Honeybee comb-inspired stiffness gradient-amplified catapult for solid particle repellency.

Natural surfaces that repel foreign matter are ubiquitous and crucial for living organisms. Despite remarkable liquid repellency driven by surface energy in many organisms, repelling tiny solid particles from surfaces is rare. The main challenge lies in the unfavourable scaling of inertia versus adhesion in the microscale and the inability of solids to release surface energy. Here we report a previously unexplored solid repellency on a honeybee's comb: a catapult-like effect to immediately eject pollen after grooming dirty antennae for self-cleaning. Nanoindentation tests revealed the 38-µm-long comb features a stiffness gradient spanning nearly two orders of magnitude from ~25 MPa at the tip to ~645 MPa at the base. This significantly augments the elastic energy storage and accelerates the subsequent conversion into kinetic energy. The reinforcement in energy storage and conversion allows the particle's otherwise weak inertia to outweigh its adhesion, thereby suppressing the unfavourable scaling effect and realizing solid repellency that is impossible in conventional uniform designs. We capitalize on this to build an elastomeric bioinspired stiffness-gradient catapult and demonstrate its generality and practicality. Our findings advance the fundamental understanding of natural catapult phenomena with the potential to develop bioinspired stiffness-gradient materials, catapult-based actuators and robotic cleaners.

Microstructural Evolution and Mechanical Properties of a Ni-Based Alloy with High Boron Content for the Pre-Sintered Preform (PSP) Application.

The pre-sintered preform (PSP) is an advanced technology for repairing the Ni-based superalloy blade in a turbine. In general, boron is added to the Ni-based superalloys in small quantities (<0.1 wt.%) to increase boundary strength and cohesivity. Despite this, the effect of high B content (>1.0 wt.%) on the microstructure evolution and mechanical properties in Ni-based superalloys for the PSP application is rarely studied. The variety, composition and evolution of the precipitates during solution heat treatment in the alloy with high B content were determined by EBSD, EPMA and SEM. The results indicate that Cr, W and Mo-rich M5B3 type borides precipitate from the matrix and its area fraction reaches up to about 8%. The area fraction of boride decreases with the prolonging of solution time and the increase of temperature higher than 1120 °C. The borides nearly disappear after solution treatment at 1160 °C for 2 h. The redissolution of boride and eutectic results in the formation of B-rich area with low incipient melting (about 1189 °C). It can bond metallurgically with the blade under the melting point of the blade, which decreases the precipitation of harmful phases of the blade after PSP repairing. The microhardness within the grain in the PSP work-blank first decreases (lower than 1160 °C) and then increases (higher than 1185 °C) with the increase of solution heat treatment temperature due to the dissolving and precipitation of borides. The tensile strength of the combination of PSP work-blank and Mar-M247 matrix at room temperature after solution treatment is related to the area fraction of boride, incipient melting and the cohesion between PSP work-blank and Mar-M247 matrix.

Self-Adaptive Droplet Bouncing on a Dual Gradient Surface.

Rapid detachment of impacting droplets from underlying substrate is highly preferred for mass, momentum, and energy exchange in many practical applications. Driven by this, the past several years have witnessed a surge in engineering macrotexture to reduce solid-liquid contact time. Despite these advances, these strategies in reducing contact time necessitate the elegant control of either the spatial location for droplet contact or the range of impacting velocity. Here, this work circumvents these limitations by designing a dual gradient surface consisting of a vertical spacing gradient made of tapered pillar arrays and a lateral curvature gradient characterized as macroscopic convex. This design enables the impacting droplets to self-adapt to asymmetric or pancake bouncing mode accordingly, which renders significant contact time reduction (up to ≈70%) for a broad range of impacting velocities (≈0.4-1.4 m s-1 ) irrespective of the spatial impacting location. This new design provides a new insight for designing liquid-repellent surfaces, and offers opportunities for applications including dropwise condensation, energy conversion, and anti-icing.

Achieving Extreme Pressure Resistance to Liquids on a Super-Omniphobic Surface with Armored Reentrants.

