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Cell penetrating peptides (CPPs) hold immense potential for the transport of therapeutic agents to their active targets, due to their low cytotoxicity and high transduction efficiency. Adoption of CPPs as delivery systems, and development of novel peptides has been hampered by the variety of mechanisms and complexity of factors involved in cellular uptake. Quantitatively analyzing these systems is further hindered by the inability to compare data among reports due to varying experimental conditions. In this study we investigate the translocation of seventeen CPPs, representing cationic, amphipathic and hydrophobic physicochemical classes, through a DOPC membrane using molecular dynamics simulations. Free energy profiles for individual peptides inserting into the lipid bilayer were generated giving insight into both the approach and adsorption of different CPPs to cell membranes, and the feasibility of their direct translocation. The control of physical conditions and composition allows objective comparison of different peptides and analyze the effect of sequence on the adsorption and translocation energetics. Our results indicate that positively charged residues impart repulsion, while hydrophobic residues increase bilayer interaction. This study is the first step in fully understanding the processes and energetics involved in the passive translocation mechanisms of CPPs, which usually involve multiple peptides.

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Producción Científica, Zinc plays an important role in the regulation of many cellular functions; it is a signaling molecule involved in the transduction of several cascades in response to intra and extracellular stimuli. Labile zinc is a small fraction of total intracellular zinc, that is loosely bound to proteins and is easily interchangeable. At the cellular level, several molecules can bind labile zinc and promote its passage across lipophilic membranes. Such molecules are known as ionophores. Several of these compounds are known in the scientific literature, but most of them can be harmful to human health and are therefore not allowed for medical use. We here performed a theoretical three-dimensional study of known zinc ionophores, together with a computational energetic study and propose that some dietary flavonoids, glutathione and amino acids could form zinc complexes and facilitate the transport of zinc, with the possible biological implications and potential health benefits of these natural compounds. The study is based on obtaining a molecular conformational structure of the zinc complexes with the lowest possible energy content. The discovery of novel substances that act as zinc ionophores is an attractive research topic that offers exciting opportunities in medicinal chemistry. We propose that these novel complexes could be promising candidates for drug design to provide new solutions for conditions and diseases related to zinc deficiency or impairment derived from the dysregulation of this important metal., Junta de Castilla y León y Fondo Europeo de Desarrollo Regional (FEDER) - (Projects VA115P17 and VA149G18), Fondo Europeo de Desarrollo Regional (FEDER) y Agencia Canaria de Investigación, Innovación y Sociedad de la Información (ACIISI) del Gobierno de Canarias - (Project ProID2020010134), CajaCanarias (project 2019SP43), Ministerio de Economía, Industria y Competitividad - (Grant PID2019-105838RB-C31)

The development of a bidirectional catalyst for oxygen reduction and water oxidation is the key to establishing sustainable energy transduction from renewable resources. We report a stable homogene...

Materials that exhibit nanooptomechanical transduction in their single-crystal form have prospective use in light-driven molecular machinery, nanotechnology, and quantum computing. Linkage photoisomerization is typically the source of such transduction in coordination complexes, although the isomers tend to undergo only partial photoconversion. We present a nanooptomechanical transducer, trans-[Ru(SO2)(NH3)4(3-bromopyridine)]tosylate2, whose S-bound η1-SO2 isomer fully converts into an O-bound η1-OSO photoisomer that is metastable while kept at 100 K. Its 100% photoconversion is confirmed structurally via photocrystallography, while single-crystal optical absorption and Raman spectroscopies reveal its metal-to-ligand charge-transfer and temperature-dependent characteristics. This perfect optical switching affords the material good prospects for nanooptomechanical transduction with single-photon control.

The carbon nanotube (CNT) yarn supercapacitor has high potential for in vivo energy storage because it can be used in aqueous environments and stitched to inner parts of the body, such as blood vessels. The biocompatibility issue for frequently used pseudocapacitive materials, such as metal oxides, is controversial in the human body. Here, we report an implantable CNT yarn supercapacitor inspired by the cellular redox system. In all living cells, nicotinamide adenine dinucleotide (NAD) is a key redox biomolecule responsible for cellular energy transduction to produce adenosine triphosphate (ATP). Based on this redox system, CNT yarn electrodes were fabricated by inserting a twist in CNT sheets with electrochemically deposited NAD and benzoquinone for redox shuttling. Consequently, the NAD/BQ/CNT yarn electrodes exhibited the maximum area capacitance (55.73 mF cm-2 ) under physiological conditions, such as phosphate-buffered saline and serum. In addition, the yarn electrodes showed a negligible loss of capacitance after 10 000 repeated charge/discharge cycles and deformation tests (bending/knotting). More importantly, NAD/BQ/CNT yarn electrodes implanted into the abdominal cavity of a rat's skin exhibited the stable in vivo electrical performance of a supercapacitor. Therefore, these findings demonstrate a redox biomolecule-applied platform for implantable energy storage devices.

The bacterial skin studied here is a several centimeter-wide colony of Acetobacter aceti living on a cellulose-based hydrogel. We demonstrate that the colony exhibits trains of spikes of extracellular electrical potential, with amplitudes of the spikes varying from 1 to 17 mV. The bacterial pad responds to mechanical stimulation with distinctive changes in its electrical activity. While studying the passive electrical properties of the bacterial pad, we found that the pad provides an open-circuit voltage drop (between 7 and 25 mV) and a small short-circuit current (1.5–4 nA). We also observed by pulsed tomography and spatially resolved impedance spectroscopy that the conduction occurs along preferential paths, with the peculiar side-effect of having a higher resistance between closer electrodes. We speculate that the Acetobacter biofilms could be utilized in the development of living skin for soft robots: such skin will act as an electrochemical battery and a reactive tactile sensor. It could even be used for wearable devices.

