Imaging Mass Spectrometry: Hype or Hope?

Label-free imaging mass spectrometry provides a new look into different research areas. Will chemical mass microscopy on a biological system move from hype to hope?

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Surface neutralization/surface reionization (Ping–Pong) mass spectrometry

Experiments are reported that utilize surface neutralization of hyperthermal organic ions to obtain hyperthermal neutral species that are reionized on oxygen-activated rhenium surface and detected by mass spectrometry. A special Ping–Pong mass spectrometer was designed and coupled to a double-focusing mass spectrometer to allow energy and angle-resolved measurements. Neutralization of pyridine and benzene ions on gold, copper, and aluminum surfaces generated substantial ion currents into the collecting plate. The ion currents obtained on gold surfaces were found to depend on the recombination energy of the ion projectile. Hyperthermal neutrals coming off the first surface were found to mainly originate from hydrocarbon adsorbates.     

A Microreactor with Thousands of Subcompartments: Enzyme‐Loaded Liposomes within Polymer Capsules

Fully loaded : Noncovalent anchoring of liposomes into polymer multilayered films with cholesterol‐modified polymers allows the preparation of capsosomes—liposome‐compartmentalized polymer capsules (see picture). A quantitative enzymatic reaction confirmed the presence of active cargo within the capsosomes and was used to determine the number of subcompartments within this novel biomedical carrier system.

     

Development of a Gas-Tight Syringe Headspace GC-FID Method for the Detection of Ethanol,and a Description of the Legal and Practical Framework for Its Analysis,in Samples of English and Welsh Motorists’ Blood and Urine

Ethanol is the most commonly used recreational drug worldwide. This study describes the development and validation of a headspace gas chromatography flame ionisation detection (HS-GC-FID) method using dual columns and detectors for simultaneous separation and quantitation. The use of a dual-column, dual-detector HS-GC-FID to quantitate ethanol is a common analytical technique in forensic toxicology; however, most analytical systems utilise pressure-balance injection rather than a simplified gas-tight syringe, as per this technique. This study is the first to develop and validate a technique that meets the specifications of the United Kingdom’s requirements for road traffic toxicology testing using a Shimadzu GC-2014 gas-tight syringe. The calibration ranged from 10 to 400 mg/100 mL, with a target minimum linearity of r2 > 0.999, using tertiary butanol as the internal standard marker. The method has an expanded uncertainty at 99.73% confidence of 3.64% at 80 mg/100 mL, which is the blood alcohol limit for drink driving in England and Wales. In addition, at 200 mg%—the limit at which a custodial sentence may be imposed on the defendant—the expanded uncertainty was 1.95%. For both the 80 mg% and 200 mg% concentrations, no bias was present in the analytical method. This method displays sufficient separation for other alcohols, such as methanol, isopropanol, acetaldehyde, and acetone. The validation of this technique complies with the recommended laboratory guidelines set out by United Kingdom and Ireland Association of Forensic Toxicologists (UKIAFT), the recently issued Laboratory 51 guidelines by the United Kingdom Accreditation Service (UKAS), and the criteria set out by the California Code of Regulations (CCR), 17 CCR § 1220.1.     

Weak Noncovalent Interactions in Three Closely Related Adamantane-Linked 1,2,4-Triazole N-Mannich Bases: Insights from Energy Frameworks,Hirshfeld Surface Analysis,In Silico 11β-HSD1 Molecular Docking and ADMET Prediction

Structural analysis and docking studies of three adamantane-linked 1,2,4-triazole N-Mannich bases (1–3) are presented. Compounds 1, 2 and 3 crystallized in the monoclinic P2₁/c, P2₁ and P2₁/n space groups, respectively. Crystal packing of 1 was stabilized by intermolecular C-H⋯O interactions, whereas compounds 2 and 3 were stabilized through intermolecular C-H⋯N, C-H⋯S and C-H⋯π interactions. The energy frameworks for crystal structures of 1–3 were described. The substituent effect on the intermolecular interactions and their contributions were described on the basis of Hirshfeld surface analyses. The 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) inhibition potential, pharmacokinetic and toxicity profiles of compounds 1–3 were determined using in silico techniques. Molecular docking of the compounds into the 11β-HSD1 active site showed comparable binding affinity scores (−7.50 to −8.92 kcal/mol) to the 11β-HSD1 co-crystallized ligand 4YQ (−8.48 kcal/mol, 11β-HSD1 IC₅₀ = 9.9 nM). The compounds interacted with key active site residues, namely Ser170 and Tyr183, via strong hydrogen bond interactions. The predicted pharmacokinetic and toxicity profiles of the compounds were assessed, and were found to exhibit excellent ADMET potential.     

