Molecular implementation of sequential and reversible logic through photochromic energy transfer switching

Photochromic spiropyrans modified with fluorophores were investigated as molecular platforms for the achievement of fluorescence switching through modulation of energy transfer. The dyads were designed in such a way that energy transfer is only observed for the open forms of the photochrome (merocyanine and protonated merocyanine), whereas the closed spiropyran is inactive as an energy acceptor. This was made possible through a deliberate choice of fluorophores (4‐amino‐1,8‐naphthalimide, dansyl, and perylene) that produce zero spectral overlap with the spiro form and considerable overlap for the merocyanine forms. From the Förster theory, energy transfer is predicted to be highly efficient and in some cases of 100 % efficiency. The combined switching by photonic (light of λ>530 nm) and chemical (base) inputs enabled the creation of a sequential logic device, which is the basic element of a keypad lock. Furthermore, in combination with an anthracene‐based acidochromic fluorescence switch, a reversible logic device was designed. This enables the unambiguous coding of different input combinations through multicolour fluorescence signalling. All devices can be conveniently reset to their initial states and repeatedly cycled.     

Compliance switching for adhesion control

Climbing lizards display numerous advanced features in their locomotion, notably a method to quickly switch between a state of low and high adhesive force capacity. Inspired by the gecko's adhesive switching, a method of mechanically switching between low and high adhesive states is reported. In particular, the first switching of an adhesive system using only a change in system compliance is demonstrated. Mechanical clamping and a novel magnetic clamping system are used to switch an iron/PDMS composite adhesive between a soft and rigid state. The switch in compliance directly influences the maximum load of the adhesive as measured in lap‐shear. Notably, contact area and the contact chemistry remain unaltered despite significant changes in force capacity. The demonstration of a compliance‐only switching mechanism has broad implications for understanding natural adhesive systems—especially in organisms that can dynamically alter their rigidity (e.g. cells). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 48–57     

Aqueous developable dual switching photoresists for nanolithography

Photon‐mediated switching of polymer solubility plays a crucial role in the manufacture of integrated circuits by photolithography. Conventional photoresists typically rely on a single switching mechanism based on either a change in polarity or, molecular weight of the polymer. Here we report a photoresist platform that uses both mechanisms. The molecular weight switch was achieved by using a poly(olefin sulfone) designed to undergo photo‐induced chain scission. The polarity switch was achieved using pendant groups functionalized with o‐nitrobenzyl esters. These are hydrophobic photosensitive‐protecting groups for hydrophilic carboxylic acids. On irradiation, they are cleaved, making the polymer soluble in aqueous base. Importantly, the resists do not contain photoacid generator, so do not suffer from problems associated with acid diffusion that are detrimental to pattern fidelity. The 193 nm photochemistry of polymer thin films was followed using grazing angle attenuated total reflectance Fourier transform infrared spectroscopy, variable angle spectroscopic ellipsometry, and measurements of solubility in aqueous base. The nanoscale patterning performance of the polymers was also assessed using 193 nm interference lithography and electron‐beam lithography. The implications of using dual switching mechanisms are discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Electrochemical fluorescence switching properties of conjugated polymers composed of triphenylamine,fluorene, and cyclic urea moieties

The study of the electrochemical fluorescence switching properties of the conjugated copolymers containing fluorene, triphenylamine, and 1,3‐diphenylimidazolidin‐2‐one moieties is reported. The polymers show high fluorescence quantum yields, excellent thermal stability, and good solubility in polar organic solvents. While the polymer emits blue light under UV irradiation, the fluorescence intensity is quenched upon electrochemical oxidation. The fluorescent behavior can be reversibly switched between nonfluorescent (oxidized) state and strong fluorescence (neutral) state with a high contrast ratio (I_f/I_f0) of 16.3. The role of the electrochemical oxidation of the triphenylamine moieties is to generate the corresponding radical cations that lead to fluorescence quenching in the solid matrix. © 2012 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym Chem, 2012     

Classical and quantum-mechanical plane switching in CO2

Classical plane switching takes place in systems with a pronounced 1:2 resonance, where the degree of freedom with the lowest frequency is doubly degenerate. Under appropriate conditions, one observes a periodic and abrupt precession of the plane in which the doubly degenerate motion takes place. In this article, we show that quantum plane switching exists in CO(2). Based on our analytical solutions of classical Hamilton's equations of motion, we describe the dependence on vibrational angular momentum and energy of the frequency of switches and the plane switching angle. Using these results, we find optimal initial wave-packet conditions for CO(2) and show, through quantum-mechanical propagation, that such a wave packet indeed displays plane switching at energies around 10 000 cm(-1) above the ground state on time scales of about 100 fs.     