In this study the low-temperature sintering effects and improved piezoelectric properties of CuO-doped 0.69 Pb(Zr0.47Ti0.53)O3-0.31[Pb(Zn0.4Ni0.6)1/3Nb2/3]O3 ceramics were investigated. At high temperatures, a sintered Pb(Zr,Ti)O3–Pb(Zn,Ni)NbO3 material has excellent piezoelectric properties such as a high piezoelectric charge coefficient (d33), high electromechanical coupling coefficient (kp), and high relative dielectric permittivity (er). However, low-temperature sintering of functional ceramics is important for industrial device applications. For sensor applications, sintering or fabrication temperature is important because processing temperatures can interfere with process and material compatibility. Therefore, in this study, low-temperature sintering effects were investigated by employing low-temperature sintering aids while maintaining the piezoelectric properties. CuO was selected as the sintering aid for these applications. We will investigate and discuss the effects of the low-temperature sintering aid of CuO on the Pb(Zr,Ti)O3–P(Zn,Ni)NbO3 material in device applications. By employing the CuO dopant to Pb(Zr,Ti)O3–P(Zn,Ni)NbO3 material, the strain and transduction values were increased while reducing the sintering temperature.

Single-crystal nanooptomechanical transduction occurs in [Ru(SO2)(NH3)4(H2O)]chlorobenzenesulfonate2, reaching maximal levels within 40 s at 100 K when photostimulated by 505 nm light. Its in situ light-induced crystal structure reveals the molecular origins of this optical actuation: 26.0(3)% of the η1-SO2 ligand photoconverts into an η1-OSO photoisomer which, in turn, induces a 49.6(9)° arene ring rotation in its neighbouring counter ion.

The self-assembled systems of surfactants/polymers, which are capable of supporting energy funneling between fluorophores, have recently gained significant attraction. Surfactant and polymeric micelles form nanoscale structures spanning a radius of 2-10 nm are generally suitable for the transduction of energy among fluorophores. These systems have shown great potential in Förster resonance energy transfer (FRET) due to their unique characteristics of being aqueous based, tendency to remain self-assembled, spontaneous formation, tunable nature, and responsiveness to different external stimuli. This review presents current developments in the field of energy transfer, particularly the multi-step FRET processes in the self-assembled nanostructures of surfactants/polymers. The part one of this review presents a background and brief overview of soft systems and discusses certain aspects of the self-assemblies of surfactants/polymers and their co-solubilization property to bring fluorophores to close proximity to transduce energy. The second part of this review deals with single-step and multi-step FRET in the self-assemblies of surfactants/polymers and links FRET systems with advanced smart technologies including multicolor formation, data encryption, and artificial antenna systems. This review also discusses the diverse examples in the literature to present the emerging applications of FRET. Finally, the prospects regarding further improvement of FRET in self-assembled soft systems are outlined.

A detailed understanding of the fundamental processes that govern mechanical transduction in covalent polymer mechanochemistry is essential to advance innovation in this field. In contrast to progress in the development of new mechanophores, the influence of polymer structure and composition on mechanochemical activity has received relatively little attention. In order to address this gap in knowledge, a continuous flow system with synchronous UV–vis absorption capabilities was designed to quantify the ultrasound-induced mechanical activation of a spiropyran mechanophore in real-time. Measurements of reaction kinetics with polymer tethers of varying repeating unit structure demonstrate that degree of polymerization is the key descriptor of mechanochemical activity, independent of molecular weight and pendant group constitution. These results have important implications for the rationalization of mechanochemical properties and the design of new mechanochemically active polymer systems.

Phytochrome photoreceptors operate via photoisomerization of a bound bilin chromophore. Their typical architecture consists of GAF, PAS and PHY domains. Knotless phytochromes lack the PAS domain, while retaining photoconversion abilities, with some being able to photoconvert with just the GAF domain. Therefore, we investigated the ultrafast photoisomerization of the Pr state of a knotless phytochrome to reveal the effect of the PHY domain and its “tongue” region on the transduction of the light signal. We show that the PHY domain does not affect the initial conformational dynamics of the chromophore. However, it significantly accelerates the consecutively induced reorganizational dynamics of the protein, necessary for the progression of the photoisomerization. Consequently, the PHY domain keeps the bilin and its binding pocket in a more reactive conformation, which decreases the extent of protein reorganization required for the chromophore isomerization. Thereby, less energy is lost along nonproductive reaction pathways, resulting in increased efficiency., More reactive, more efficient: The influence of the PHY domain on the photoconversion of a knotless phytochrome was investigated. The interaction of its “tongue” region with the GAF domain keeps the bilin chromophore and the binding pocket in a more reactive conformation. This results in accelerated reorganization of the protein environment necessary to accommodate the photoisomerization of the chromophore and, in effect, in an increased overall quantum efficiency.

Electrochemiluminescence (ECL) is a powerful transduction technique in biosensing and diagnostics, while mechanistic studies are still scarce. Herein we report the combined use of microtube electrode (MTE) and microscopy to measure the thickness of ECL layer (TEL) to decipher reaction mechanisms. For the classical system involving tris(2,2'-bipyridyl)ruthenium and tri-n-propylamine, the ECL pattern generated at the MTE tends to change from ring to spot upon increasing the luminophore concentration, with the TEL varying from ca. 3.1 μm to >4.5 μm. This variation is rationalized to arise from the contribution of the so-called catalytic route. While using 2-(dibutylamino)ethanol as the co-reactant, the ECL pattern remains ring-shaped and independent on the luminophore concentration. The TEL in this case is ca. 2.1 μm, implying that ECL generation is always surface-confined. MTEs can thus act as optical rulers for measuring the TEL and providing insightful mechanistic information.

