Speciation of nitrogen containing aromatics by atmospheric pressure photoionization or electrospray ionization fourier transform ion cyclotron resonance mass spectrometry

We determine the elemental compositions of aromatic nitrogen model compounds as well as a petroleum sample by atmospheric pressure photoionization (APPI) and electrospray Ionization (ESI) with a 9.4 Tesla Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. From the double-bond equivalents calculated for the nitrogen-containing ions from a petroleum sample, we can infer the aromatic core structure (pyridinic versus pyrrolic nitrogen heterocycle) based on the presence of M(+.) (odd-electron) versus [M+H](+) (even-electron) ions. Specifically, nitrogen speciation can be determined from either a single positive-ion APPI spectrum or two ESI (positive- and negative-ion) spectra. APPI operates at comparatively higher temperature than ESI and also produces radical cations that may fragment before detection. However, APPI fragmentation of aromatics can be eliminated by judicious choice of instrumental parameters.     

Spatially polarizing autocloned elements

A space-variant polarization converting element is introduced that utilizes an autocloning effect to produce high aspect ratio from birefringent gratings. This method utilizes a multilayer deposition process on a template to convert a linearly polarized incident beam to an azimuthally polarized output at a wavelength of 1.55 microm with more than 90% efficiency.     

Microcontact click printing for templating ultrathin films of metal-organic frameworks

The controlled growth of metal-organic frameworks (MOFs) over surfaces has been investigated using a variety of surface analytical techniques. The use of microcontact printing to prepare surfaces, patterned with regions capable of nucleating the growth of MOFs, has been explored by employing copper-catalyzed alkyne-azide cycloaddition (CuAAC) to pattern silicon wafers with carboxylic acids, a functional group that has been shown to nucleate the growth of MOFs on surfaces. Upon subjecting the patterned silicon surfaces to solvothermal conditions, MOF thin films were obtained and characterized subsequently by AFM, SEM, and grazing-incidence XRD (GIXRD). Large crystals (～0.5 mm) have also been nucleated, as indicated by the presence of a bas-relief of the original pattern on one surface of the crystal, suggesting that it is possible to transfer the template surface pattern onto a single crystal of a MOF.     

Cubic Nonlinearity in Elastic Materials: Theoretical Prediction and Computer Modelling of New Wave Effects

Our object of interest is nonlinear interaction of waves in elastic materials. The new model of a material is proposed that takes into account the mechanism of simultaneous quadratic and cubic nonlinear deformations. Introduction of cubic nonlinearity into the model makes the general wave picture more complicated and creates new possibilities for the wave analysis. We present four possibilities for the evolution of profiles of plane harmonic waves. It is noted that quadratic and cubic nonlinearities emerge first of all in the second and third harmonics generation, respectively. Further, we discuss the results of computer modelling of the wave profile evolution. The influence of the progress of second and third harmonics on the wave profile evolution is studied separately. We study separately how second and third harmonics influence the evolution of the wave profile. We also investigate how the progress of harmonics depends on the initial frequency and amplitude. We find two distinct schemes of the evolution progress: the scheme (in) with four stages for the second harmonics and the scheme with three stages for the third harmonics. As a result the influence of both harmonics could be observed simultaneously, and such a case is demonstrated in the paper. Nevertheless this phenomenon is not necessarily present in every material which explains the absence of experimental observations of the third harmonics by this time.     

Nanoporous carbohydrate metal-organic frameworks

The binding of alkali and alkaline earth metal cations by macrocyclic and diazamacrobicyclic polyethers, composed of ordered arrays of hard oxygen (and nitrogen) donor atoms, underpinned the development of host-guest supramolecular chemistry in the 1970s and 1980s. The arrangement of -OCCO- and -OCCN- chelating units in these preorganized receptors, including, but not limited to, crown ethers and cryptands, is responsible for the very high binding constants observed for their complexes with Group IA and IIA cations. The cyclodextrins (CDs), cyclic oligosaccharides derived microbiologically from starch, also display this -OCCO- bidentate motif on both their primary and secondary faces. The self-assembly, in aqueous alcohol, of infinite networks of extended structures, which have been termed CD-MOFs, wherein γ-cyclodextrin (γ-CD) is linked by coordination to Group IA and IIA metal cations to form metal-organic frameworks (MOFs), is reported. CD-MOF-1 and CD-MOF-2, prepared on the gram-scale from KOH and RbOH, respectively, form body-centered cubic arrangements of (γ-CD)(6) cubes linked by eight-coordinate alkali metal cations. These cubic CD-MOFs are (i) stable to the removal of solvents, (ii) permanently porous, with surface areas of ~1200 m(2) g(-1), and (iii) capable of storing gases and small molecules within their pores. The fact that the -OCCO- moieties of γ-CD are not prearranged in a manner conducive to encapsulating single metal cations has led to our isolating other infinite frameworks, with different topologies, from salts of Na(+), Cs(+), and Sr(2+). This lack of preorganization is expressed emphatically in the case of Cs(+), where two polymorphs assemble under identical conditions. CD-MOF-3 has the cubic topology observed for CD-MOFs 1 and 2, while CD-MOF-4 displays a channel structure wherein γ-CD tori are perfectly stacked in one dimension in a manner reminiscent of the structures of some γ-CD solvates, but with added crystal stability imparted by metal-ion coordination. These new MOFs demonstrate that the CDs can indeed function as ligands for alkali and alkaline earth metal cations in a manner similar to that found with crown ethers. These inexpensive, green, nanoporous materials exhibit absorption properties which make them realistic candidates for commercial development, not least of all because edible derivatives, fit for human consumption, can be prepared entirely from food-grade ingredients.     

