Electrospray Ionization Technique Research Articles

Engineering pH and Temperature-Triggered Drug Release with Metal-Organic Frameworks and Fatty Acids

This study reports the successful synthesis of core-shell microparticles utilizing coaxial electrospray techniques, with zeolitic imidazolate framework-8 (ZIF-8) encapsulating rhodamine B (RhB) in the core and a phase change material (PCM) shell composed of a eutectic mixture of lauric acid (LA) and stearic acid (SA). ZIF-8 is well-recognized for its pH-responsive degradation and biocompatibility, making it an ideal candidate for targeted drug delivery. The LA-SA PCM mixture, with a melting point near physiological temperature (39 °C), enables temperature-triggered drug release, enhancing therapeutic precision. The structural properties of the microparticles were extensively characterized through scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Drug release studies revealed a dual-stimuli response, where the release of RhB was significantly influenced by both temperature and pH. Under mildly acidic conditions (pH 4.0) at 40 °C, a rapid and complete release of RhB was observed within 120 h, while at 37 °C, the release rate was notably slower. Specifically, the release at 40 °C was 79% higher than at 37 °C, confirming the temperature sensitivity of the system. Moreover, at physiological pH (7.4), minimal drug release occurred, demonstrating the system’s potential for minimizing premature drug release under neutral conditions. This dual-stimuli approach holds promise for improving therapeutic outcomes in cancer treatment by enabling precise control over drug release in response to both pH and localized hyperthermia, reducing off-target effects and improving patient compliance.

An Affordable Dual Purpose Spray Setup for Lithium-Ion Batteries Thin Film Electrode Deposition

This work presents a versatile and cost-effective spray setup that integrates both compressed air spray and electrospray techniques, specifically designed for small-scale laboratory use. This setup provides researchers with an accessible tool to explore spray methods for growing battery electrodes. While these techniques hold significant industrial promise, affordable and simple methods for their use in research settings have been limited. To address this, the setup includes custom control software and detailed information on costs and materials, offering an easy-to-implement solution. The system was tested with three samples per technique, using identical settings, to evaluate the repeatability of each method and gain insights into the uniformity and structure of the resulting films. The structural and morphological characteristics of the samples were analyzed using X-ray diffraction and scanning electron microscopy. The air-spray samples showed greater consistency and repeatability, whereas the electrospray samples exhibited better deposition results in terms of material coverage and higher crystallinity films. Cracking was observed in the air-spray samples, which was related to thermal stress, and both techniques exhibited solvent evaporation issues. The issues encountered with the setup and samples are summarized, along with possible solutions and the next steps for future upgrades and research.

Dual-network hydrogel capsules for controlled molecular transport via pH and temperature responsiveness

We have developed innovative core–shell hydrogel capsules with a dual-network shell structure designed for precise control of molecular transport in response to external stimuli such as pH and temperature. The capsules were fabricated using a combination of microfluidic electrospray techniques and water-in-water (w/w) core–shell droplets templating. The primary network of the shell, calcium alginate (Ca-Alg), with a pKa around 3.4, exhibits sensitivity to pH. The secondary network of the shell, poly(ethylene glycol) methyl ether methacrylate (PEGMA), undergoes a volume phase transition near 60 °C. These properties enable precise molecular transport control in/out of the capsules by modulating the surface charges through varying pH and modifying pore size through temperature changes. Moreover, the dual-network shell structure not only significantly enhances the mechanical strength of the capsules but also improves their stability under external stimulus, ensuring structural integrity during the transport of molecules. This research lays the groundwork for further investigations into the multimodal stimuli-responsive hydrogel systems to control molecular transport, important in applications such as sensors and reactors for chemical cascade reactions.

Development of magnesium hydroxide-doped nanofibrous spheres for repairing infected skin wounds

The healing of skin wounds is a continuous and coordinated process, typically accompanied by microbial colonization and growth. This may result in wound infection and subsequent delay in wound healing. Therefore, it is of particular importance to inhibit the growth of microorganisms in the wound environment. In this study, magnesium hydroxide-doped polycaprolactone (PCL/MH) nanofibrous spheres were fabricated by electrospinning and electrospray techniques to investigate their effects on infected wound healing. The prepared PCL/MH nanofibrous spheres had good porous structure and biocompatibility, providing a favorable environment for the delivery and proliferation of adipose stem cells. The incorporation of MH significantly enhanced the antimicrobial properties of the spheres, in particular, the inhibition of the growth of S. aureus and E. coli. We showed that such PCL/MH nanofibrous spheres had good antimicrobial properties and effectively promoted the regeneration of infected wound tissues, which provided a new idea for the clinical treatment of infected wounds.

