parts and age of the equipment to be serviced, the expected failure rate associated with each working part, and the acceptable level of service. We model the problem of consolidation of spare parts to reduce overall inventory as an integer program with a nonlinear objective function. A linear reformulation of this model is obtained that helps solve some practical instances. A more compact implicit formulation is developed and solved using a specialized branch-and-price technique. We also demonstrate how this specialized branch-and-price technique is modified to devise a very effective heuristic procedure with a prespecifiable guarantee of quality of solution produced. This provides a practical and efficient methodology for maintenance spare consolidation.