The article reports an innovative optical system that is designed to interrogate the health condition of macroscopically intact rail specimens by measuring its inherent nonlinearity using the narrowband Rayleigh waves. A line-arrayed pattern is developed through the optical system that generates narrowband Rayleigh waves with high power on the surface of the rail. As a result of lattice-anharmonicity, a second harmonic is produced in the wave that is sensed by a scanning laser Doppler vibrometer. The spectral amplitudes of the first and generated second harmonics are used to calculate the inherent nonlinearity using an amplitude-based nonlinearity equation. These measurements are carried out on the head, web, and foot of the rail. The performance of the non-contact experiment is also compared with that of a contact experiment carried out using wedge transducers. The experimentally evaluated nonlinearity of the rail steel is further compared with that obtained using a physics-based nonlinearity equation that relies on the higher-order elastic constants. Agreement of the results shows that the new optical system is effective in generating Rayleigh waves in rails and thereby measuring the inherent nonlinearity of the rail track. The estimation of inherent nonlinearity may help in diagnosing the health status of the macroscopically intact rail specimens in terms of their microstructural consistency and level of dissolved impurities before fixing them on a track.

Nano-sensor materials, especially if they target biological purposes, require fine control and tuning of the properties at the molecular scale when intramolecular properties have to be exploited, for example, in optical sensors. By means of optical spectroscopies (namely, spectrophotometry, spectrofluorimetry, and surface differential reflectivity), we demonstrate that thin films of porphycene show a spectacular chromatic change when exposed to acid vapors (specifically to hydrochloric acid). After exposure, the original optical properties of the porphycene films are recovered within a few seconds and without any thermal annealing. In addition, since clear spectroscopic signatures are observed both in absorption and in reflectivity, the parent porphycene is shown to be suitable even for deposition of films onto opaque substrates. These findings are of significant interest in view of potential engineering of the molecules and implementation in devices.

Five new and one unsual known bioactive compounds have been isolated from the methanol extract of Kuji amber which was subjected to silica gel column chromatography in order to yield lipophilic compounds. A new clerodane derivative, named Kujione A (15-nor-2-oxo-3-cleroden-13-ol), was isolated from the medium polar fractions. This was done using Kujione A’s growth-restoring activity against a mutant Saccharomyces cerevisiae strain (zds1Δ erg3Δ pdr1/3Δ) that is hypersensitive with respect to Ca²+-signal transduction. The structure was elucidated by spectroscopic data, HREIMS, along with 1D- and 2D-NMR, among others. 15-norclerodane has been categorized as a new and distinct compound because it has a conjugated carbonyl functional group; it has not been found in isolated constituents from Kuji amber.

Nonlinear energy harvesting devices in the form of stiffness nonlinearity have emerged as among the effective solutions to overcome the performance limit of linear energy harvesting devices. However, up to now, researches on the nonlinear devices are only focusing on the ability to widen the bandwidth while the limit of employing linear transduction coefficient in a nonlinear system has yet to be heavily discussed. This paper investigates on the transduction coefficient for both linear and nonlinear systems of an electromagnetic energy harvesting device as a function of the excitation frequency. It is proven that the transduction coefficient of the nonlinear device is larger than its equivalent linear device, especially in the multi-stable solutions region. In common practice, the nonlinearity in the nonlinear system is considered weak, and its transduction coefficient is assumed to converge to the one produced by the linear system. The limits to which the transduction coefficient of a linear system can be employed on the nonlinear system were drawn based on the experimental analysis conducted on the proposed device. The device was designed to perform as a linear or nonlinear system, where the degree of nonlinearity was changed by varying the gap between the magnets. The limit of the transduction coefficient was determined from the analysis of the harmonic ratio. The results show that the linear transduction coefficient is valid to be employed to the nonlinear system when the harmonic ratio is less than five per cent at the multi-stable solutions region.

Large transduction coefficient ( d 33 × g 33 ) is difficult to obtain in piezoelectric ceramics because these two parameters show opposite trends with compositional modifications. Herein, the Pb(Zr0.53Ti0.47)O3 ceramic powders were calcinated under different temperatures (A:830 °C, B:860 °C, and C:890 °C), and then mixed together according to different weight ratios (1A:1B:1C, 1A:2B:1C, 1A:2B:3C and 3A:2B:1C) for ceramics preparation. Both d33 and g33 are improved successfully, and the transduction coefficient with the weight ratio of 1A:2B:3C reaches up to 17,500 × 10−15 m2/N, which is 60 % higher than that with the powders calcinated under 830 °C, and at least twice those of commercial PZT-4, PZT-5A and PZT-8 ceramics. The improved transduction coefficient is owing to the enhanced piezoelectric constant and spontaneous polarization resulted from the increased grain size, relative density and the fraction of tetragonal phase. These results indicate that this is a simple but effective way to tailor the transduction coefficient in piezoelectric ceramics.

Large-conductance Ca 2+ and voltage-activated K + (BK) channels control membrane excitability in many cell types. BK channels are tetrameric. Each subunit is composed of a voltage sensor domain (VSD), a central pore-gate domain, and a large cytoplasmic domain (CTD) that contains the Ca 2+ sensors. While it is known that BK channels are activated by voltage and Ca 2+ , and that voltage and Ca 2+ activations interact, less is known about the mechanisms involved. We explore here these mechanisms by examining the gating contribution of an interface formed between the VSDs and the αB helices located at the top of the CTDs. Proline mutations in the αB helix greatly decreased voltage activation while having negligible effects on gating currents. Analysis with the Horrigan, Cui, and Aldrich model indicated a decreased coupling between voltage sensors and pore gate. Proline mutations decreased Ca 2+ activation for both Ca 2+ bowl and RCK1 Ca 2+ sites, suggesting that both high-affinity Ca 2+ sites transduce their effect, at least in part, through the αB helix. Mg 2+ activation also decreased. The crystal structure of the CTD with proline mutation L390P showed a flattening of the first helical turn in the αB helix compared to wild type, without other notable differences in the CTD, indicating that structural changes from the mutation were confined to the αB helix. These findings indicate that an intact αB helix/VSD interface is required for effective coupling of Ca 2+ binding and voltage depolarization to pore opening and that shared Ca 2+ and voltage transduction pathways involving the αB helix may be involved.