Rapid analysis of the chemical constituents of traditional Tibetan medicine Sbyor-bzo-ghi-wang using ballpoint electrospray ionization technique.

The chemical constituents of traditional Tibetan medicines (TTM) can be identified using high-performance liquid chromatography and high-resolution mass spectrometry (HPLC-MS/MS) technique. However, the HPLC-MS/MS technique requires the sample to be pretreated and then separated using the specific liquid chromatography method, which is time consuming. This study developed a ballpoint electrospray ionization (BPESI) technique for analyzing the chemical constituents of Sbyor-bzo-ghi-wang. This technique is a simple and inexpensive method for the rapid identification of the chemical constituents of TTMs. After the important parameters of the homemade BPESI device were optimized, the chemical constituents of Sbyor-bzo-ghi-wang were quickly identified without sample pretreatment. The raw data were converted to mzML file using MSConvert and then identified using SIRIUS 5 software. The results showed that 30 compounds were identified from Sbyor-bzo-ghi-wang, namely eight bile acids, six flavonoids, four alkaloids, three amino acids, and nine others. Compared to the ultra-high-performance liquid chromatography-Q/Orbitrap and high-resolution mass spectrometry (UHPLC-Q/Orbitrap HRMS) technique, the BPESI technique identified almost similar types of compounds and also a comparable number of compounds. Compared with the traditional HPLC-MS/MS methods, the BPESI technique does not require complex sample pretreatment and subsequent chromatographic separation steps; also it consumes a small quantity of samples. Therefore, BPESI can be used for the qualitative analysis of the chemical constituents of Sbyor-bzo-ghi-wang.

Protein Nanoparticles Laden In situ Gel for Topical Ocular Drug Delivery.

Topical ocular delivery of drugs is most commonly preferred route by the patient and physician for the treatment of ocular diseases. The topical route is always followed with the disadvantages like tear turnover, nasolacrimal drainage, reduction in precorneal residence time, etc</i>. To overcome these hindrances associated with topical ocular route, a novel drug delivery system is used for targeting the drug at a specific site. In the Novel Drug delivery System, protein-based nanoparticles are an attractive class of nanoparticles designed to deliver the drug at targeted site in slow and sustained release manner. They have a size in the range of 1-100 nm. Protein nanoparticles are leading, particularly for the topical ocular delivery like reduction in intra ocular pressure, providing sustained release and targeted drug delivery at the site of its action. Various methods are used for formulation of protein nanoparticles like desolvation, emulsification, complex coacervation, electrospray techniques. The characterization parameters include particle size, surface morphology, drug loading and entrapment efficiency. Protein nanoparticles can also be loaded in to the in situ</i> gel forming polymers for increasing precorneal residence time of nanoparticles. The characterization parameters of in situ</i> gelling systems are gelling time, rheological properties, gel strength. The review mainly describes the use of various proteins in preparation of protein nanoparticles, methods for preparation of protein nanoparticles, polymers used in in situ</i> gelling system and evaluation as well as characterization parameters of protein nanoparticles, in situ</i> gelling systems & patented information related to protein nanoparticles and in situ</i> gelling system for ocular drug delivery.

Fabrication of fiber-particle structures by electrospinning/electrospray combination as an intrinsic antioxidant and oxygen-releasing wound dressing.