Preparative separation of anti‐oxidative constituents from Rubia cordifolia by column‐switching counter‐current chromatography

An effective column‐switching counter‐current chromatography (CCC) protocol combining stepwise elution mode was successfully developed for simultaneous and preparative separation of anti‐oxidative components from ethyl acetate extract of traditional Chinese herbal medicine Rubia cordifolia. The column‐switching CCC system was interfaced by a commercial low‐pressure six‐port switching valve equipped with a sample loop, allowing large volume introduction from the first dimension (1^st‐D) to the second dimension (2^nd‐D). Moreover, to extend the polarity window, three biphasic liquid systems composed of n‐hexane/ethyl acetate/methanol/water (1:2:1:2, 2:3:2:3, 5:6:5:6 v/v) were employed using stepwise elution mode in the 1^st‐D. By valve switching technique the whole interested region of 1^st‐D could be introduced to second dimension for further separation with the solvent system 5:5:4:6 v/v. Using the present column‐switching CCC protocol, 500 mg of crude R. cordifolia extract were separated, producing milligram‐amounts of four anti‐oxidative components over 90% pure. Structures of purified compounds were identified by ¹H and ¹³C NMR.     

Silicon–oxygen‐bonded oligomers having thermoelectric switching properties

The electrical properties of siloxane oligomers prepared from the reaction of 1,4‐naphthalenediol or 1,4‐naphthoquinone with diphenylsilane using different palladium catalysts, such as PdCl₂, Pd(TMEDA)Cl₂, Pd(TEEDA)Cl₂ (where TMEDA = N,N′‐tetramethylethylenediamine, TEEDA = N,N′‐tetraethylethylenediamine), are dependent on the catalyst. Thermoelectric switching properties can be obtained from the siloxane prepared from the coupling reaction of diphenylsilane with 1,4‐naphthoquinone or 1,4‐naphthalenediol using Pd(TMEDA)Cl₂ as catalyst. Copyright © 2001 John Wiley & Sons, Ltd.     

Fast switching immobilized photochromic dyes

A novel photochromic dye conjugate architecture is described, which allows both covalent tethering to a polymeric host matrix and fast photochromic switching. The new conjugates consist of a photochromic dye covalently bound to two different substituents via a Y‐branching linker (hetero Y‐branching), one being a polymerizable methacrylate moiety and the other a soft (low T_g) poly(dimethylsiloxane) oligomer. The novel conjugates gave faster photochromic decoloration in the host lens matrix compared with the electronically equivalent nonmatrix‐bound and unconjugated parent control dyes. In addition, further acceleration of fade speed kinetics was observed with a longer linker between photochromic dye and methacrylate moiety. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Resistive switching polymer materials based on poly(aryl ether)s containing triphenylamine and 1,2,4‐triazole moieties

A series of poly(aryl ether)s were successfully prepared via aromatic nucleophilic substitution reaction from various bisphenols and a novel bipolar aryl difluoride monomer containing electron‐donor triphenylamine and electron‐acceptor 1,2,4‐triazole moieties. The poly(aryl ether)s exhibited excellent solubility in organic solvents such as dimethylformamide, chloroform, and tetrahydrofuran at room temperature. The poly(aryl ether)s showed high thermal stability with T_d10 higher than 500 °C and glass transition temperatures (T_g) higher than 187 °C. The thin films of the poly(aryl ether)s indicated bistable resistive switching behavior with ON/OFF current ratios as high as 10³. The switching on and switching off bias voltages of the poly(aryl ether)s were affected by the bisphenol moiety. The good resistive switching behavior of the poly(aryl ether)s made them promising candidates for future nonvolatile memory applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6861–6871, 2008     

Optically controlled resonance energy transfer: mechanism and configuration for all-optical switching

In a molecular system of energy donors and acceptors, resonance energy transfer is the primary mechanism by means of which electronic energy is redistributed between molecules, following the excitation of a donor. Given a suitable geometric configuration it is possible to completely inhibit this energy transfer in such a way that it can only be activated by application of an off-resonant laser beam: this is the principle of optically controlled resonance energy transfer, the basis for an all-optical switch. This paper begins with an investigation of optically controlled energy transfer between a single donor and acceptor molecule, identifying the symmetry and structural constraints and analyzing in detail the dependence on molecular energy level positioning. Spatially correlated donor and acceptor arrays with linear, square, and hexagonally structured arrangements are then assessed as potential configurations for all-optical switching. Built on quantum electrodynamical principles the concept of transfer fidelity, a parameter quantifying the efficiency of energy transportation, is introduced and defined. Results are explored by employing numerical simulations and graphical analysis. Finally, a discussion focuses on the advantages of such energy transfer based processes over all-optical switching of other proposed forms.     

