Are Most Micrometer Droplets (>10 µm) Wasted in Electrospray Ionization? An Insight from Real-Time High-Speed Imaging.

Electrospray ionization (ESI) is one of the main techniques used in mass spectrometry (MS) of nonvolatile compounds. ESI is a disordered process, in which a large number of polydisperse droplets are projected from a fluctuating Taylor cone and jet protruding ESI emitter. Here, we disclose a system for sectioning electrospray plumes to discrete packets with millisecond and submillisecond lifetime, which are introduced to the MS orifice, one at a time. A high-speed camera was triggered at 10,000 frames per second to capture consecutive images of the electrospray packets transmitted to the mass spectrometer. We further correlated the high-speed images of electrospray packets with MS signals of a test analyte (acetaminophen). Following computational treatment of the images, we determined the number of droplet observations (<300), average diameter of droplets (∼10-20 µm), and average volume of droplets (few tens of picoliters) in the individual electrospray packets. The result shows that most micrometer droplets (>10 µm) do not have any significant contribution to the MS signals. This finding is in agreement with the prior conjecture that most of the MS signals are mainly attributed to nanodroplets. Based on this finding, one can deduce that only a small number of the initial microdroplets effectively carry analyte molecules that undergo ionization. We discuss that, in future, one may propose a way to "recharge" the emitted initial micrometer droplets to increase the efficiency of conventional ESI setups.

Vending-Machine-Style Skin Excretion Sensing.

Skin metabolites show huge potential for use in clinical diagnostics. However, skin sampling and analysis workflows are tedious and time-consuming. Here, we demonstrate a vending-machine-style skin excretion sensing platform based on hydrogel-assisted sampling of skin metabolites. In this sensing platform, a sampling probe with hydrogel is held by a robotic arm. The robotic arm manoeuvres the probe to press it onto the forearm of a human subject. Due to the highly hydrophilic nature of the hydrogel, water-soluble metabolites─released by skin─are collected into the hydrogel, leaving behind the nonpolar metabolites. The probe is then inserted into a custom-made open port sampling interface coupled to an electrospray ion source of a high-resolution quadrupole-time-of-flight mass spectrometer. Metabolites in the hydrogel are immediately extracted by a solvent liquid junction in the interface and analyzed using the mass spectrometer. The ion current of the target analyte is displayed on a customized graphical user interface, which can also be used to control the key components of the analytical platform. The automated sampling and analysis workflow starts after the user inserts coins or presents an insurance card, presses a button, and extends an arm on the sampling area. The platform relies on low-cost mechanical and electronic modules (a robotic arm, a single-board computer, and two microcontroller boards). The limits of detection for standard analytes─arginine, citrulline, and histidine─embedded in agarose gel beds were 148, 205, and 199 nM, respectively. Various low-molecular-weight metabolites from human skin have been identified with the high-resolution mass spectrometer.

Tuning Electrospray Ionization with Low-Frequency Sound.

Electrospray ionization (ESI) mass spectrometry (MS) is one of the key techniques used in biomolecular analysis nowadays. It relies on formation of polydisperse microdroplets, which undergo desolvation and liberate ions to the gas phase. Here we demonstrate low-frequency-sound-modulated ESI for analysis of biomolecules. By using a low-frequency (50-350 Hz) sound, it is possible to deflect electrospray microdroplets toward the mass spectrometer's orifice. Microdroplets of different sizes are deflected to a different extent leading to a partial size segregation. This effect leads to either an increase or decrease of MS signal intensity as well as signal-to-noise ratio. It also affects the selectivity of the ESI-MS analysis. The observations are rationalized by taking into account different pathways of ion formation and the likelihood of deflecting microdroplets of certain size. The online ESI-MS observations are supported with offline shadowgraphs obtained at varied sound frequencies, signal amplitudes, and phase shifts.

Telechemistry 2.0: Remote monitoring of fluorescent chemical reactions.