In this study, we employed a combination of electrospinning and electrospray techniques to fabricate wound dressings with a particle-fiber structure, providing dual characteristics of oxygen-releasing and intrinsic antioxidant properties, simultaneously. The electrospun part of the dressing was prepared from a blend of polycaprolactone/gallic acid-grafted-gelatin (GA-g-GE), enabling intrinsic ROS scavenging. To the best of our knowledge, this is the first time that PCL/GA-g-GE was fabricated by electrospinning. Furthermore, polyvinyl pyrrolidone (PVP) microparticles, containing calcium peroxide nanoparticles (CNPs), were considered as the oxygen production agent through the electrospray part. The CNP content was 1% and 3% w/w of PVP while biopolymer:PCL was 10% w/w. The fabricated structures were characterized in terms of fiber/particle morphology, elemental analysis, oxygen release behavior, ROS inhibition capacity, and water contact angle assessments. The covalent bonding of gallic acid to gelatin was confirmed by 1H-NMR, UV spectroscopy, and FTIR. According to the SEM results, the morphology of the prepared PCL/biopolymer fibers was bead-free and with a uniform average diameter. The analysis of released oxygen showed that by increasing the weight percentage of CNPs from 1 to 3 wt%, the amount of released oxygen increased from 120 mmHg to 195 mmHg in 24 h, which remained almost constant until 72 h. The obtained DPPH assay results revealed that the introduction of GA-g-GE into the fibrous structure could significantly improve the antioxidant properties of wound dressing compared to the control group without CNPs and modified gelatine. In vitro, the fabricated wound dressings were evaluated in terms of biocompatibility and the potential of the dressing to protect human dermal fibroblasts under oxidative stress and hypoxia conditions by an MTT assay. The presence of GA-g-GE led to remarkable protection of the cells against oxidative stress and hypoxia conditions. In vivo studies revealed that the incorporation of intrinsic ROS inhibition and oxygen-releasing properties could significantly accelerate the wound closure rate during the experimental period (7, 14, and 21 days). Additionally, histopathological investigations in terms of H&E and Masson's trichrome staining showed that the incorporation of the two mentioned capabilities remarkably facilitated the wound-healing process.

Arc-Induced Electrospray Ionization Mass Spectrometry.

Arc-induced electrospray ionization mass spectrometry (AESI-MS) was developed during which alternating current electrospray is simply achieved through the arc plasma. The AESI source exploits the arc's temperature and charge properties to generate aerosols consisting of charged microdroplets. The electrospray region, in which organic molecules are contained within microdroplets, partially overlaps with the arc plasma region. Guided by the electric field, these molecules undergo ionization, yielding ionic target analytes. AESI represents a soft ionization method that combines the mechanisms of atmospheric pressure chemical ionization and electrospray ionization, facilitating the ionization of analytes with wide ranging polarities. The precisely targeted spraying area enhances ion entry into the mass analyzer, thereby enabling excellent ionization efficiency. The AESI source exhibits several notable advantages over the electrospray ionization source, including an elevated but comparable level of active species concentrations and types, simplified mass spectra for direct amino acid analysis, high salt tolerance, versatile analysis of compounds with varying polarities, and reliable quantitative analysis of amino acids in complex matrices. Overall, AESI broadens the methodologies employed to generate microdroplets, providing a technological and scientific framework for creating distinctive electrospray ionization techniques.

Alginate-Based Patch for Middle Ear Delivery of Probiotics: A Preliminary Study Using Electrospray and Electrospinning

Antimicrobial resistance poses a growing challenge in respiratory tract diseases like otitis media, often necessitating surgical interventions due to pharmacological treatment limitations. Bacteriotherapy, involving probiotics and/or their bioproducts, emerges as a promising alternative in such a scenario. This study aims to pave the way to middle ear bacteriotherapy by developing an innovative sodium alginate (SA)-based probiotic delivery system using electrospinning and electrospray techniques. Electrospray enabled the precise production of probiotic-laden SA microparticles, demonstrating potential for targeted bacterial delivery. By overcoming challenges due to the SA molecular structure, we successfully electrospun SA-based fiber meshes with poly(ethylene oxide) (PEO) as a support polymer. The rheologic behavior of the probiotic/SA solutions and the morphology of the obtained microparticles and fibers was evaluated, along with the diameter variation over time. The cytocompatibility of the produced microparticles and fibers was assessed using human dermal keratinocytes and their antimicrobial activity was tested against E. coli. The incorporation of probiotic-laden SA microparticles within electrospun SA/PEO fiber meshes finally offered a patch-like structure to be applied on the tympanic membrane or on the outer auditory canal, which could be a versatile and ideally safe treatment strategy in chronic otitis media. This innovative approach holds promise for clinical applications dealing with inflammatory processes, infections and dysbiosis, thus possibly addressing the complex healing process of chronic upper respiratory diseases while mitigating antimicrobial resistance.

