Giorgio Famiglini

University of Urbino | UNIURB · Department of Earth, Life and Environmental Sciences DISTEVA

Mass spectrometry (MS) enables precise identification and quantification of molecules, particularly when combined with chromatography. The advent of atmospheric pressure ionization (API) techniques allowed the efficient coupling of liquid chromatography with MS (LC-MS), extending analyses to nonvolatile and thermolabile compounds. API techniques pr...

Per- and polyfluoroalkyl substances (PFASs) are a class of aliphatic manufactured compounds comprising fluoro-chemicals with varied functional groups and stable carbon-fluorine bonds. They are defined as “forever chemicals”, due to their persistent and bio-accumulative character. These substances have been detected in various environmental samples,...

First proof of concept of the coupling between normal-phase liquid chromatography and electron ionization mass spectrometry using a Liquid Electron Ionization (LEI) interface.

This work presents a sustainable and rapid method for halogenated pesticide analysis without chromatographic separation. The system is composed of a microfluidic open interface (MOI) for solid-phase microextraction (SPME) liquid phase desorption, connected to a liquid electron ionization mass spectrometry interface (LEI-MS). Either a triple quadrup...

One of modern analytical chemistry main challenges is providing as fast as possible results in different application fields. In this view, real-time analysis techniques are experiencing ever-increasing success as they can provide data quickly, almost without sample preparation steps. Most of real-time approaches are based on direct mass spectrometr...

Solid-phase microextraction (SPME) directly coupled to MS is a widespread technique for determining small molecules in different matrices in many application fields. Here we present a modified microfluidic open interface (MOI) connected to a passive-flow-splitter device (PFS) for the direct coupling of SPME to a liquid-electron ionization (LEI) int...

Negative chemical ionization (NCI) and electron-capture negative ionization (ECNI) are gas chromatography–mass spectrometry (GC–MS) techniques that generate negative ions in the gas phase for compounds containing electronegative atoms or functional groups. In ECNI, gas-phase thermal electrons can be transferred to electrophilic substances to produc...

Extra virgin olive oil (EVOO) is one of the main ingredients of the Mediterranean diet. It is claimed as a functional food for its unique content of health-promoting compounds. Tyrosol (Tyr), Hydroxytyrosol (Htyr), and their phenolic derivatives present in EVOO show beneficial properties, and their identification and quantification, both in their f...

This review article traces the history of the use of liquid chromatography coupled with mass spectrometry (LC-MS) using electron ionization (EI) from the first attempts up to the present day. At the time of the first efforts to couple LC to MS, 70 eV EI was the most common ionization technique, typically used in gas chromatography-mass spectrometry...

We present a modified microfluidic open interface (MOI) for the direct coupling of Bio-SPME to a liquid electron ionization-tandem mass spectrometry (LEI-MS/MS) system as a sensitive technique that can directly analyze biological samples without the need for sample cleanup or chromatographic separations as well as without measurable matrix effects...

Herein we present an efficient, column-switching method that relies on a custom-made T-union passive diffusion micromixer to assist water dilution and promote trap solute focusing of a high sample volume dissolved in pure organic solvent using a 0.075 mm i.d. nano-LC column. This method allows injecting 20 μL (or higher) of sample volume, speeding...

Mass spectrometry has been the “gold standard” for drugs of abuse (DoA) analysis for many decades because of the selectivity and sensitivity it affords. Recent progress in all aspects of mass spectrometry has seen significant developments in the field of DoA analysis. Mass spectrometry is particularly well suited to address the rapidly proliferatin...

Current mass spectrometry-based methodologies for synthetic organic reaction monitoring largely use electrospray ionization (ESI), or other related atmospheric pressure ionization-based approaches. Monitoring of complex, heterogeneous systems may be problematic because of sampling hardware limitations, and many relevant analytes (neutrals) exhibit...

Liquid Electron Ionization (LEI), is an innovative liquid chromatography-mass spectrometry (LC–MS) interface that converts liquid HPLC eluent to the gas-phase in a mass spectrometer equipped with an electron ionization (EI) source. LEI extends the electronic spectra libraries access to liquid chromatography, providing a powerful tool in the untarge...

Buprenorphine and its metabolites are routinely monitored to assess patient compliance with drug detoxification programs or as pain killers. A rapid method for the simultaneous analysis of buprenorphine, norbuprenorphine, and glucuronides in urine using ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was develope...