Static repellency and pressure resistance to liquids are essential for high-performance super-omniphobic surfaces. However, these two merits appear mutually exclusive in conventional designs because of their conflicting structural demands: Static liquid repellency necessitates minimal solid-liquid contact, which in turn inevitably undercuts the surface's ability to resist liquid invasion exerted by the elevated pressure. Here, inspired by the Springtail, these two merits can be simultaneously realized by structuring surfaces at two size scales, with a micrometric reentrant structure providing static liquid repellency and a nanometric reentrant structure providing pressure resistance, which dexterously avoids the dilemma of their structural conflicts. The nanometric reentrants are densely packed on the micrometric ones, serving as "armor" that prevents liquids invasion by generating multilevel energy barriers, thus naming the surface as the armored reentrants (AR) surface. The AR surface could repel liquids with very low surface tensions, such as silicone oil (21 mN m-1 ), and simultaneously resist great pressure from the liquids, exemplified by enduring the impact of low-surface-tension liquids under a high weber number (>400), the highest-pressure resistance ever reported. With its scalable fabrication and enhanced performance, our design could extend the application scope of liquid-repellent surfaces toward ultimate industrial settings.

Recent Progress on Bioinspired Antibacterial Surfaces for Biomedical Application.

Surface bacterial fouling has become an urgent global challenge that calls for resilient solutions. Despite the effectiveness in combating bacterial invasion, antibiotics are susceptible to causing microbial antibiotic resistance that threatens human health and compromises the medication efficacy. In nature, many organisms have evolved a myriad of surfaces with specific physicochemical properties to combat bacteria in diverse environments, providing important inspirations for implementing bioinspired approaches. This review highlights representative natural antibacterial surfaces and discusses their corresponding mechanisms, including repelling adherent bacteria through tailoring surface wettability and mechanically killing bacteria via engineering surface textures. Following this, we present the recent progress in bioinspired active and passive antibacterial strategies. Finally, the biomedical applications and the prospects of these antibacterial surfaces are discussed.

A new scaling number reveals droplet dynamics on vibratory surfaces.

HYPOTHESIS: Droplet spreading on surfaces is a ubiquitous phenomenon in nature and is relevant with a wide range of applications. In practical scenarios, surfaces are usually associated with certain levels of vibration. Although vertical or horizontal modes of vibration have been used to promote droplet dewetting, bouncing from immiscible medium, directional transport, etc., a quantitative understanding of how external vibration mediates the droplet behaviors remains to be revealed. METHODS: We studied droplets impacting on stationary and vibratory surfaces, respectively. In analogy to the Weber number We=ρUi2D0/γ, we define the vibration Weber number We*=ρUv2D0/γ to quantitively analyze the vibration-induced dynamic pressure on droplet behaviors on vibratory surfaces, where ρ,γ,D0,UiandUv are liquid density, surface tension, initial droplet diameter, impact velocity of the droplet, and velocity amplitude of vibration, respectively. FINDINGS: We demonstrate that the effect of vibration on promoting droplet spreading can be captured by a new scaling number expressed as We*/[We1\2sin(θ/2)], leading to (Dm - Dm0)/Dm0 âˆ We*/[We1\2sin(θ/2)], where θ is the contact angle, and Dm0 and Dm are the maximum diameter of the droplet on stationary and vibratory surfaces, respectively. The scaling number illustrates the relative importance of vibration-induced dynamic pressure compared to inertial force and surface tension. Together with other well-established non-dimensional numbers, this scaling number provides a new dimension and framework for understanding and controlling droplet dynamics. Our findings can also find applications such as improving the power generation efficiency, intensifying the deposition of paint, and enhancing the heat transfer of droplets.

Parenteral formulation and thermal degradation pathways of a potent rebeccamycin based indolocarbazole topoisomerase I inhibitor.

The development of a practical and pharmaceutically acceptable parenteral dosage form of 1 is described. A cosolvent formulation strategy was selected to achieve the necessary human dose of 1 for administration via intravenous infusion. The final market formulation of 1 chosen for commercial development and Phase II clinical supplies was the topoisomerase inhibitor dissolved in a 50% aqueous propylene glycol solution vehicle with 50mM citrate buffered to pH 4. The thermal degradation pathways of 1 in this aqueous propylene glycol vehicle in the pH range of 3-5 were determined by relative kinetics and degradation product identification using LC/MS, LC/MS/MS, and NMR analysis. The primary mode of degradation of 1 in this aqueous cosolvent formulation is hydrolysis affording the anhydride 2 (in equilibrium with the dicarboxylic acid 3) and release of the hydrazine diol side chain 11. Subsequent oxidative degradation of 11 occurs in several chemical steps which yield a complicated mixture of secondary reaction products that have been structurally identified.