Highly Efficient Access to Both Geometric Isomers of Silyl Enol Ethers: Sequential 1,2‐Brook/Wittig Reactions

Novel sequential 1,2‐Brook/Wittig reactions were developed for the preparation of silyl enol ethers. This method enables highly selective preparation of both geometric isomers of glyoxylate silyl enol ethers, using aldehydes (E‐selective) and tosylimines (Z‐selective) as a Wittig electrophile. The salt‐free conditions of this reaction system are likely to be advantageous for switching the selectivity. The optimal reaction conditions and generality of the reaction were investigated, and plausible explanations for the observed selectivity were also discussed.     

Effect of crosslinking polymer networks on the molecular reorientation and electro‐optical performance of in‐plane switching vertically aligned liquid crystal devices

The effects of crosslinking polymer networks (PNs) on the molecular reorientation and electro‐optical properties of vertically aligned (VA) liquid crystal (LC) devices are investigated by applying an in‐plane switching (IPS) electric field. Through the polymerization process, crosslinking PNs are developed on the substrate surface, effectively increasing the anchoring energy and governing the LC molecular reorientation. With its stronger anchoring effect, the PNs cell shows good light transmittance and excellent vertical alignment quality, as compared to the pure LC cell. Furthermore, the alignment transformation and transmittance bounce resulting from the transient process of LC molecular reorientation are eliminated when the cell is operated at high voltages. The rising‐time (t_r) and falling‐time (t_f) responses of the PNs cell are significantly improved, and around 36% improvement in the optical switching response is obtained. In addition, the dynamic gray‐level t_r and t_f responses of the PNs cell are enhanced by around 55% and 42%, respectively, at a low driving voltage (～12 V). This developed VA‐IPS LC/PNs cell benefits not only the LC molecular alignment but also the electro‐optical performance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1123–1130     

Stimuli‐Responsive Reversible Switching of Intersystem Crossing in Pure Organic Material for Smart Photodynamic Therapy

Photosensitizers (PSs) with stimuli‐responsive reversible switching of intersystem crossing (ISC) are highly promising for smart photodynamic therapy (PDT), but achieving this goal remains a tremendous challenge. This study introduces a strategy to obtain such reversible switching of ISC in a new class of PSs, which exhibit stimuli‐initiated twisting of conjugated backbone. We present a multidisciplinary approach that includes femtosecond transient absorption spectroscopy and quantum chemical calculations. The organic structures reported show remarkably enhanced ISC efficiency (Φ_ISC), switching from nearly 0 to 90 %, through an increase in the degree of twisting, providing an innovative mechanism to promote ISC. This leads us to propose here and demonstrate the concept of smart PDT, where pH‐induced reversible twisting maximizes the ISC rate, and thus enables strong photodynamic action only under pathological stimulus (such as change in pH, hypoxia, or exposure to enzymes). The ISC process is turned off to deactivate PDT ability, when the PS is transferred or metabolized away from pathological region.     

Shotgun lipidomics on a LTQ Orbitrap mass spectrometer by successive switching between acquisition polarity modes

Top–down shotgun lipidomics relies on direct infusion of total lipid extracts into a high‐resolution tandem mass spectrometer and implies that individual lipids are recognized by their accurately determined m/z. Lipid ionization efficiency and detection specificity strongly depend on the acquisition polarity, and therefore it is beneficial to analyze lipid mixtures in both positive and negative modes. Hybrid LTQ Orbitrap mass spectrometers are widely applied in top–down lipidomics; however, rapid polarity switching was previously unfeasible because of the severe and immediate degradation of mass accuracy. Here, we report on a method to rapidly acquire high‐resolution spectra in both polarity modes with sub‐ppm mass accuracy and demonstrate that it not only simplifies and accelerates shotgun lipidomics analyses but also improves the lipidome coverage because more lipid classes and more individual species within each class are recognized. In this way, shotgun analysis of total lipid extracts of human blood plasma enabled to quantify 222 species from 15 major lipid classes within 7 min acquisition cycle. Copyright © 2012 John Wiley & Sons, Ltd.     