PolyMOF Nanoparticles: Dual Roles of a Multivalent polyMOF Ligand in Size Control and Surface Functionalization

Metal–organic framework nanoparticles (MOF NPs) have emerged as an important class of materials that display significantly enhanced performance in many applications compared to bulk MOF materials; their synthesis, however, commonly involves a tedious sequence that controls particle size and surface properties in separate steps. Now, a simple strategy to access functional MOF NPs in one pot is reported that uses a polyMOF ligand possessing a polymer block for surface functionalization and a coordination block with tunable multivalency for size control. This strategy produces uniform polyMOF‐5 NPs with sizes down to 20 nm, displaying exceptional structural and colloidal stability upon exposure to ambient conditions. A detailed time‐dependent study revealed that the polyMOF NPs were formed following an aggregation‐confined crystallization mechanism. Generality was demonstrated through the synthesis of well‐defined polyUiO‐66 NPs.     

Electro‐osmotic surface effects generation in an electrokinetic‐based transport device: A comparison of RF and MW plasma generating sources

It is a common practice in insulator‐based dielectrophoretic separation to use and reuse PDMS‐constructed microdevice for an extended period of time while performing biological and technical replicate experiments. This is usually done to rule out any effects of device variation on separation efficiency. Ensuring that all experimental conditions remain the same is critical to the conclusion that can be drawn from such repeated experiments. One important contributing factor to the flow of materials within the device is electro‐osmotic velocity, which stems from the surface condition of the device construction materials. In this paper, we present an affordable microwave‐based (MESA‐Mgen) oxygen plasma cleaner developed for approximately less than $100 using readily obtainable parts from an average local hardware store with no specialized tools. This low‐cost room‐air microwave plasma generator was designed using an R‐4055, 400 W, 2450 MHz half‐pint household microwave oven (Sharp ® ) for exploring the possibility of sealing polydimethylsiloxane (PDMS) devices onto glass with minimal budgetary commitment. Microfluidic channels generated using MESA‐Mgen were evaluated for their electro‐osmotic velocities while factors including contact angles, storage‐solvent, half‐way hydrophobicity period were also explored with MESA‐Mgen, and the results were compared to those obtained from the commercially available plasma cleaner (COM‐PC). These outcomes revealed that the MESA‐Mgen induced hydrophilicity and ensured leak‐free sealing of PDMS substrates in a manner comparable with the COM‐PC.     

Fluctuations of the Increment of the Argument for the Gaussian Entire Function

The Gaussian entire function is a random entire function, characterised by a certain invariance with respect to isometries of the plane. We study the fluctuations of the increment of the argument of the Gaussian entire function along planar curves. We introduce an inner product on finite formal linear combinations of curves (with real coefficients), that we call the signed length, which describes the limiting covariance of the increment. We also establish asymptotic normality of fluctuations.     

Brush‐first and Click: Efficient Synthesis of Nanoparticles that Degrade and Release Doxorubicin in Response to Light

New strategies for the synthesis of multifunctional particles that respond to external stimuli and release biologically relevant agents will enable the discovery of new formulations for drug delivery. In this article, we combine two powerful methods: brush‐first ring‐opening metathesis polymerization and copper‐catalyzed azide–alkyne cycloaddition click chemistry, for the synthesis of a novel class of brush‐arm star polymers (BASPs) that simultaneously degrade and release the anticancer drug doxorubicin (DOX) in response to 365 nm light. In vitro cell viability studies were performed to study the toxicity of azide‐ and DOX‐loaded BASPs. The former were completely nontoxic. The latter showed minimal toxicity in the absence of light; UV‐triggered DOX release led to IC₅₀ values that were similar to that of free DOX.     

Janus Graft Block Copolymers: Design of a Polymer Architecture for Independently Tuned Nanostructures and Polymer Properties

The graft‐through synthesis of Janus graft block copolymers (GBCPs) from branched macromonomers composed of various combinations of homopolymers is presented. Self‐assembly of GBCPs resulted in ordered nanostructures with ultra‐small domain sizes down to 2.8 nm (half‐pitch). The grafted architecture introduces an additional parameter, the backbone length, which enables control over the thermomechanical properties and processability of the GBCPs independently of their self‐assembled nanostructures. The simple synthetic route to GBCPs and the possibility of using a variety of polymer combinations contribute to the universality of this technique.