Radical cations from dicyclopropylidenemethane and its octamethyl derivative.

The radical cations of dicyclopropylidenemethane (2) and its octamethyl derivative (2-Me8) are prone to rearrangements into those of (2-methylallylidene)cyclopropane (2a) and its octamethyl derivative (2a-Me8), respectively, by opening one three-membered ring. In contrast to the radical cations of bicyclopropylidene (1) and its octamethyl derivative (1-Me8), 2*+ and 2-Me8*+ are stable to opening of the second ring, because in this case the resulting species would be a non-Kekulé hydrocarbon with a quartet ground state. Similarly to 1, octamethyl substitution in 2 promotes the tendency to rearrangement. Thus, ESR and ENDOR studies indicate that the primary radical cation 2*+, which is formed upon gamma-irradiation of 2 in a CFCl3 matrix at 77 K, does not rearrange up to 150 K. On the other hand, when 2-Me8 is treated in the same way, only the rearranged radical cation 2a-Me8*+ can be observed and characterized by its ESR and ENDOR spectra. Nevertheless, the existence of the two "missing" species, 2a*+ and 2-Me8*+, is revealed by other methods. According to UV and IR studies, X irradiation of 2 in an Ar matrix leads directly to the ring-opened radical cation 2a*+. Moreover, magnetic field effects on the decay of fluorescence, which appears upon recombination of the radical anion of p-terphenyl with a radical cation generated from 2-Me8 in liquid octane, strongly suggest that 2-Me8*+ (and not 2a-Me8*+) is formed initially. From the temperature dependence of the decay, the activation energy of the ring-opening process 2-Me8*+ --> 2a-Me8*+ is estimated. The radical cations 2a*+ and 2a-Me8*+ are formally distonic with the spin residing in the allylic moiety and the charge accommodated on the central carbon atom of the allene pi-system. The intact cyclopropylidenemethylidene moiety assumes a "bisected" conformation, thus favoring an optimal interaction with the positively charged center on the pi-system.

Application of liquid chromatography/mass spectrometry and nuclear magnetic resonance to the identification of degradates of a novel insulin sensitizer in aqueous solutions.

Degradation of a novel insulin sensitizer in aqueous solutions was studied using high pressure liquid chromatography/mass spectrometry (LC/MS). The insulin sensitizer, containing a thiazolidine-2,4-dione (TZD), was a new class of antidiabetic agent for the treatment of type II diabetes. Chemical stability of the insulin sensitizer was evaluated by stressing its aqueous solutions at 40 degrees C for 24 h. Oxygen was removed from one of the solutions by bubbling pure nitrogen through to identify non-oxidative pathways. LC/MS analyses of the stressed solutions revealed that hydrolysis and oxidation are the primary degradation pathways for the studied compound. A alpha-thiol acetic acid, acyl amide, and two dimeric diastereomers were the main degradates of the insulin sensitizer. The alpha-thiol acetic acid served as an intermediate-like species, and oxidized to two dimeric degradates upon exposing to air. All of them were identified as ring-opening products of the TZD. The entities of the acyl amide and dimeric degradates were respectively verified by a synthetic standard or NMR following isolation of a diastereomeric degradate. Characterization using MS in both positive and negative ion scans were discussed for an isolated diastereomeric degradate. Mechanisms of fragmentation and formation for those degradates are presented based on the MS result.

Novel rearrangements of an N-oxide degradate formed from oxidation of a morpholine acetal substance P antagonist.

Compound 1 [5-[2(R)-[1(R)-(3,5-bistrifluoromethylphenyl) ethoxy]-3(s)-(4-fluorophenyl)morpholin-4-ylmethyl]-3h-[1,2,3] triazol-4-ylmethyl]dimethylamine represents a new class of potent, orally active substance P antagonists, which possess a characteristic structural feature-a cis-2-alkoxy-3-arylmorpholine core. The oxidative degradation of 1 in drug substance and formulations was found to occur through the two trialkylamine oxides, which undergo secondary degradations to give rise to observed degradation products. In this study, the five primary degradation products of the N-oxide 2 formed from the oxidation of the morpholine core of 1 were identified by LC/MS and MS/MS. The N-oxide 2 undergoes novel thermal rearrangements, which were proposed to follow elimination/addition mechanisms. An unusual, facile [1,3]-sigmatropic rearrangement was also demonstrated.