Environmental context Marine mining activities are potential sources of environmental pollution. Diethylene glycol used in offshore platforms has been suspected to facilitate the release of toxic substances into the sea. The results obtained elucidate that this release is not significant for the metals examined here, apart from iron, nor for polycy...

Electron ionization (EI) is a unique and advantageous ionization technique typically employed in gas chromatography-mass spectrometry (GC-MS). Here are presented two different approaches to benefit from EI in liquid chromatography-mass spectrometry (LC-MS). The first EI-based interface exploits EI of vibrationally cold molecules in supersonic molec...

In this article, a detailed overview of the current high‐performance liquid chromatography/mass spectrometry (HPLC/MS) instrumentation, suitable for the determination of a large number of pesticides, is reported. Particular emphasis is given to the role of the mass spectrometric apparatus involved in each interfacing technique with several informat...

A novel liquid chromatography-mass spectrometry (LC-MS) interfacing concept is presented and discussed. The new interface, called Liquid-EI (LEI), is based on electron ionization (EI) but, differently from any previous attempt, the vaporization of solutes and mobile phase takes place at atmospheric pressure into a specifically designed region, call...

This article describes a nano-scale method for the determination and quantification of five benzodiazepines (BDZ) in an alcoholic grappa drink (chlordiazepoxide; lorazepam; diazepam; oxazepam; medazepam). BDZ are typically used in drug-facilitated crimes (DFC) for their accessibility and synergistic effects with alcohol. Specimens collected on the...

The aim of this study was to monitor for the first time the oligosaccharide pattern in the northwestern Adriatic Sea. Oligosaccharides are components of the low-molecular-weight fraction of dissolved organic matter (DOM). They perform an important ecological function in the microbial loop prompting substrates for bacterial degradation. In particula...

This is the first application based on electron ionization (EI) using a Direct-EI LC interface and MS/MS to detect unequivocally target compounds in a very small real sample. The determination and quantification of benzodiazepines (BDZ) in very small residues of beverages, collected at the scene of drug-facilitated crimes (DFC) are mandatory in leg...

Polycyclic aromatic hydrocarbons (PAHs) are USEPA regulated priority pollutants. Their low aqueous solubility requires very sensitive analytical methods for their detection, typically involving preconcentration steps. Presented is the first demonstrated ‘proof of concept’ use of condensed phase membrane introduction mass spectrometry (CP-MIMS) coup...

Detection of target and non-target substances and their characterization in complex samples is a challenging task. Here we demonstrate that coating the electron ionization (EI) ion source of an LC-MS system with a sol-gel ceramic film can drastically improve the detection of high-molecular weight and high-boiling analytes. A new ion source coated w...

Benzodiazepines (BDZs) are widely used as tranquilizers and anti-depressive drugs in common clinical practice. However, their ready availability and their synergistic effects with alcohol make them attractive for criminal intentions. To prove criminal action for legal reasons, it is often necessary to analyze beverage residues from a crime scene. M...

Sudden infant death syndrome (SIDS) and sudden intrauterine unexpected death syndrome (SIUDS) are an unresolved teaser in the social-medical and health setting of modern medicine and are the result of multifactorial interactions. Recently, prenatal exposure to environmental contaminants has been associated with negative pregnancy outcomes, and veri...

An LC-MS method for the analysis of personal care and household products without sample preparation is presented. The method takes advantage of the Direct-EI LC-MS interface for the quantitation of principal components, as well as for the identification of unknown or undeclared ingredients. The technique has proven its inertness towards matrix effe...

Nano-LC columns of different lengths (14–35 cm), 75 μm i.d., were packed with solid-core C18 particles using a conventional HPLC system at low pressure (375 bar) and without expensive tools and fittings. Solid-core particles consist of a solid, non-porous core surrounded with a shell of a porous layer with a very narrow particle size distribution....

Electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photo-ionization (APPI) are the most important techniques for the ionization of liquid samples. However, working under atmospheric pressure conditions, all these techniques involve some chemical rather than purely physical processes, and therefo...

We investigated the effect of temperature on the packing procedure of nano-LC columns (up to 50 cm) and on their performance. Several slurries of stationary phase were prepared using different solvent mixtures. Their stability was evaluated at several temperatures: 70°C, 50°C, and room temperature. At the higher temperature (70°C) the suspensions r...