Designing High-Donicity Anions for Rechargeable Potassium Superoxide/Peroxide Batteries

A battery cathode based on the superoxide/peroxide redox not only inherits the advantage of oxygen (O₂) batteries in high capacities and low costs but also overcomes the disadvantages in O₂ storage, electrolyte evaporation, and anode deactivation due to O₂ crossover. Herein, we report an enhanced potassium superoxide (KO₂)/peroxide (K₂O₂) conversion by adopting a high-donicity anion additive in the ether-based electrolyte. Such an anion was synthesized via a “Solvent-in-Anion” strategy and validated to enhance the electron donicity of the electrolyte. The use of high-donicity anion could lead to enhanced KO₂ utilization (≈90.2 %) by retarding electrode passivation and allow the full charging back of K₂O₂ through the solution-mediated pathway without electrocatalysts. No apparent cell degradation is observed during the first 120 cycles by controlling the reversible depth-of-discharge capacity at 292 mAh g⁻¹ within an O₂-free region. The K−KO₂ cell delivers a high energy efficiency (>84.4 %) and a lifespan of over 1440 hours.     

A Hybrid Magneto-Optic Capacitive Memory with Picosecond Writing Time

The long-term future of information storage requires the use of sustainable nanomaterials in architectures operating at high frequencies. Interfaces can play a key role in this pursuit via emergent functionalities that break out from conventional operation methods. Here, spin-filtering effects and photocurrents are combined at metal-molecular-oxide junctions in a hybrid magneto-capacitive memory. Light exposure of metal-fullerene-metal oxide devices results in spin-polarized charge trapping and the formation of a magnetic interface. Because the magnetism is generated by a photocurrent, the writing time is determined by exciton formation and splitting, electron hopping, and spin-dependent trapping. Transient absorption spectroscopy measurements show changes in the electronic states as a function of the magnetic history of the device within picoseconds of the optical pumping. The stored information is read using time-resolved scanning magneto optic Kerr effect measurements during microwave irradiation. The emergence of a magnetic interface in the picosecond timescale opens new paths of research to design hybrid magneto-optic structures operating at high frequencies for sensing, computing, and information storage.     

Two-Photon Polymerization of Sugar Responsive 4D Microstructures

Stimuli-responsive hydrogels have attracted much attention owing to the versatility of their programmed response in offering intelligent solutions for biomimicry applications, such as soft robotics, tissue engineering, and drug delivery. To achieve the complexity of biomimetic structures, two photon polymerization (2PP) has provided a means of fabricating intricate 3D structures from stimuli-responsive hydrogels. Rapid swelling hydrogel microstructures are advantageous for osmotically driven stimuli-response, where actuation speed, that is reliant on the diffusion of analytes or bioanalytes, can be optimized. Herein, the flexibility of 2PP is exploited to showcase a novel sugar-responsive, phenylboronic acid-based photoresist. This offers a remarkable solution for achieving fast response hydrogel systems that have been often hindered by the volume-dependent diffusion times of analytes to receptor sites. A phenylboronic acid-based photoresist compatible with 2PP is presented to fabricate stimuli-responsive microstructures with accelerated response times. Moreover, microstructures with programmable actuation (i.e., bending and opening) are fabricated using the same photoresist within a one-step fabrication process. By combining the flexibility of 2PP with an easily adaptable photoresist, an accessible fabrication method is showcased for sophisticated and chemo-responsive 3D hydrogel actuators.