Collision-induced dissociation of the negative ions of simvastatin hydroxy acid and related species.

Simvastatin hydroxy acid (1) is a well-known, potent HMG-CoA reductase inhibitor for the treatment of hypercholesterolemia. Its lactone, simvastatin (commercial name Zocor) (a prodrug of 1), has been widely prescribed in the USA and throughout the world. In this work, collision-induced dissociation (CID) of the negative ion of 1 (m/z 435), a carboxylic anion, was analyzed in detail. The major fragmentation pathway of this ion is a novel de-esterification to form the negative product ions at m/z 319 and 115. The ion at m/z 319 undergoes further collision-induced rearrangements to form the negative ions at m/z 215, 159 and 85. Possible mechanisms of the de-esterification are discussed in terms of both charge-initiated and charge-remote fragmentations. The de-esterification of the negative ion of 1 and the rearrangements of the ion at m/z 319 are rationalized by charge transfer and negative-charge initiated fragmentation. This study deepens our understanding of collision-induced fragmentations of carboxylic anions with multi-functional groups. A comparison of the CID data for the negative ions of 1 and 5 (a major oxidation degradate of 1) indicates that the analysis of the CID data for 1 can serve as a basis for identification of oxidation degradation products or metabolites of 1. The analysis of the CID data for the negative ion of 1 also reveals the fundamental characteristics of the CID data for the negative ions of other statin hydroxy acids such as lovastatin (3) and pravastatin (4).

The importance of chromatographic separation in LC/MS/MS quantitation of drugs in biological fluids: detection, characterization, and synthesis of a previously unknown low-level nitrone metabolite of a substance P antagonist.

The observation of an interference peak in plasma samples from dogs dosed with compound I led to the discovery of an unidentified metabolite. The unknown metabolite had the same molecular weight as the parent drug, and their fragmentation profiles were also quite similar. LC/MS/ MS analysis of the plasma extracts of dogs and rats dosed with I and its deuterium-labeled analogue suggested a nitrone structure for the unknown metabolite. Synthesized nitrone matched the unknown metabolite with identical retention time and nearly identical fragmentation profile. The nitrone slowly decomposed in acidic aqueous solution at ambient temperature and also underwent in-source, thermal-induced hydrolysis during electrospray ionization mass spectrometric analysis. The reaction of the nitrone with diethyl acetylenedicarboxylate readily generated a [2 + 3] cycloaddition product. The example shown here clearly demonstrates that precautions must be taken when LC/MS/MS quantitation is conducted in the selected reaction monitoring mode.

Tandem mass spectrum of a growth hormone secretagogue: amide bond cleavage and resultant gas-phase rearrangement.

Compound 1 [N-[1(R)-[(1,2-dihydro-1-methylsulfonylspiro[3H-indole-3,4'-piperidin]-1'-yl)carbonyl]-2-(phenylmethyloxy)ethyl]-2-amino-2-methylpropanamide](MW 528) is an orally-active growth hormone secretagogue (GHS). As part of a continual effort to analyze the ESI/MS and MSn data of novel drugs, the ESI/MS and MS/MS data of protonated 1 (m/z 529) are analyzed and reported here. The analyses reveal that under low-energy collision-induced dissociation (CID) in an ion trap or a quadrupole collision cell, protonated 1 undergoes a gas-phase rearrangement to form protonated 3 (m/z 357) which competes with the y- and b-type product ions during the amide bond cleavages of protonated 1. It is proposed that when the b-type ion is formed by cleavage of the piperidine amide bond, piperidine (a neutral species) and the b-ion (a cation) form an ion-neutral complex. In this complex, piperidine functions as a nucleophile to attack the benzylic carbon of the b-ion, and the protonated ether group in the b-ion acts as a leaving group, which results in the migration of the benzylic group to the piperidine amine to form protonated 3. Protonated 2 (an analog of 1) was studied under the same experimental conditions. The results show that protonated 2 undergoes a similar rearrangement to form protonated 3. While this rearrangement is a relatively minor fragmentation process for protonated 1, it is a predominant process for protonated 2. This phenomenon is explained in terms of the proposed ion-neutral-complex mechanism.