Pyrethrum extract is a mixture of six insecticidal compounds from the flower heads of Chrysanthemum cinerariaefolium L.. Since they only have low to moderate mammalian toxicity they can be used as natural insecticides in agriculture or to develop low cost and safe dermatological formulations. Because of the thermal instability of pyrethrins, analyt...

An innovative approach for nano-liquid chromatography (LC) gradient generation is presented. This system represents an optimized and refined version of a prototype proposed by the authors a few years ago: the current version is characterized by a new configuration that guarantees complete automation and easier operation. The core of the system is a...

One of the crucial tasks of pharmaceutical industry is to quantify the potential genotoxic impurities (PGIs) coming from the process of drug production. The European Medicines Agency (EMEA) imposes analytical testing limits in the order of μg/g, depending on drug dosage and exposure period, that means the need of a sensitive and selective method of...

We propose a new analytical approach, based on liquid chromatography (LC) coupled to electron ionization mass spectrometry (EI-MS), using a Direct-EI interface, for dermal absorption evaluation studies. Penetration through the skin of a given compound is evaluated by means of in vitro assays using diffusion cells. Currently, the most popular approa...

This review article will give an up-to-date and exhaustive overview on the efficient use of electron ionization (EI) to couple liquid chromatography and mass spectrometry (LC-MS) with an innovative interface called Direct-EI. EI is based on the gas-phase ionization of the analytes, and it is suitable for many applications in a wide range of LC-amen...

This paper focuses on the development of a novel approach to analyze underivatized fatty acids in human plasma. The method is based on liquid-liquid extraction followed by reversed phase liquid chromatography coupled to direct-electron ionization mass spectrometry (LC-Direct-EI-MS). The assay is validated. Calibrations show satisfactory linearity a...

The purpose of this article is to underline the possibility of efficiently using electron ionization (EI) in liquid chromatography (LC) and mass spectrometry (MS). From a historical perspective, EI accompanied the first attempts in LC-MS but, owing to several technical shortcomings, it was soon outshined by soft, atmospheric pressure ionization (AP...

Matrix-dependent signal suppression or enhancement represents a major drawback in quantitative analysis with liquid chromatography coupled to atmospheric pressure ionization mass spectrometry (LC-API-MS). Because matrix effects (ME) might exert a detrimental impact on important method parameters (limit of detection, limit of quantification, lineari...

Produced formation waters (PFWs) represent the largest aqueous wastes that are normally discharged into the marine environment during the offshore gas production processes. The chemical additive diethylene glycol (DEG) is widely used in the gas production line and therefore can be found in the PFW, becoming of environmental concern. In this study,...

Water pollution by organochlorine pesticides (OCPs) is considered as an analytical challenge, since these persistent and nonbiodegradable pollutants are not amenable by liquid chromatography coupled to atmospheric pressure ionization mass spectrometry (LC/API-MS). This represents a significant constraint in multiresidue analysis of real samples, wh...

A major limitation in quantitative analysis with electrospray ionization mass spectrometry (ESI-MS) is represented by the so-called matrix effects in which the matrix coextracted with the analytes can alter the signal response, causing either suppression or enhancement, resulting in poor analytical accuracy, linearity, and reproducibility. In the d...

The mucilage phenomenon, a sporadic but massive accumulation of gelatinous material, can cause serious damage to the tourism and fishing industries along the Adriatic coast. Mucilage is presently thought to be the result of the aggregation of dissolved organic matter (DOM) into particulate organic matter (POM). Three principal classes of compounds...

Contamination of water resources by organochlorine pesticides (OCPs) continues to receive widespread attention because of the increasing concern regarding their high persistence and bioaccumulation. These organic pollutants are not amenable by liquid chromatography (LC) coupled to atmospheric pressure ionization-mass spectrometry, which represents...

Produced formation waters (PFWs), a by-product of both oil and gas extraction, are separated from hydrocarbons onboard oil platforms and then discharged into the sea through submarine outfalls. The dispersion of PFWs into the environment may have a potential impact on marine ecosystems. We reproduce the initial PFW-seawater mixing process by means...

Diethylene glycol (DEG) is extensively used on offshore gas platforms to prevent the hydrate formation during the gas-water separation process and to inhibit corrosion events. This chemical might enter in the marine environment via the produced formation water (PFW) discharge. In this study, a new approach was applied to the investigation of the DE...