SO2 linkage photoisomerization in crystalline ruthenium-based complexes has demonstrated nanophotonic phenomena such as optical switching and nano-optomechanical transduction. Molecular insights in...

Chemically modified field-effect transistor (FET) nanodevices were shown to be a selective and extremely sensitive detection platform. In FET-based sensors, signal amplification and transduction is based on electrostatic gating of the nanometric semiconductor channel by analyte–receptor interactions, which measurably affect the transconductance of the device. However, chemically modified FETs must overcome several fundamental limitations before they can be effectively deployed as real-time sensors for bioevents occurring on their surface in complex biofluids. Here, we demonstrate the development of amperoFET devices for the real-time continuous monitoring of small molecular metabolites in biofluids. The surface of the nanowires is covalently modified with a redox reversible moiety, which is easily oxidized in the presence of H2O2. The reversible redox transformation of the surface-confined molecules is carried out by a hot electron injection mechanism, conducted simply by the modulation of the source–drain current through the nanoFET sensing device. By this approach, electrons may be injected by the nanowire element into the surface-confined redox moiety and thus maintain a whole-electrically actuated redox system in which the oxidation state is completely controlled by the current applied to the amperoFET system. The modulation of the source–drain current allows the control of the reduced versus oxidized redox moieties population on the nanowire surface, and this, in turn, is applied as the main sensing mechanism. At a given constant source–drain and gate voltage, the chemical perturbation exerted by the presence of chemical oxidants in the tested biofluid will lead to a measurable conductance change. Alteration in the concentration of the specific metabolite will chemically regulate the extent of perturbation applied to the redox system, which can be utilized for the quantification of the molecular metabolite of interest. These ‘equilibrium’-type sensors are fully electrically operated and can be further used in implantable sensing applications.

Dye-sensitized solar cells (DSSCs) have been highlighted as the promising alternative to generate clean energy based on low pay-back time materials. These devices have been designed to mimic solar energy conversion processes from photosynthetic organisms (the most efficient energy transduction phenomenon observed in nature) with the aid of low-cost materials. Recently, light-harvesting complexes (LHC) have been proposed as potential dyes in DSSCs based on their higher light-absorption efficiencies as compared to synthetic dyes. In this work, photo-electrochemical hybrid devices were rationally designed by adding for the first time Leu and Lys tags to heterologously expressed light-harvesting proteins from Chlamydomonas reinhardtii, thus allowing their proper orientation and immobilization on graphene electrodes. The light-harvesting complex 4 from C. reinhardtii (LHC4) was initially expressed in Escherichia coli, purified via affinity chromatography and subsequently immobilized on plasma-treated thin-film graphene electrodes. A photocurrent density of 40.30 \pm 9.26 \mu A/cm2 was measured on devices using liquid electrolytes supplemented with a phosphonated viologen to facilitate charge transfer. Our results suggest that a new family of graphene-based thin-film photovoltaic devices can be manufactured from rationally tagged LHC proteins and opens the possibility to further explore fundamental processes of energy transfer for biological components interfaced with synthetic materials., Comment: 17 pages, 4 figures

Significance Self-trapped light beams hold potential for optical interconnects, applications in image transmission, rerouting light, logic gates for computing and, importantly, for the next-generation light-guiding-light signal processing, which envisions a circuitry-free and reconfigurable photonics powered by the dynamic interactions of self-trapped beams. In conventional nonlinear materials, however, self-trapping suffers from either the need for large incident beam powers and loss of beam interactions at large distances, or it is slow and irreversible. We show that rapidly and repeatably switchable self-trapped laser beams with remote communication capabilities can be elicited at exceptionally small intensities in a pliant, processable hydrogel functionalized with a chromophore. The ability to generate self-trapped beams with this unique set of properties offers unprecedented opportunities to develop light-guiding-light technologies., Next-generation photonics envisions circuitry-free, rapidly reconfigurable systems powered by solitonic beams of self-trapped light and their particlelike interactions. Progress, however, has been limited by the need for reversibly responsive materials that host such nonlinear optical waves. We find that repeatedly switchable self-trapped visible laser beams, which exhibit strong pairwise interactions, can be generated in a photoresponsive hydrogel. Through comprehensive experiments and simulations, we show that the unique nonlinear conditions arise when photoisomerization of spiropyran substituents in pH-responsive poly(acrylamide-co-acrylic acid) hydrogel transduces optical energy into mechanical deformation of the 3D cross-linked hydrogel matrix. A Gaussian beam self-traps when localized isomerization-induced contraction of the hydrogel and expulsion of water generates a transient waveguide, which entraps the optical field and suppresses divergence. The waveguide is erased and reformed within seconds when the optical field is sequentially removed and reintroduced, allowing the self-trapped beam to be rapidly and repeatedly switched on and off at remarkably low powers in the milliwatt regime. Furthermore, this opto-chemo-mechanical transduction of energy mediated by the 3D cross-linked hydrogel network facilitates pairwise interactions between self-trapped beams both in the short range where there is significant overlap of their optical fields, and even in the long range––over separation distances of up to 10 times the beam width––where such overlap is negligible.