Implementation of the Internet-of-Things in chemistry research has the potential to improve research methodologies. Here, we describe a cloud-integrated real-time laboratory monitoring system for: (i) monitoring reactions involving fluorescent chemical species, and (ii) monitoring laboratory environment for safety purpose. A probe-type fluorescence detection system has been constructed to monitor reactions that involve fluorescent molecules. This device incorporates an in-house-built 3D-printed probe, two optical fibers, a light-emitting diode, a photoresistor, and a microcontroller board (MCB). The MCB relays experimental data to a single-board computer (SBC), which then uploads the data to a cloud-based platform (ThingSpeak) for data storage and visualization. The SBC is also connected to auxiliary sensors to measure relative alcohol vapor concentration, temperature, and humidity at different locations in the laboratory. The device has been validated and tested for its performance by monitoring a fluorescent chemical reaction (synthesis of fluorescent gold nanoclusters) for a period of 12 h.

Slicing Ceramics on Material Removed by a Single Abrasive Particle.

Multi-wire saw machining (MWSM) used for slicing hard-brittle materials in the semiconductor and photovoltaic industries is an important and efficient material removal process that uses free abrasives. The cutting model of single-wire saw machining (SWSM) is the basis of MWSM. The material removal mechanism of SWSM is more easily understood than MWSM. A mathematical model (includes brittle fracture and plastic deformation) is presented in this paper for SWSM ceramic with abrasives. This paper determines the effect of various machining parameters on the removal of hard-brittle materials. For brittle fracture of SWSM ceramics, the minimum strain energy density is used as a fracture criterion. For plastic deformation of SWSM ceramics, the material removal is calculated using equations of motion. Actual wire-sawing experiments are conducted to verify the results of the developed mathematical model. The theoretical results agree with experimental data and practical experience. From the developed mathematical model, brittle fracture plays a major role in material removal of SWSM ceramics. Wire speed (S) and working load (P) are positively correlated with material removal of SWSM ceramics. The coefficient of friction is low, a lateral crack, which propagates almost parallel to the working surface, leads to more brittle fracture and material removal is increased.

Facilitating chemical and biochemical experiments with electronic microcontrollers and single-board computers.

Since the advent of modern science, researchers have had to rely on their technical skills or the support of specialized workshops to construct analytical instruments. The notion of the 'fourth industrial revolution' promotes construction of customized systems by individuals using widely available, inexpensive electronic modules. This protocol shows how chemists and biochemists can utilize a broad range of microcontroller boards (MCBs) and single-board computers (SBCs) to improve experimental designs and address scientific questions. We provide seven example procedures for laboratory routines that can be expedited by implementing this technology: (i) injection of microliter-volume liquid plugs into microscale capillaries for low-volume assays; (ii) transfer of liquid extract to a mass spectrometer; (iii) liquid-gas extraction of volatile organic compounds (called 'fizzy extraction'), followed by mass spectrometric detection; (iv) monitoring of experimental conditions over the Internet cloud in real time; (v) transfer of analytes to a mass spectrometer via a liquid microjunction interface, data acquisition, and data deposition into the Internet cloud; (vi) feedback control of a biochemical reaction; and (vii) optimization of sample flow rate in direct-infusion mass spectrometry. The protocol constitutes a primer for chemists and biochemists who would like to take advantage of MCBs and SBCs in daily experimentation. It is assumed that the readers have not attended any courses related to electronics or programming. Using the instructions provided in this protocol and the cited material, readers should be able to assemble simple systems to facilitate various procedures performed in chemical and biochemical laboratories in 1-2 d.

Fabrication and Characteristics of SnAgCu Alloy Nanowires for Electrical Connection Application.

