Light‐triggered stabilization of microgel aggregates

Supramolecular assembly holds great potential in many technological applications. Such structures, however, tend to destabilize in dynamic environments due to weak interactions between their constituent entities. We report on a highly modular and biofriendly chemistry for the stabilization of supramolecular microgel aggregates. Upon irradiation, these structures undergo intermolecular cross‐linking, providing an efficient mechanism for stabilization.     

Thiol-disulfide exchange yields multivalent dendrimers of melamine

[reaction: see text] Thiol-disulfide exchange can be used to prepare multivalent conjugates of a small molecule or octapeptide displayed on dendrimers based on melamine. Exchange of four or eight thiopyridyl groups by captopril occurs at room temperature in methanol almost quantitatively. Exchange using the peptide requires higher temperatures and guanidinium chloride in DMF. While exchange on the tetravalent scaffold with four peptides is almost quantitative, sterics retard formation of the octavalent conjugate: the hexavalent conjugate forms readily.     

Stable aromatic dianion in water

Perylene diimide (PDI) bearing polyethylene glycol substituents at the imide positions was reduced in water with sodium dithionite to produce an aromatic dianion. The latter is stable for months in deoxygenated aqueous solutions, in contrast to all known aromatic dianions which readily react with water. Such stability is due to extensive electron delocalization and the aromatic character of the dianion, as evidenced by spectroscopic and theoretical studies. The dianion reacts with oxygen to restore the parent neutral compound, which can be reduced again in an inert atmosphere with sodium dithionite to give the dianion. Such reversible charging renders PDIs useful for controlled electron storage and release in aqueous media. Simple preparation of the dianion, reversible charging, high photoredox power, and stability in water can lead to development of new photofunctional and electron transfer systems in the aqueous phase.     

Light‐triggered antifouling coatings for porous silicon optical transducers

Nanostructured porous silicon (PSi) is an attractive platform for the design of biosensors because of its high sensitivity and selectivity towards various biological targets. Its use for biosensing applications, however, is compromised as a result of interfacial interactions with biological molecules that may accumulate on their surfaces and degrade their performance. We describe a new hybrid system comprising an oxidized PSi (PSiO₂) nanostructure and antifouling (anti‐adsorption), light‐triggered pre‐polymers that promote crosslinking and surface anchoring to Si walls. The incorporation of the pre‐polymers allowed the production of a thick hydrogel layer on the inorganic nanostructure. Coating completely prevents fouling of proteins on the surface without compromising biosensor performance in terms of sensitivity. The strategy developed here provides a convenient means to combine two distinct features of crosslinking and organic–inorganic hybrid fabrication in a “one‐pot” process. Copyright © 2017 John Wiley & Sons, Ltd.     

Detection of explosives and latent fingerprint residues utilizing laser pointer–based Raman spectroscopy

A modular, compact Raman spectrometer, based on a green laser pointer, an air cooled intensified charged coupled device and a x, y motorized translation stage was developed and applied for point detection. Its performance was tested for measurements of Raman spectra of liquids, trace amounts of explosives and individual particles, as well as for locating individual particles of interest and for chemical imaging of residues of latent human fingerprints. This system was found to be highly sensitive, identifying masses as low as ~1 ng in short times. The point and real-time detection capabilities of the spectrometer, together with the portability that it offers, make it a potential candidate for replacing existing Raman microscopes and for field applications.     

Realization of a sonic black hole analog in a Bose-Einstein condensate

We have created an analog of a black hole in a Bose-Einstein condensate. In this sonic black hole, sound waves, rather than light waves, cannot escape the event horizon. A steplike potential accelerates the flow of the condensate to velocities which cross and exceed the speed of sound by an order of magnitude. The Landau critical velocity is therefore surpassed. The point where the flow velocity equals the speed of sound is the sonic event horizon. The effective gravity is determined from the profiles of the velocity and speed of sound. A simulation finds negative energy excitations, by means of Bragg spectroscopy.     