A self-powered temperature sensor based on Seebeck effect transduction was designed for photothermal-thermoelectric coupled immunoassay of α-fetoprotein (AFP). In this system, glucose oxidase (GOx)-conjugated detection antibody was first captured onto the microplate by target-induced sandwich-type immunoreaction. Thereafter, the as-generated hydrogen peroxide via the GOx-glucose system oxidized 3,3',5,5'-tetrametylbenzidine (TMB) into photothermal product oxidized TMB (ox-TMB). Under near-infrared (NIR) laser irradiation, the temperature change of ox-TMB was read out in an electrical signal by the flexible thermoelectric module in a 3D-printed integrated detection device. Under optimal conditions, the photothermal-thermoelectric coupled immunoassay exhibited a limit of detection of 0.39 ng mL

Force can induce remarkable non-destructive transformations along a polymer, but we have a limited understanding of the energy transduction and product distribution in tandem mechanochemical reactions. Ladderanes consist of multiple fused cyclobutane rings and have recently been used as monomeric motifs to develop polymers that drastically change their properties in response to force. Here we show that [4]-ladderane always exhibits 'all-or-none' cascade mechanoactivations and the same stereochemical distribution of the generated dienes under various conditions and within different polymer backbones. Transition state theory fails to capture the reaction kinetics and explain the observed stereochemical distributions. Ab initio steered molecular dynamics reveals unique non-equilibrium dynamic effects: energy transduction from the first cycloreversion substantially accelerates the second cycloreversion, and bifurcation on the force-modified potential energy surface leads to the product distributions. Our findings illustrate the rich chemistry in closely coupled multi-mechanophores and an exciting potential for effective energy transduction in tandem mechanochemical reactions.

Based on the strong demand for self-powered wearable electronic devices, flexible piezoelectric energy harvesters (FPEHs) have recently attracted much attention. A polymer-based piezocomposite is the core of an FPEH and its transduction coefficient (d33 × g33) is directly related to the material's power generation capacity. Unfortunately, the traditional 0–3 type design method generally causes a weak stress transfer and poor dispersion of the filler in the polymer matrix, making it difficult to obtain a high d33 × g33. In this work, a unique interconnected skeleton design strategy has been proposed to overcome these shortcomings. By using the freeze-casting method, an ice-templated 2–2 type composite material has been constructed with the popular piezoelectric relaxor 0.2Pb(Zn1/3Nb2/3)O3–0.8Pb(Zr1/2Ti1/2)O3 (PZN–PZT) as the filler and PDMS as the polymer matrix. Both the theoretical simulation and the experimental results revealed a remarkable enhancement in the stress transfer ability and piezoelectric response. In particular, the 2–2 type piezocomposite has an ultrahigh transduction coefficient of 58 213 × 10−15 m2 N−1, which is significantly better than those of previously reported composite materials, and even textured piezoceramics. This work provides a promising paradigm for the development of high-performance FPEH materials.

Conformation-based stimuli-responsive sensors utilize a wide range of macromolecules (referred to as probe in this manuscript) and read-out methods. The review focuses on the variables associated with the mechanistic confirmation change centered around two transduction outputs: electrochemical and fluorescence resonance energy transfer. The electrochemical readout is limited in that the responsive material is bound between the electrode surface and an electroactive tag; interaction with analyte changes the distance between the electrode surface and the electroactive tag. Variables discussed in electrochemical stimuli-responsive sensor outputs include redox tag choice, electrode surface packing density, probe architectures, and redox tag location. Fluorescence resonance energy transfer readout uses a solution-free polymer distance where a conformational change induces a change in distance between a donor fluorophore and an acceptor fluorophore, thereby affecting the degree of nonradiative energy transfer from the donor to the acceptor. Variables discussed in fluorescence resonance energy transfer readouts include fluorophore types and sensor architecture. While there are already many examples of this in the literature, we believe this to be a fertile area for further development.

The catalytic activity of thrombin and other enzymes of the blood coagulation and complement cascades is enhanced significantly by binding of Na+ to a site >15 A away from the catalytic residue S195, buried within the 180- and 220- loops that also contribute to the primary specificity of the enzyme. Rapid kinetics support a binding mechanism of conformational selection where the Na+ binding site is in equilibrium between open (N) and closed (N*) forms and the cation binds selectively to the N form. Allosteric transduction of this binding step produces enhanced catalytic activity. Molecular details on how Na+ gains access to this site and communicates allosterically with the active site remain poorly defined. In this study, we show that the rate of the N ∗ → N transition is strongly correlated with the analogous E ∗ → E transition that governs the interaction of synthetic and physiologic substrates with the active site. This correlation supports the active site as the likely point of entry for Na+ to its binding site. Mutagenesis and structural data rule out an alternative path through the pore defined by the 180- and 220- loops. We suggest that the active site communicates allosterically with the Na+ site through a network of H-bonded water molecules that embeds the primary specificity pocket. Perturbation of the mobility of S195 and its H-bonding capabilities alters interaction with this network and influences the kinetics of Na+ binding and allosteric transduction. These findings may have general mechanistic relevance for Na+-activated proteases and allosteric enzymes.

In this issue of Structure, Nojima et al. (2021) report the structure of the PGE2–EP4–Gs complex by cryo-electron microscopy. This work shows unique modes of ligand binding, transduction mechanism, and G protein coupling of EP4, and serves as a starting point for development of more selective drugs.

Rare-earth-ion doped crystals are a promising platform for applications in microwave-to-optical transduction. Erbium is of special interest because of its telecom wavelength optical transitions. This work investigates the optical and electron-spin properties of Er${}^{3+}$:YVO${}_{4}$. An initial transduction of classical microwave signal using this material is demonstrated. The measured strong optical dipole moment and narrow ensemble inhomogeneities make Er${}^{3+}$:YVO${}_{4}$ a promising material for microwave-to-optical transduction.

Hearing involves two fundamental processes: mechano-electrical transduction and signal amplification. Despite decades of studies, the molecular bases for both remain elusive. Here, we show how prestin, the electromotive molecule of outer hair cells (OHCs) that senses both voltage and membrane tension, mediates signal amplification by coupling conformational changes to alterations in membrane surface area. Cryoelectron microscopy (cryo-EM) structures of human prestin bound with chloride or salicylate at a common "anion site" adopt contracted or expanded states, respectively. Prestin is ensconced within a perimeter of well-ordered lipids, through which it induces dramatic deformation in the membrane and couples protein conformational changes to the bulk membrane. Together with computational studies, we illustrate how the anion site is allosterically coupled to changes in the transmembrane domain cross-sectional area and the surrounding membrane. These studies provide insight into OHC electromotility by providing a structure-based mechanism of the membrane motor prestin.