Major progress in interfacing liquid chromatography and electron ionization mass spectrometry is presented. The minimalism of the first prototype, called the Direct-EI interface, has been widely refined, improved, and applied to modern instrumentation. The simple interfacing principle is based on the straight connection between a nanoHPLC system an...

The massive accumulation of organic matter, which periodically occurs in the northern Adriatic Sea, and in other locations worldwide, is presently thought to be the results of the aggregation of dissolved organic matter (DOM) into particulate organic matter (POM). This phenomenon is the result of human activities and propitious weather conditions....

Water, methanol (MeOH), acetonitrile (ACN), and binary MeOH-water and ACN-water solutions of different spin probes (nitroxides), selected to mimic the behavior of different pollutants, were adsorbed onto stationary phases usually used in reversed-phase high-performance liquid chromatography (RP-HPLC). These stationary phases are constituted by poro...

We present a new method for the determination of 29 endocrine-disrupting compounds in marine water. This method is based on a solid-phase extraction preconcentration technique, followed by a nanoscale liquid chromatography/direct-electron ionization (EI) mass spectrometric analysis. Direct-EI is a novel technique for the rapid conversion of a GC/MS...

A comprehensive evaluation and a thorough discussion of the fields of possible applications of the Direct-EI interface are described in this review. Direct-EI allows the direct introduction of the effluent from a capillary HPLC column into the electron ionization (EI) ion source of a mass spectrometer. Thanks to the reduced liquid intake and an in-...

The fate of enrofloxacin present in raw sewage at a swine-breeding facility was investigated by liquid-liquid extraction and reversed-phase liquid chromatography with photodiode array detection. Samples were collected in the storage pits of each pigsty and in a nonaerated lagoon used to stock the sewage. In the pigsties, the sewage was mixed with 1...

Electron ionization (EI) takes place exclusively in the gas phase, creating a highly reproducible and characteristic fragmentation pattern that makes analyte identification easier. Achille Capiello, Giorgio Famiglini, and Pierangela Palma at the Università di Urbino (Italy) describe adapting the technique for LC/MS by using a specialized nebulizer...

We describe a method, based on a new nano-HPLC gradient generator coupled to a modified direct electron ionization (EI) LC–MS interface, for the analysis of several compounds of environmental interest. The gradient generator was installed on a conventional HPLC system and the nano-flow rate was achieved using a double splitter. Reproducible gradien...

Our recent on-line solid-phase extraction (SPE) device for micro-liquid chromatography, known as micro-solid-phase extraction (microSPE), was compared with traditional SPE for the analysis, from aqueous samples, of 4 pesticides belonging to different classes. Two different kinds of adsorbents, C18 and graphitized carbon black, were tested. A 2-stag...

A new, simple device generates accurate nano- and microflow rate gradients from any conventional HPLC system. The core of the new device is represented by an electric-actuated, computer-controlled, multiposition HPLC valve. The valve hosts six reservoirs for as many different mobile-phase compositions of increasing strength. A low flow rate stream...

A new LC/MS method for the determination of organophosphorus pesticides in water, based on the use of direct-electron ionization (EI) interface, is presented. Direct-EI is a new device that, in a very simple fashion, couples a nano-HPLC system with a mass spectrometer equipped with electron ionization capability. The nanoscale liquid flow allows fo...

A method to extract and analyze organic compounds from water is presented. A solid phase micro-trap (micro-SPE) directly connected to the micro-analytical column is used. Sensibility and specificity needed for trace analysis are guaranteed by mass spectrometric electron ionization (EI) detection. A new micro-HPLC/EI-MS interface called Capillary-EI...

A miniaturized, aerosol based interface for directly coupling a liquid chromatograph with a mass spectrometer is presented. The interface is entirely within the electron ionization (EI) source of the mass spectrometer and no additional, external devices are needed. This simple and effective approach exploits micro-flow nebulization technology provi...

I. Introduction 88 II. Cap‐EI Interface 90 A. Interface Performance 92 III. Direct‐EI Interface 93 A. Interface Performance 97 IV. Conclusions 103 Acknowledgments 103 References 103 Two recent approaches for coupling capillary scale liquid chromatography and electron ionization mass spectrometry are reviewed and discussed. The first one, Ca...