A molecular study of viscosity-causing mechanism and viscosity reduction through re-emulsification for Jimsar shale oil

The high viscosity caused by oil–water emulsification and the lack of clarity on the viscosity-causing mechanism have seriously affected the development of Jimsar shale oil. In this paper, the mechanism behind the increase in viscosity due to emulsification for Jimsar shale oil is revealed at the molecular level, using high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with Electrospray ionization (ESI) technique. The high amount of N1 compounds (carbazoles and indoles) in shale oil combine with water through the N–H bond with the pyridine ring adsorbing formation water, which enhances crude oil's emulsification and water-binding ability. A stable W/O emulsion was formed with water and significantly increased the viscosity of the formation fluid. DFT calculations showed that the interaction energy (Eint) of anionic surfactant AS-1 and AS-2 with polar macromolecules was −258.70 and −77.03 kcal/mol, respectively. The interaction energy of these two systems was much lower than that between H2O and polar macromolecules (-50.87 kcal/mol). It indicated that AS-1 and AS-2 could penetrate the oil–water interface and form stronger interactions with polar macromolecules. Thus, the W/O emulsion is in a reversed-phase, and the viscosity is reduced. The laboratory results showed that the viscosity reduction rates (VRR) of AS-1 and AS-2 due to re-emulsification were greater than 94% at 30℃. The O/AS-1/W and O/AS-2/W emulsions formed during re-emulsification have pseudoplastic fluid flow characteristics and are relatively stable. The emulsions also exhibit spontaneous destabilization and water separation properties, lowering the cost of oil–water separation of produced liquid. Through weak dipole–dipole interaction, CH-π type interaction, and some weak interactions (O∙∙∙N, O∙∙∙S, O∙∙∙H), AS-1 and AS-2 make the space between crude oil and emulsion components more open and inhibit the aggregation of polar macromolecules furthering the viscosity reduction effect.

Fabrication of amine-functionalized and multi-layered PAN-(TiO2)-gelatin nanofibrous wound dressing: In-vitro evaluation

The development of advanced multifunctional wound dressings remains a major challenge. Herein, a novel multilayer (ML) electrospun nanofibers (NFs) wound dressing based on diethylenetriamine (DETA) functionalized polyacrylonitrile (PAN), TiO2 nanoparticles (NPs) coating (Ct), and bioderived gelatin (Gel) was developed for potential applications in wound healing. The ML PAN-DETA-Ct-Gel membrane was developed by combining electrospinning, chemical functionalization, synthesis, and electrospray techniques, using a layer-by-layer method. The ML PAN-DETA-Ct-Gel membrane is comprised of an outer layer of PAN-DETA as a barrier to external microorganisms and structural support, an interlayer TiO2 NPs (Ct) as antibacterial function, and a contact layer (Gel) to improve biocompatibility and cell viability. The NFs membranes were characterized by scanning electron microscopy (SEM), surface profilometry, BET analysis, and water contact angle techniques to investigate their morphology, surface roughness, porosity, and wettability. The ML PAN-DETA-Ct-Gel wound dressing exhibited good surface roughness, porosity, and better wettability. Cell morphology, proliferation, and viability were determined using fibroblasts (3T3), and antibacterial assays were performed against six pathogens. The ML PAN-DETA-Ct-Gel NFs membrane showed good cell morphology, proliferation, viability, and antibacterial activity compared with other membranes. This new class of ML NFs membranes offers a multifunctional architecture with adequate biocompatibility, cell viability, and antibacterial activity.

Mass Spectral Imaging to Map Plant-Microbe Interactions.

Plant-microbe interactions are of rising interest in plant sustainability, biomass production, plant biology, and systems biology. These interactions have been a challenge to detect until recent advancements in mass spectrometry imaging. Plants and microbes interact in four main regions within the plant, the rhizosphere, endosphere, phyllosphere, and spermosphere. This mini review covers the challenges within investigations of plant and microbe interactions. We highlight the importance of sample preparation and comparisons among time-of-flight secondary ion mass spectroscopy (ToF-SIMS), matrix-assisted laser desorption/ionization (MALDI), laser desorption ionization (LDI/LDPI), and desorption electrospray ionization (DESI) techniques used for the analysis of these interactions. Using mass spectral imaging (MSI) to study plants and microbes offers advantages in understanding microbe and host interactions at the molecular level with single-cell and community communication information. More research utilizing MSI has emerged in the past several years. We first introduce the principles of major MSI techniques that have been employed in the research of microorganisms. An overview of proper sample preparation methods is offered as a prerequisite for successful MSI analysis. Traditionally, dried or cryogenically prepared, frozen samples have been used; however, they do not provide a true representation of the bacterial biofilms compared to living cell analysis and chemical imaging. New developments such as microfluidic devices that can be used under a vacuum are highly desirable for the application of MSI techniques, such as ToF-SIMS, because they have a subcellular spatial resolution to map and image plant and microbe interactions, including the potential to elucidate metabolic pathways and cell-to-cell interactions. Promising results due to recent MSI advancements in the past five years are selected and highlighted. The latest developments utilizing machine learning are captured as an important outlook for maximal output using MSI to study microorganisms.