Myosin is biological molecular motor that transduces the chemical energy ATP hydrolysis into force and/or motion to drives many forms of cellular motility from muscle contraction to cell division. While the transduction process has been extensively studied key details remain unclear. Most importantly the timing of the force-generating powerstroke relative to the release of phosphate (Pi), a product of ATP hydrolysis, is not clear and the source of intense debate. We examined the ability of single-headed myosin Va to generate a displacement (i.e. powerstroke) of an actin filament in a kinetic, fluorescent energy transfer (FRET) and single molecule laser trap assays while maintaining Pi in its catalytic site by introducing a mutation that impedes Pi-release from the catalytic site (S217A). Kinetic experiments confirmed that the Pi-release rate was slowed ~5-fold by the S217A substitution, and FRET experiments suggested that the mutation slowed myosin’s rate of attachment to actin. At the single molecule level Wild type myosin Va (WT) generated a 7 nm powerstroke at a rate of ~600/s and the S217A myosin generated a statistically similar size powerstroke (8nm) at a similar rate (600/s) despite impeding the release of Pi from the active site. These findings are consistent with myosin Va generating a powerstroke while Pi is still in the catalytic site, and therefore challenge the hypothesis that Pi-release gates, and therefore precedes, the powerstroke. Our findings imply that myosin’s key mechanical event is triggered by binding to the actin filament, and not by the biochemical event of Pi-release. This provides important new insight into the mechanism of energy transduction by myosin, and evolutionarily related motor proteins.

Citrus species grown to different localities of Kokrajhar district were identified in 2016 and thereafter another investigation was undertaken for determination of chlorophyll content in seven selected Citrus species during 2017-18. The primary aim of the study was to find out the chlorophyll concentration and its relationship with growth and development of the said plant species. Therefore, estimation and quantification of Chl a, Chl b and total chlorophyll (Chl a + Chl b) content in each species were carried out in Biotech Hub laboratory. An established fact is that green plants synthesize a wide range of primary and secondary metabolites in different quantity. Chlorophylls belong to the primary metabolites that give the color of the leaves and fruits, especially in the unripe stage. The spectral properties of chlorophylls are essential in harvesting light energy and in the transduction of absorbed light energy for photosynthesis. Like other plants, the variation of leaf colour as well as photosynthetic activity in Citrus species is dependent on chlorophyll concentration. Chlorophyll content determines the photosynthetic capacity of the plant per unit area of leaf, stress and nutritional deficiencies. The study has revealed district variation in terms of chlorophyll concentration among the studied species.

Myosins are a family of motor proteins responsible for various forms of cellular motility, including muscle contraction and vesicular transport. The most fundamental aspect of myosin is its ability to transduce the chemical energy from the hydrolysis of ATP into mechanical work, in the form of force and/or motion. A key unanswered question of the transduction process is the timing of the force-generating powerstroke relative to the release of phosphate (Pi ) from the active site. We examined the ability of single-headed myosin Va to generate a powerstroke in a single molecule laser trap assay while maintaining Pi in its active site, by either elevating Pi in solution or by introducing a mutation in myosin's active site (S217A) to slow Pi -release from the active site. Upon binding to the actin filament, WT myosin generated a powerstoke rapidly (≥500 s-1 ) and without a detectable delay, both in the absence and presence of 30 mM Pi . The elevated levels of Pi did, however, affect event lifetime, eliminating the longest 25% of binding events, confirming that Pi rebound to myosin's active site and accelerated detachment. The S217A construct also generated a powerstroke similar in size and rate upon binding to actin despite the slower Pi release rate. These findings provide direct evidence that myosin Va generates a powerstroke with Pi still in its active site. Therefore, the findings are most consistent with a model in which the powerstroke occurs prior to the release of Pi from the active site.

Mechanically coupled proton transduction offers potential for stress-responsive polymeric materials whose properties can be switched via acid-triggered coloration, polymerization/cross-linking, or degradation. The utility of currently available mechanoacids, however, is limited by modest force-free stability or a scissile response that caps mechanoacid generation at one proton per strained polymer chain. Here, we report a new mechanoacid based on 2-methoxy-substituted gem-dichlorocyclopropane (MeO-gDCC). Pulsed ultrasonication leads to the mechanochemical ring opening of the MeO-gDCC and the subsequent elimination of either HCl or MeCl, with ∼0.58 equiv of HCl released per mechanophore activation and ∼67 protons per chain scission event. Single-molecule force spectroscopy reveals that the methoxy substituent lowers the force required for rapid (kopen ∼102 s-1) ring opening to ca. 900 pN, vs 1300 pN required for the parent gDCC. The utility of the mechanoacid is demonstrated in silicone elastomers, where its mechanical activation leads to a strain-triggered color change prior to fracture of the elastomer. The postactivation kinetics of coloration are used to demonstrate a new concept in mechanochromism, namely, a spectroscopic indicator of not only whether and where a mechanical event has occurred but when it occurred.

Protocell analogs (lipid vesicles) to modern cell membranes have been postulated as compartments that may have been involved in primordial metabolism during the transition from geochemistry to biochemistry on early Earth. The transduction of light energy into chemical energy for metabolism was a key step in the transition from the earliest metabolisms to phototrophy. Photocatalytic minerals may have served the role of enzymes during these transitional stages. Here, we demonstrate a simple photoheterotrophic protometabolism promoted by photocatalytic minerals across a model protocell (vesicle) membrane. These minerals in the extra-vesicular medium utilized light energy to drive a coupled, multi-step transmembrane electron transfer reaction (TMETR), while simultaneously generating a transmembrane pH gradient and reducing nicotinamide adenine dinucleotide (NAD+) to NADH within the vesicle. The proton gradient or chemiosmotic potential could have provided a basis for adenosine triphosphate (ATP) synthesis and NADH could potentially have driven further metabolic chemistry inside the protocells.