As electronic products become more functional, the devices are required to provide better performances and meet ever smaller form factor requirements. To achieve a higher I/O density within the smallest form factor package, applying nanotechniques to electronic packaging can be regarded as a possible approach in microelectronic technology. Sn-3.0 wt% Ag-0.5 wt% Cu (SAC305) is a common solder material of electrical connections in microelectronic devices. In this study, SAC305 alloy nanowire was fabricated in a porous alumina membrane with a pore diameter of 50 nm by the pressure casting method. The crystal structure and composition analyses of SAC305 nanowires show that the main structure of the nanowire is ß-Sn, and the intermetallic compound, Ag3Sn, locates randomly but always appears on the top of the nanowire. Furthermore, differential scanning calorimetry (DSC) results indicate the melting point of SAC305 alloy nanowire is around 227.7 °C. The melting point of SAC305 alloy nanowire is significantly higher than that of SAC305 bulk alloy (219.4 °C). It is supposed that the non-uniform phase distribution and composite difference between the nanowires causes the change of melting temperature.

Effects of NH3 PECVD treatment time on the performance of multiwall carbon nanotubes for antibody immobilization.

This work presents an amino plasma-enhanced chemical vapour deposition (NH3 PECVD) treatment to modify multiwall carbon nanotubes (MWCNTs) for the immobilization of antibodies (IgG-gold), and the effects of treatment time were studied. A titanium nitride (TiN) buffer layer and a nickel catalyst layer were deposited on silicon substrates for synthesis of MWCNTs using thermal CVD. The MWCNTs were modified by amine (NH2 (-) ) or amino (NH(-) ) functional groups for 1, 3, and 5 min by PECVD, respectively. Mouse IgG-golds were immobilized on the modified MWCNTs using glutaraldehyde (GA) as a crosslinker. The performance of the modified MWCNTs was characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectroscopy (FT-IR), contact angle system (CA), X-ray photoelectron spectroscopy (XPS, ESCA), and UV-visible spectroscopy. Results show that the efficiency of IgG-gold immobilization was increased with the increase of NH3 PECVD treatment time. The NH3 PECVD treatment changed the surface properties of the MWCNTs, tuning them more hydrophilic without affecting their structure. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1343-1351, 2016.

The Fabrication of Flow Field Plates for Direct Methanol Fuel Cell Using Lithography and Radio Frequency Sputtering.

This study uses lithography to etch flow fields on a single side of a printed circuit board (PCB) and combines a flow field plate with a collector plate to make innovative anode flow field plates and cathode flow field plates for a direct methanol fuel cell (DMFC). TiO2 thin film is also sputtered on the anode flow field plate using radio frequency (RF) sputtering. The experimental results show that the prepared DMFC has a better maximum power density of 11.928 mW/cm2. Furthermore, when a TiO2 thin film is sputtered on the flow field plate of the assembled DMFC, the maximum power density is 14.426 mW/cm2, which is actually 21% more than that for a DMFC with no TiO2 thin film coated on the flow field plate.

Local awakening: regional reorganizations of brain oscillations after sleep.

Brain functions express rhythmic fluctuations accompanied by sleep and wakefulness each day, but how sleep regulates brain rhythms remains unclear. Following the dose-dependent local sleep concept, two succeeding questions emerge: (1) is the sleep regulation a network-specific process; and (2) is the awakening state dependent on the previous sleep stages? To answer the questions, we conducted simultaneous EEG and fMRI recordings over 22 healthy male participants, along pre-sleep, nocturnal sleep and awakening. Using paired comparisons between awakening and pre-sleep conditions, three scenarios of the regional specificity were demonstrated on awakening: (1) the default-mode and hippocampal networks maintained similar connectivity and spectral power; (2) the sensorimotor network presented reduced connectivity and spectral power; and (3) the thalamus demonstrated substantially enhanced connectivity to the neo-cortex with decreased spectral power. With regard to the stage effect, the deep sleep group had significant changes in both functional connectivity and spectral power on awakening, whereas the indices of light sleep group remained relatively quiescent after sleep. The phenomena implied that slow-wave sleep could be key to rebooting the BOLD fluctuations after sleep. In conclusion, the regional specificity and the stage effect were verified in support of the local awakening concept, indicating that sleep regulation leads to the reorganization of brain networks upon awakening.