Automated high-throughput characterization of microbial metabolites and species using array ballpoint electrospray ionization technique.

Microbial metabolites are widely used in agriculture, food, environment, and medicine. However, there is a lack of high-throughput, nonclogging, and simple methods for the identification of microbial metabolites and their subspecies using ambient mass spectrometry (MS). Here, we proposed a method for analyzing the microbial metabolites and identifying their species using the array ballpoint electrospray ionization (aBPESI) technique. The previously developed BPESI was combined with the array analysis technique to form a high-throughput analysis technique called aBPESI. The bacteria cultured on the plate medium were directly analyzed using MS with aBPESI. Principal component analysis-linear discriminant analysis (PCA-LDA)algorithm was used to analyze the different subspecies groups. The results showed that aBPESI was capable of completing a sample analysis within 30 s, and the level of metabolite detection was comparable to existing techniques. The accuracy of bacterial subspecies identification was 90% (Pseudomonas aeruginosa) and 100% (Serratia marcescens). A new high-throughput and robust MS technique aBPESI was proposed. It does not require sample pretreatment and greatly reduces the sample analysis time. aBPESI shows a strong ability in microbial analysis and is expected to be further applied in other research fields.

High-Throughput Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry Method Validation for the Estimation of Atorvastatin and Active Metabolites in Human Plasma

A highly selective, sensitive, rugged, and rapid ultra high-performance liquid chromatography-tandem mass spectrometry method (UPLC-MS/MS) is optimized and validated for reliable quantification of atorvastatin (ATR) and its active metabolites, 2-hydroxy atorvastatin (2-ATR) and 4-hydroxy atorvastatin (4-ATR) in human plasma using atorvastatin-D5 (ATR-D5), 2-hydroxy atorvastatin-D5 (2-ATR-D5), and 4-hydroxy atorvastatin-D5 (4-ATR-D5) as deuterium-labeled internal standards (ISTDs), respectively. Isocratic mode chromatographic separation was used with a reverse-phase C18 Symmetry Shield (150 × 4.6 mm, 5.0 μm) column and a mobile phase of acetonitrile:2 mM ammonium formate (pH-3.0) [65:35%v/v] at a flow rate of 0.7 mL/min. Electrospray ionization technique with positive ion mode polarity was applied to achieve the best signal intensity and stable response. Solid-phase extraction by direct elution method was applied to extract the drugs from the plasma sample. The calibration curve range was validated from a concentration range of 0.500-250 ng/mL for ATR and 2-ATR and 0.200-20 ng/mL for 4-ATR. The within-batch and between-batch precision and accuracy were found to be consistent and reproducible for all the analytes across the validation. Extraction recoveries were >80% for all analytes and ISTDs. All peaks of analytes and the respective ISTDs were eluted within 5.2 min. In this validated method, selective multivariate analytical approaches were utilized such as best fit linearity range for different strength formulations, preventive measures for in vivo and ex vivo autodegradation of metabolites, and shorter analysis time. This validated method can be useful for challenging quantification of ATR and its active metabolites for therapeutic drug monitoring and in high-throughput clinical study sample analysis.

Preparation and evaluation of astaxanthin-loaded 2-hydroxypropyl-beta-cyclodextrin and Soluplus® nanoparticles based on electrospray technology.