A new solid-phase extraction on-line device for micro-HPLC is presented. This device optimizes the injection of very dilute samples into a packed capillary column. It consists of two capillary, reversed-phase, HPLC columns of different length that can be linked together as a single chromatographic column. The first segment, only 2 cm long is connec...

The use of a new LC-MS interface (cap-EI), part of a Waters Integrity system, capable of generating EI spectra at micro flow rates is presented. The cap-EI interface relies on the production of a fine aerosol by means of a nebulizer and supported by a nitrogen jet. Sensitivity, response linearity, reproducibility, and LC compatibility of the interf...

A capillary-scale particle beam interface was used to detect 18 phenolic compounds in red wine samples. This technique allows reproducible, library searchable electron ionization spectra at only 1 microliter/min mobile phase flow-rate for a sensitive detection of the analytes in complex matrices. The method makes use of a narrow bore, reversed-phas...

A new ion-interaction micro-HPLC method, for the simultaneous separation of acidic and base-neutral pesticides, was coupled to a capillary-scale particle beam LC/MS interface for EI mass spectrometric detection of the analytes. The method was employed for analysis of tap water in which a large number of functionally different pesticides can be dete...

Some people look at the particle-beam interface as an object of the past in a changing world of promising new instrumentation. We believe that generating EI spectra, when possible, is a short cut to the solution of many analytical problems. We are convinced that this approach is valid, but the hardware can surely benefit of new ideas in order to fo...

The use of nonvolatile buffers like phosphate and citrate is usually incompatible with mass spectrometric detection or may heavily interfere with ion generation. In the case of conventional HPLC flow rates, the continuous buffer deposition produces fouling of the mass spectrometer ion source and may worsen the performance of any LC/MS interface as...

Modern liquid chromatography-mass spectrometry interfaces often require a limited intake of mobile phase to work properly. Packed capillary columns combine high chromatographic efficiency, reduced flow-rate and an appreciable reliability and can be successfully employed in such applications. Acidic pesticides, a group of important compounds widely...

High-performance liquid chromatography (HPLC) packed capillary columns have gained a great deal of interest for their role in conjunction with other analytical techniques, particularly mass spectrometry. However, the advantages offered by the low mobile phase flow-rate are often compromised by modest method detection limits due to sub-microliter in...

A method for the analysis of four widely used explosives based on reversed-phase liquid chromatography coupled to a quadrupole mass spectrometer is presented. A microflow rate particle beam interface was employed that offers simplified operation procedures and improved interfacing performance. A positive role played by the reduced size of the aeros...

A new method for the determination of 18 acidic pesticides in water by liquid chromatography/mass spectrometry is presented. A liquid-solid extraction procedure for the isolation of the pesticides from the aqueous samples was employed. The method, which avails of a micro-flow rate particle beam interface, offers improved performance far the analysi...

A new method for the analysis of aflatoxins in food extracts, based on liquid chromatography/mass spectrometry interfacing, is presented. The chromatographic separation was performed with a reversed phase packed capillary column coupled with a modified particle beam interface capable of handling microliter per minute flow rates. This system allows...

Coumarins are a large group of compounds that are naturally present in plant tissues and that exhibit a wide range of pharmacological properties. Analytical methods based on chromatographic techniques and conventional detectors are inadequate to accurately analyze coumarins in complex matrices such as plant extracts. In this article a new method ba...

In a particle beam interface, HPLC amenable compounds are transformed in solute particles and then rapidly vaporized to undergo electron impact ionization. The heat transferred and the time spent in this process are minimal, due to the submicrometer size of the solute particles obtained from today's nebulizers. In spite of this, some heat-sensitive...

A modified Hewlett-Packard LC/MS particle beam interface which allows the use of mobile phase microflow rates (down to 1 mu L/min) has been refined and evaluated. Its overall performance was accurately investigated to discover and underline positive contributions to liquid chromatography/mass spectrometry interfacing. Several aspects of the couplin...

A new method for the determination of 32 base/neutral and 13 acidic pesticides in water, which has been proven to be particularly amenable to high-performance liquid chromatography, is discussed. A liquid/solid extraction procedure for the isolation of pesticides from aqueous samples is employed. The LC/MS analysis is carried out with a LC-18 rever...

The generation of a micro-gradient for micro HPLC capillary columns is described. The system used is a modified and improved version of a split flow gradient elution device. Gradient tests have been performed and have shown good reproducibility under all conditions. The system has been successfully coupled with a particle beam LC-MS interface and t...