A method for dynamic system characterization using hydraulic series resistance

The pressure required to drive flow through a microfluidic device is an important characteristic of that device. We present a method to measure the flow rate through microfluidic components and systems, including micropumps and microvalves. The measurement platform is composed of two pressure sensors and a glass tube, which provides series resistance. The principle of the measurement is the fluid dynamical equivalent of Ohm's law, which defines the relationship between current, resistance, and voltage that are analogues to flow rate, hydraulic resistance, and pressure drop, respectively. Once the series resistance is known, it is possible to compute the flow rate through a device based on pressure alone. In addition, the dynamic system characteristics of the device-resistance and capacitance-can be computed. The benefits of this method are its simple configuration, capability of measuring flow rate accurately from the more easily measured pressure, and the ability to predict the dynamic response of microfluidic devices.     

Determining Hilbert modular forms by central values of Rankin–Selberg convolutions: the weight aspect

The purpose of this paper is to prove that a primitive Hilbert cusp form \(\mathbf{g}\) is uniquely determined by the central values of the Rankin–Selberg L-functions \(L(\mathbf{f}\otimes \mathbf{g}, \frac{1}{2})\), where \(\mathbf{f}\) runs through all primitive Hilbert cusp forms of weight \(k\) for infinitely many weight vectors \(k\). This result is a generalization of the work of Ganguly et al. (Math Ann 345:843–857, 2009) to the setting of totally real number fields, and it is a weight aspect analogue of our previous work (Hamieh and Tanabe in Trans Am Math Soc, arXiv:1609.07209, 2016).     

Coumarin synthesis on π-acidic surfaces

Catalysis with anion–π interactions is emerging as an important topic in supramolecular chemistry. Among the reactions explored so far on π-acidic surfaces, coumarin synthesis stands out as a cascade process with several coupled anionic transition states. Increasing π-acidity has been shown in a different context to increase transition-state stabilisation and thus catalytic activity. In this report, we explore the possible use of macrocycles to accelerate coumarin synthesis between two π-acidic surfaces. To our disappointment, we found that compared to monomeric π-acids, coumarin synthesis within divalent macrocycles is clearly slower. Hindered access to an overly confined active site within the macrocycles could possibly account for this loss in activity, but several other explanations are certainly possible. However, operational coumarin synthesis on monomeric π-acidic surfaces is shown to tolerate structural modifications. Best results are obtained with structures that aim for proximity without obstructing transition-state stabilisation on the π-acidic surface.     

Mechanosensitive membrane probes: push-pull papillons

ABSTRACT

Design, synthesis and evaluation of push-pull N,N′-diphenyl-dihydrodibenzo[a,c]phenazines are reported. Consistent with theoretical predictions, donors and acceptors attached to the bent mechanophore are shown to shift absorption maxima to either red or blue, depending on their positioning in the chromophore. Redshifted excitation of push-pull fluorophores is reflected in redshifted emission of both bent and planar excited states. The intensity ratios of the dual emission in more and less polar solvents imply that excited-state (ES) planarization decelerates with increasing fluorophore macrodipole, presumably due to attraction between the wings of closed papillons. ES planarization of highly polarisable papillons is not observed in lipid bilayer membranes. All push-pull papillon amphiphiles excel with aggregation-induced emission (AIE) from bent ES as micelles in water and mechanosensitivity in viscous solvents. They are not solvatochromic and only weakly fluorescent (QY < 4%).     

Big,Strong, Neutral,Twisted, and Chiral π Acids

General synthetic access to expanded π‐acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion–π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron‐withdrawing substituents decreases and the high π acidity needed for strong anion–π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion–π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from ?3.96 to ?4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X‐ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation–π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches ?4.45 eV, whereas two sulfone moieties give a value of ?4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion–π interactions, these conceptually innovative π‐acidic surfaces are also of interest as electron transporters in conductive materials.     

Novel one-pot approach to synthesis of indanones through Sb(V)-catalyzed reaction of phenylalkynes with aldehydes

Catalytic SbF5 and the use of EtOH as an additive efficiently converted a mixture of phenylalkynes and aldehydes to indanone compounds in one pot, and the reaction stereoselectively afforded the corresponding 2,3-disubstituted indanones as a single trans-isomer.     

Interactions of ibuprofen with hybrid lipid bilayers probed by complementary surface-enhanced vibrational spectroscopies

The incorporation of small molecules into lipid bilayers is a process of biological importance and clinical relevance that can change the material properties of cell membranes and cause deleterious side effects for certain drugs. Here we report the direct observation, using surface-enhanced Raman and IR spectroscopies (SERS, SEIRA), of the insertion of ibuprofen molecules into hybrid lipid bilayers. The alkanethiol-phospholipid hybrid bilayers were formed onto gold nanoshells by self-assembly, where the underlying nanoshell substrates provided the necessary enhancements for SERS and SEIRA. The spectroscopic data reveal specific interactions between ibuprofen and phospholipid moieties and indicate that the overall hydrophobicity of ibuprofen plays an important role in its intercalation in these membrane mimics.     

Substituent effects in selenoxide elimination chemistry

2α-(Arylseleno)cholestan-3-ones (3), 2α-(arylseleno)cholest-4-en-3-ones (4), and 4β-(arylseleno)-24-nor-5β-cholan-3-ones (5) were prepared and their stabilities toward oxidative elimination assessed. Simple competitive experiments demonstrate that electron-withdrawing substituents stabilize arylselenides toward oxidation, while electron-donating groups accelerate the oxidation process. In addition, ab initio and density functional calculations on model systems reveal that selenoxides are relatively insensitive to the nature of substituents on selenium toward elimination, suggesting that the oxidation step is rate-determining during oxidative elimination of selenides. Some results for sulfur and tellurium are also presented.     

Anion-(π)n-π Catalytic Micelles

Anion-π catalysis operates by stabilizing anionic transition states on π-acidic aromatic surfaces. In anion-(π)_n-π catalysis, π stacks add polarizability to strengthen interactions. In search of synthetic methods to extend π stacks beyond the limits of foldamers, the self-assembly of micelles from amphiphilic naphthalenediimides (NDIs) is introduced. To interface substrates and catalysts, charge-transfer complexes with dialkoxynaphthalenes (DANs), a classic in supramolecular chemistry, are installed. In π-stacked micelles, the rates of bioinspired ether cyclizations exceed rates on monomers in organic solvents by far. This is particularly impressive considering that anion-π catalysis in water has been elusive so far. Increasing rates with increasing π acidity of the micelles evince operational anion-(π)_n-π catalysis. At maximal π acidity, autocatalytic behavior emerges. Dependence on position and order in confined micellar space promises access to emergent properties. Anion-(π)_n-π catalytic micelles in water thus expand supramolecular systems catalysis accessible with anion-π interactions with an inspiring topic of general interest and great perspectives.