Astaxanthin is a type of food-derived active ingredient with antioxidant, antidiabetic and non-toxicity functions, but its poor solubility and low bioavailability hinder further application in food industry. In the present study, through inclusion technologies, micellar solubilization and electrospray techniques, we prepared astaxanthin nanoparticles before optimizing the formulation to regulate the physical and chemical properties of micelles. We accomplished the preparation of astaxanthin nanoparticle delivery system based on single needle electrospray technology through use of 2-hydroxypropyl-β-cyclodextrin and Soluplus® to improveme the release behavior of the nanocarrier. Through this experiment, we successfully prepared astaxanthin nanoparticles with a particle size of approximately 80 nm, which was further verified with scanning electron microscopy and transmission electron microscopy. Furthermore, the encapsulation of astaxanthin molecules into the carrier nanoparticles was verified via the results of attenuated total reflectance intensity and X-ray powder diffraction techniques. The in vitro release behavior of astaxanthin nanoparticles was different in media that contained 0.5% Tween 80 (pH1.2, 4.5 and 6.8) buffer solution and distilled water. Also, we carried out a pharmacokinetic study of astaxanthin nanoparticles, in which it was observed that astaxanthin nanoparticle showed an effect of immediate release and significant improved bioavailability. 2-hydroxypropyl-β-cyclodextrin and Soluplus® were used in the present study as a hydrophilic nanocarrier that could provide a simple way of encapsulating natural function food with repsect to improving the solubility and bioavailability of poorly water-soluble ingredients. © 2023 Society of Chemical Industry.

Coated Blade Spray with a Barrier: Improving Negative Electrospray Ionization and Sample Preparation.

Substrate-based electrospray ionization (ESI) techniques like paper, wooden tip, plastic tip, and metal-needle-based spray suffer from corona discharge, high background noise, and unstable spray in negative ionization mode, especially for the analysis of complex biological matrices, such as blood and urine. Coated blade spray coupled with mass spectrometry (CBS-MS) combines solid-phase microextraction's (SPME) efficient sample clean-up and enrichment and ambient MS's fast analysis and has proven to be an appealing alternative tool for the fast screening of target analytes in complex matrices. This paper documents the development of a new CBS blade design that features a barrier at the far end of the ESI tip. The findings of this work show that the addition of this simple barrier enabled the total RSD% to be reduced to less than 10% for sample preparation, ionization, and the MS detection of several drugs of abuse in negative mode, without compensation using internal standards. The improved stability of ESI in negative mode was investigated by observing the ESI process with a microscope camera and testing via CBS-MS. The new design was applied for the analysis of three drugs of abuse in urine, with the calibration curve correlation coefficient (R2 ≥ 0.9997) being calculated without the use of internal standards. The overall RSD% of the peak area for one compound in 42 samples was 6.9%, which highlights the method's incredible reproducibility compared to other ambient MS techniques for analyzing real samples. The CBS device with a barrier was also applied for the on-blade sampling of 14 drugs of abuse in 20 μL of plasma spot in positive ionization mode. The results of these tests yielded a calibration curve correlation coefficient of R2 ≥ 0.9883 and limits of quantification (LOQs) between 0.25 and 25 ng/mL. The obtained results provide guidance on CBS device design optimization and the effective automation of the protocol.

Real-Time Sniffing Mass Spectrometry Aided by Venturi Self-Pumping Applicable to Gaseous and Solid Surface Analysis.

Based on the Venturi self-pumping effect, real-time sniffing with mass spectrometry (R-sniffing MS) is developed as a tool for direct and real-time mass spectrometric analysis of both gaseous and solid samples. It is capable of dual-mode operation in either gaseous or solid phase, with the corresponding techniques termed as Rg-sniffing MS and Rs-sniffing MS, respectively. In its gaseous mode, Rg-sniffing MS is capable of analyzing a gaseous mixture with response time (0.8-2.1 s rise time and 7.3-9.6 s fall time), spatial resolution (<80 μm), three-dimensional diffusion imaging, and aroma distribution imaging of red pepper. In its solid mode, an appropriate solvent droplet desorbs the sample from a solid surface, followed by the aspiration of the mixture using the Venturi self-pumping effect into the mass spectrometer, wherein it is ionized by a standard ion source. Compared with the desorption electrospray ionization (DESI) technique, Rs-sniffing MS demonstrated considerably improved limit of detection (LOD) values for arginine (0.07 μg/cm2 Rs-sniffing vs 1.47 μg/cm2 DESI), thymopentin (0.10 μg/cm2 vs 2.67 μg/cm2), and bacitracin (0.16 μg/cm2 vs 2.28 μg/cm2). Rs-sniffing is applicable for the detection of C60(OCH3)6Cl-, an intermediate in the methoxylation reaction involving C60Cl6 (solid) and methanol (liquid). The convenient and highly sensitive R-sniffing MS has a characteristic separation of desorption from the ionization process, in which the matrix atmosphere of desorption can be interfaced by a pipe channel and self-pumped by the Venturi effect with consequent integration using a standard ion source. The R-sniffing MS operates in a voltage-, heat-, and vibration-free environment, wherein the analyte is ionized by a standard ion source. Consequently, a wide range of samples can be analyzed simultaneously by the R-sniffing MS technique, regardless of their physical state.