Supramolecular polymers in aqueous medium: rational design based on directional hydrophobic interactions

Self-assembly in aqueous medium is of primary importance and widely employs hydrophobic interactions. Yet, unlike directional hydrogen bonds, hydrophobic interactions lack directionality, making difficult rational self-assembly design. Directional hydrophobic motif would significantly enhance rational design in aqueous self-assembly, yet general approaches to such interactions are currently lacking. Here, we show that pairwise directional hydrophobic/π-stacking interactions can be designed using well-defined sterics and supramolecular multivalency. Our system utilizes a hexasubstituted benzene scaffold decorated with 3 (compound 1) or 6 (compound 2) amphiphilc perylene diimides. It imposes a pairwise self-assembly mode, leading to well-defined supramolecular polymers in aqueous medium. the assemblies were characterized using cryogenic electron microscopy, small-angle X-ray scattering, optical spectroscopy, and EPR. Supramolecular polymerization studies in the case of 2 revealed association constants in 10(8) M(-1) range, and significant enthalpic contribution to the polymerization free energy. The pairwise PDI motif enables exciton confinement and localized emission in the polymers based on 1 and 2's unique photonic behavior, untypical of the extended π-stacked systems. Directional pairwise hydrophobic interactions introduce a novel strategy for rational design of noncovalent assemblies in aqueous medium, and bring about a unique photofunction.     

Uno Ferro,a de novo Designed Protein,Binds Transition Metals with High Affinity and Stabilizes Semiquinone Radical Anion

Metalloenzymes often utilize radicals in order to facilitate chemical reactions. Recently, DeGrado and co-workers have discovered that model proteins can efficiently stabilize semiquinone radical anion produced by oxidation of 3,5-di-tert-butylcatechol (DTBC) in the presence of two zinc ions. Here, we show that the number and the nature of metal ions have relatively minor effect on semiquinone stabilization in model proteins, with a single metal ion being sufficient for radical stabilization. The radical is stabilized by both metal ion, hydrophobic sequestration, and interactions with the hydrophilic residues in the protein interior resulting in a remarkable, nearly 500 mV change in the redox potential of the SQ ^{. −}/catechol couple compared to bulk aqueous solution. Moreover, we have created 4G-UFsc, a single metal ion-binding protein with pm affinity for zinc that is higher than any other reported model systems and is on par with many natural zinc-containing proteins. We expect that the robust and easy-to-modify DFsc/UFsc family of proteins will become a versatile tool for mechanistic model studies of metalloenzymes.     

The Metric Integral of Set-Valued Functions

This paper introduces a new integral of univariate set-valued functions of bounded variation with compact images in \({\mathbb {R}}^d\). The new integral, termed the metric integral, is defined using metric linear combinations of sets and is shown to consist of integrals of all the metric selections of the integrated multifunction. The metric integral is a subset of the Aumann integral, but in contrast to the latter, it is not necessarily convex. For a special class of segment functions equality of the two integrals is shown. Properties of the metric selections and related properties of the metric integral are studied. Several indicative examples are presented.     

In-plane and out-of-plane defectivity in thin films of lamellar block copolymers

We investigate the ordering of poly(styrene-b-methyl methacrylate) (PS-PMMA) lamellar copolymers (periodicity L₀ = 46 nm) confined between a free surface and brushed poly(styrene-r-methyl methacrylate) silicon substrate. The processing temperature was selected to eliminate wetting layers at the top and bottom interfaces, producing approximately neutral boundaries that stabilize perpendicular domain orientations. The PS-PMMA film thickness (t = 0.5L₀ − 2.5L₀) and brush grafting density (Σ = 0.2–0.6 nm⁻²) were systematically varied to examine their impacts on in-plane and out-of-plane ordering. Samples were characterized with a combination of high-resolution microscopy, X-ray reflectivity, and grazing-incidence small-angle X-ray scattering. In-plane order at the top of the film (quantified through calculation of orientational correlation lengths) improved with tⁿ, where the exponent n increased from 0.75 to 1 as Σ decreased from 0.6 to 0.2 nm⁻². Out-of-plane defects such as tilted domains were detected in all films, and the distribution of domain tilt angles was nearly independent of t and Σ. These studies demonstrate that defectivity in perpendicular lamellar phases is three-dimensional, comprised of in-plane topological defects and out-of-plane domain tilt, with little or no correlation between these two types of disorder. Strong interactions between the block copolymer and underlying substrate may trap both kinds of thermally generated defects. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 339–352