Reversible Shape‐Morphing and Fluorescence‐Switching in Supramolecular Nanomaterials Consisting of Amphiphilic Cyanostilbene and Cucurbit[7]uril

We demonstrate a reversible shape‐morphing with concurrent fluorescence switching in the nanomaterials which are complexed with cucurbit[7]uril (CB[7]) in water. The cyanostilbene derivative alone forms ribbon‐like two‐dimensional (2D) nanocrystals with bright yellow excimeric emission in water (λ_em=540 nm, Φ_F=42 %). Upon CB[7] addition, however, the ribbon‐like 2D nanocrystals immediately transform to spherical nanoparticles with significant fluorescence quenching and blue‐shifting (λ_em=490 nm, Φ_F=1 %) through the supramolecular complexation of the cyanostilbene and CB[7]. Based on this reversible fluorescence switching and shape morphing, we could demonstrate a novel strategy of turn‐on fluorescence sensing of spermine and also monitoring of lysine decarboxylase activity.     

Dielectric enhancement of chiral flexoelectro-optic switching

The chiral flexoelectro-optic effect is a candidate for realising sub-millisecond electro-optic technologies. Here, we discuss how flexoelectro-optic switching in cholesteric structures can be enhanced by using the dielectric coupling of the field to materials with negative dielectric anisotropy. An experiment is described that can measure the dielectric effect on flexoelectric switching, and the technique is applied to a chiral nematic mixture E7+3.5%R5011. We explore numerically the optimal liquid crystal parameters to best exploit the effect. An enhancement of up to 1° is demonstrated numerically.     

Fully automated reagent peak‐free liquid chromatography fluorescence analysis of highly polar carboxylic acids using a column‐switching system and fluorous scavenging derivatization

In this study, we combined a column‐switching system with a fluorous scavenging derivatization method to develop a fully automated reagent peak‐free LC fluorescence detection protocol for the analysis of highly polar carboxylic acids. In this method, highly polar carboxylic acids were derivatized with fluorescent 1‐pyrenemethylamine in the presence of 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide and 1‐hydroxy‐1H‐benzotriazole. Residual excess of the unreacted reagent was tagged with 2‐(perfluorooctyl)ethyl isocyanate and then removed selectively using a fluorous column‐switching system placed in front of an analytical reversed‐phase column. The signal of the fluorous‐tagged unreacted reagent was completely absent in the resulting chromatograms; therefore, it did not interfere with the quantification of each acid especially those eluted before 20 min. The detection limits (S/N = 3) for the examined acids were in the range from 4.0 to 22 fmol per injection. We have applied this method to comparative analysis of highly polar carboxylic acids in urine samples obtained from diabetes mellitus type‐II model mice and their control.     

Exploring sequential quantum adiabatic switching across supersymmetric partners for finding the eigenstates of a system

We demonstrate that one can exhaustively determine the n‐bound eigenstates of a Hamiltonian H by constructing a sequence of supersymmetric (SUSY) partner Hamiltonians and invoking a time‐dependent quantum adiabatic switching algorithm for passage from the ground state of one to the other. The ground states of the initial pair H⁽⁰⁾ and H⁽¹⁾ are constructed by solving the Riccati equation for the superpotential ?⁽⁰⁾ for H⁽⁰⁾ and adiabatically switching from the ground state Ψ of H⁽⁰⁾ to the ground state Ψ of H⁽¹⁾. The charge operator Q is then used to recover the first excited state Ψ of H⁽⁰⁾. The procedure is repeated for the ground states of SUSY pairs H^{(n + 1)} and H^{(n + 2)}, and appropriate charge operators lead to the excited states Ψ of H⁽⁰⁾ with , thereby exhausting the full eigenspectrum of H⁽⁰⁾. The workability of the proposed method is shown with several well‐known examples. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Anion-coordination-driven single–double helix switching and chiroptical molecular switching based on oligoureas

Synthetic foldamers with helical conformation are widely seen, but controllable interconversion amongst different geometries (helical structure and sense) is challenging. Here, a family of oligourea (tetra-, penta-, and hexa-) ligands bearing stereocenters at both ends are designed and shown to switch between single and double helices with concomitant inversion of helical senses upon anion coordination. The tetraurea ligand forms a right-handed single helix upon chloride anion (Cl⁻) binding and is converted into a left-handed double helix when phosphate anion (PO₄³⁻) is coordinated. The helical senses of the single and double helices are opposite, and the conversion is further found to be dependent on the stoichiometry of the ligand and phosphate anion. In contrast, only a single helix is formed for the hexaurea ligand with the phosphate anion. This distinction is attributed to the fact that the characteristic phosphate anion coordination geometry is satisfied by six urea moieties with twelve H-bonds. Our study revealed unusual single–double helix interconversion accompanied by unexpected chiroptical switching of helical senses.

Two-in-one switching of single–double helical forms and helicities is demonstrated using anion-coordination-driven oligourea foldamers.