Interaction of a natural compound nanoemulsion with Gram negative and Gram positive bacterial membrane; a mechanism based study using a microfluidic chip and DESI technique

The antibacterial activity of a nanoemulsion prepared from Satureja Khusitanica essential oil against a Gram-negative (Escherichia coli) and a Gram-positive (Bacillus atrophaeus) bacteria evaluated using microfluidic and conventional techniques. The effect of different residence time and concentrations on the antibacterial activity of nanoemulsion was studied by measuring the release of protein, nucleic acids, potassium, and also recording the MIC, MBC and time killing assays. Remarkable intensification was observed by employing microfluidic chip regarding a high-contact surface area between nanodroplets and bacterial membrane. The MIC and MBC values for E. coli and B. atrophaeus in conventional method were 400 and 1600 µg mL−1, respectively, whereas these values reduced to 11 to 50 µg mL−1 using microfluidic system. B. atrophaeus seemed to be more resistant than E. coli to the nanoemulsion treatment, perhaps due to different cell wall structures. Bacterial cell wall changes were examined using a desorption electrospray ionization (DESI) technique. It was found that the structural changes were more imminent in Gram negative E. coli by detecting a number of released lipids including phosphatidyl glycerol and phosphatidyl ethanolamines. The DESI spectra of B. atrophaeus revealed no M/Z related lipid release. These findings may help providing novel nano based natural antibacterials.

Photoelectron Circular Dichroism of Electrosprayed Gramicidin Anions.

Many sophisticated approaches for analyzing properties of chiral matter have been developed in recent years. But in general, the available chiroptical methods are limited to either solvated or small gaseous molecules. Studying the chirality of large biopolymers in the gas phase, including aspects of the secondary structure, becomes accessible by combining the electrospray ionization technique with chiroptical detection protocols. Here, laser-induced photodetachment from gramicidin anions, a peptide consisting of 15 amino acids has been investigated. The angular distribution of photoelectrons is demonstrated to be sensitive to the substitution of protons by cesium ions, which is accompanied by a conformational change. The photoelectron circular dichroism (PECD) is -0.5% for bare gramicidin, whereas gramicidin with several Cs+ ions attached exhibits a PECD of +0.5%. The results are complemented and supported by ion mobility studies. The presented approach offers the prospect of studying chirality and the secondary structure of various biopolymers.

Development and validation of a sensitive LCMS/MS method for the simultaneous quantification of Azelnidipine and Chlorthalidone in human plasma

Highly resolved, selective and sensitive liquid chromatography/tandem mass spectrometry (LC–MS/MS) method was optimised for the simultaneous quantification and recently approved combined medication for the treatment of hypertension viz. azelnidipine and chlorthalidone in spiked human plasma. The study utilizes nifedipine as internal standard. In the extraction of analytes from spiked plasma, acetonitrile was used to induce protein precipitation and then liquid – liquid extraction was carried using ethyl acetate solvent followed by the LCMS-MS analysis. The analytes were separated on Inertsil ODS C18 (4.6 mm×100 mm, 5 μm) column at room temperature with 65:35 (v/v) ratio of acetonitrile and 0.1% formic acid as the mobile phase at 0.5 mL/min flow rate. Detection was performed on a triple quadrupole mass spectrometer employing electrospray ionization technique, operating in multiple reaction monitoring with the transitions of m/z 583 → 331, 339 → 321 and 347 → 328 respectively for azelnidipine, chlorthalidone and nifedipine. The analytes were detected at a retention time of 1.72 min, 2.62 min and 3.12 min respectively for azelnidipine, chlorthalidone and nifedipine and the analysis was completed within run time of 5 min. The analysis was carried in the calibration range of 5-500 ng/mL with a very sensitive detection limit of 1.5 ng/mL. The method was validated as per FDA guidelines for bioanalytical method validation and the results in all the validation parameters were in the acceptable limit. Results proved that the method was selective, sensitive, accurate, precise and stable and hence can be applicable for the routine analysis of azelnidipine and chlorthalidone in biological samples.