Conversion of the free energy of NTP hydrolysis efficiently into mechanical work and/or information by transducing enzymes sustains living systems far from equilibrium, and so has been of interest for many decades. Detailed molecular mechanisms, however, remain puzzling and incomplete. We previously reported that catalysis of tryptophan activation by tryptophanyl-tRNA synthetase, TrpRS, requires relative domain motion to re-position the catalytic Mg(2+) ion, noting the analogy between that conditional hydrolysis of ATP and the escapement mechanism of a mechanical clock. The escapement allows the time-keeping mechanism to advance discretely, one gear at a time, if and only if the pendulum swings, thereby converting energy from the weight driving the pendulum into rotation of the hands. Coupling of catalysis to domain motion, however, mimics only half of the escapement mechanism, suggesting that domain motion may also be reciprocally coupled to catalysis, completing the escapement metaphor. Computational studies of the free energy surface restraining the domain motion later confirmed that reciprocal coupling: the catalytic domain motion is thermodynamically unfavorable unless the PPi product is released from the active site. These two conditional phenomena—demonstrated together only for the TrpRS mechanism—function as reciprocally-coupled gates. As we and others have noted, such an escapement mechanism is essential to the efficient transduction of NTP hydrolysis free energy into other useful forms of mechanical or chemical work and/or information. Some implementation of both gating mechanisms—catalysis by domain motion and domain motion by catalysis—will thus likely be found in many other systems.

The thermomechanical motion imposes the fundamental noise limit in room-temperature resonant sensors and oscillators. Due to the inherently low sensitivity of capacitive transduction in microelectromechanical (MEM) resonators, its effects are often masked by noise in the subsequent amplifier and measurement stages. In this work, we demonstrate a capacitive transduction scheme for measuring kHz-MHz frequency MEM resonators across 1 $\mu \text{m}$ capacitive gaps with 99.8% thermomechanical-noise-limited resolution. We delineate the transimpedance gain and noise of our custom off-chip differential transimpedance amplifier setup. The thermomechanical noise spectrum can provide estimates of the resonant frequency, quality factor, and electromechanical transduction factor comparable to the commonly used driven response, without the downsides of capacitive feedthrough or nonlinearity. [2019-0115]

© 2019 Elsevier B.V. This study has focussed on the effect of low temperature storage on the postharvest ripening of green tomatoes; more specifically, on the ethylene signal transduction in relation to the ethylene biosynthesis pathway. To this end, the first elements of the ethylene signal transduction, ethylene receptors, CTR and EIN2 have been analysed in tomatoes stored at three different temperatures in terms of both their gene and protein expression levels. These results have been related to quality changes and enzymes and intermediates of the ethylene biosynthesis pathway to better understand the ethylene control of ripening under low temperatures. The first changes observed during low temperature storage took place at the ethylene biosynthesis level, which might enhance changes in the ethylene signal transduction. Although expression of most ethylene signalling genes decreased with chilling, none of the protein levels showed a significant decrease, pointing at a differential regulation at the gene and protein level. ispartof: POSTHARVEST BIOLOGY AND TECHNOLOGY vol:155 pages:1-10 status: published

Single-crystal optical actuators are emerging as a prospective material form for nano-optical mechanical switching, sensing, or transduction device applications in nanotechnology and quantum techno...

The purpose of this manuscript is to propose a mechanism for a cancer cure claim resulting from exogenous stimulation of cancer tumors by very intense pressure pulses (VIPPs) treatments from commercially available energy hardware (CellSonic). Could it be that exogenous continuous pulsating waves alter the cellular lipid bilayer; and this in turn also influence intracellular cell signaling? In Vitro experiments are presented supporting the above-stated thesis. The evidence will show via in vitro experiments how trapping energy from bursting oxygen bubbles induces static electricity discharges up to causing luminescence of intracellular lipid droplets. Figures and video recordings documenting the above-mentioned phenomena are presented. In summary, proposed is a mechanism explaining a cancer cure claim via VIPPs. 1 AAE: Idealized, designed wrote manuscript and conducted in vitro experiments possibly demonstrating a mechanism for VIPPs cancer cure. 2 SH: Added theoretical principles in the discussion supporting the proposed VIPPs mechanism to cancer cure.

This work reports the rubber electrostatic potential due to repeated strain as a function of time for periods as long as the lifetime of the sample. Rubber potential depends on two main contributions: hygroelectricity added to the mechanochemical reactions evidenced by spectroscopy and microscopy/microanalytical experiments. Hygroelectricity produces fast periodic charging in phase with rubber strain, while a slower charging process is assigned to the mechanochemical reaction products, in conjunction with residual hygroelectricity. This result explains the significant negative potential displayed by rubber over long periods in the absence of any external applied voltage. These findings may contribute to improving dielectric elastomer performance in many applications that are currently of great interest in robotics and energy harvesting. Additionally, electric potential real-time measurements show desirable features as a tool for real-time, non-contact detection of rubber structural change and fatigue.

We present a chemomechanical network model of the rotary molecular motor F1-ATPase which quantitatively describes not only the rotary motor dynamics driven by ATP hydrolysis but also the ATP synthesis caused by forced reverse rotations. We observe a high reversibility of F1-ATPase, that is, the main cycle of ATP synthesis corresponds to the reversal of the main cycle in the hydrolysis-driven motor rotation. However, our quantitative analysis indicates that torque-induced mechanical slip without chemomechanical coupling occurs under high external torque and reduces the maximal efficiency of the free energy transduction to 40–80% below the optimal efficiency. Heat irreversibly dissipates not only through the viscous friction of the probe but also directly from the motor due to torque-induced mechanical slip. Such irreversible heat dissipation is a crucial limitation for achieving a 100% free-energy transduction efficiency with biological nanomachines because biomolecules are easily deformed by external torque.

Two kinds of biologically active compounds were isolated from the MeOH extract of the Early Cretaceous Burmese amber [99 million years ago (Ma)], which is older than the K-Pg boundary (65 Ma). These compounds had inhibitory activity against the hypersensitive mutant yeast strain (zds1∆ erg3∆ pdr1∆ pdr3∆) with respect to Ca2+ signal transduction. They were identified as 16,17-bisnordehydroabietic acid (1) and 16,17-bisnorcallitrisic acid (2), respectively, on the basis of spectral analyses including HREIMS, 1D, and 2D NMR. Both have faint growth restoring activities around the clear inhibition zone against the mutant yeast on the 0.31–0.16 μg/spot. This is the first report of direct structural elucidation of 1 and 2 and the biologically active compounds derived from Burmese amber.

A different type of biologically active compound from Kuji amber (Late Cretaceous, Japan) before the K-Pg boundary [65 million years ago (Ma)] was isolated based on the growth-restoring activity of a mutant yeast involving Ca2+ signal transduction. It was identified as a spirolactone norditerpenoid, (4R*, 5S*, 8R*, 9R*, 10S*)-14,15,16,19-tetranor-labdan-13,9-olide (1) from spectral analyses with high-resolution electron ionization mass spectrometry (HREIMS), 1D and 2D nuclear magnetic resonance (NMR). Although the planar structure of 1 is known as an artificial derivative from marrubiin, it was isolated as a natural product from Kuji amber and its structure was elucidated for the first time. It had a growth-restoring activity against the mutant yeast through the direct or indirect inhibition of calcineurin activity [protein phosphatase, Mg2+/Mn2+-dependent 1A (PPM1A) activation]. Furthermore, the compound had potent inhibitory effect against the degranulation of rat basophilic leukemia 2H3 (RBL-2H3) cells.

A fundamental limitation of potentiometric ion sensors is their relatively low sensitivity due to the logarithmic dependence between potential and activity. Here we address this issue by exploring a recently developed coulometric transduction method for solid-contact ion-selective electrodes (SCISEs). Spin-coated thin-layer ion-selective membranes are used to lower the membrane resistance and shorten the response time of the SCISEs. When using coulometric transduction, an optimized design of the K+-SCISE is able to detect a concentration change of 5 μM at a concentration level of 5 mM, corresponding to a 0.1% change in K+ activity. This indicates that SCISEs can provide extremely high sensitivity when employing coulometric transduction. Impedance measurements show that the coulometric transduction process for the K+-SCISE is limited by diffusion even for very thin ion-selective membranes. On the other hand, the H+-SCISE shows a low impedance and a fast coulometric response that is related to the high mobility of H+ in the H+-selective polymeric membrane as well as in the solid contact layer. The coulometric transduction method was used to detect small changes of pH in seawater and found to improve the sensitivity compared to classical potentiometry. The coulometric method was briefly tested also for determining activity changes of K+ in a serum sample.

We consider the autonomous piston engine in a coupled cavity scheme in an optomechanical setup. Treating the radiation field as working fluid, we investigate the transduction of virtual photons due to ground state excitations. Rabi-like energy splittings and Casimir effect are shown by avoided crossing in the eigenfunction spectrum. Second order coherence functions are employed to analyze the bunching of the cavity and mechanical mode in optomechanical implementation of Brownian motors. The imbalance in occupation numbers of the working modes is investigated for the power for work extraction. We explore the guidance of the radiation field in work extraction. We study the synchronicity between virtual photon conversion and power in the mechanical mode. Generation and amplification of virtual photon transduction are modulated by mutual interactions between the qubit, piston, and mechanical mode in the absence of external driving fields.

Conveyances of physical energies (such as force, heat, and electricity) from one to another exist in nature and have initiated manifold useful applications. Piezothermic transduction refers to a change in the thermal conduction of a material when a mechanical strain is applied, which can be applied in high-performance pressure sensing and smart energy control. Here, we propose the piezothermic concept and investigate the mechanism of its transduction in three functional composite materials, that is, particle-reinforced composites, porous materials, and series-model materials. Theoretical models for analyzing relatedness effects of material properties (e.g., thermal conductivity, Young's modulus, and volume fraction) are established and validated by both finite element analyses and experimental measurements. The piezothermic transduction provides novel and promising strategies to implement high-performance mechanical sensing as well as energy control through optimizing composite materials. As a demonstration, a pressure sensor with a super high range-to-limit ratio of 50 000 that has a lower detection limit of 3.9 Pa and a large measurement range of 200 kPa is developed.

Poor selectivity is one important limitation of gas sensors based on chemisorption or physisorption. This poor selectivity is usually tackled through the use of a gas sensor array, whose individual elements have diverse selectivity. Gas identification can be achieved by analyzing the unique response patterns of the sensor array. However, such an approach is costly due to its complexity. In this paper, we investigate an alternative solution enabling single sensor gas identification through the integration of two transduction mechanisms in one sensor. We demonstrate this approach through the design of a novel dual transduction gas sensor capable of simultaneously detecting gas-induced variations in the mass and resistance of the sensing material. The relative independence of acquired gravimetric and resistive responses is shown to enable subsequent gas identification. In addition, the proposed approach can also improve the overall limit of detection (LOD) to different gases by exploiting the individual responses with the best LODs. The proposed dual transduction gas sensor was implemented by integrating a film bulk acoustic wave resonator (FBAR) together with interdigitated electrodes. A configurable dual-mode oscillator circuit is also proposed to simultaneously read-out both responses from the sensor.