Full Chemical Characterization Research Articles

Optimization of the recycled aggregate processing using the full factorial design approach, chemical, physical and microstructural characterization of treated aggregates by pre-coated with cementitious paste

The present study aims to study the treatment of (RCA) faction (16/25) by their encapsulation into cement slurry with a (W/C) ratio of (0.5). A complete factorial plan 23was applied by considering three independent factors, namely the state of RCA (GR), the soaking time into slurry (DT) and the hardening time (RCA) (A). The selected responses are the compressive strength and the water accessible porosity (voids) of concrete incorporate treated (RCA), after 28 days of curing. The results were analyzed using the statistical software JMP Trial 16.The compressive strength of concretes showed an increase between 20.5 % and 21.04 % with respect to (NCA).However, the porosity of concretes showed a decline with respect to RCA. The main factor that conditions the two responses is the cure time (A), followed by the RCA state. According to the physical characteristics of RCATi, the encapsulation leads to increased water absorption, bulk, and absolute density. The XRD and TGA techniques confirmed the presence of hydrates and quartz in RCA and RCAT. The microstructural analysis of RCAT seems to be in favor of (dry RCAT) soaked in the cement slurry for 10 min where the adhesion is stronger and the (ITZ) is denser.

Non-pyrogenicity and biocompatibility of parylene-coated magnetic bead implants.

Clinical grade magnetic bead implants have important applications in interfacing with the human body, providing contactless mechanical attachment or wireless communication through human tissue. We recently developed a new strategy, magnetomicrometry, that uses magnetic bead implants as passive communication devices to wirelessly sense muscle tissue lengths. We manufactured clinical-grade magnetic bead implants and verified their biocompatibility via intramuscular implantation, cytotoxicity, sensitization, and intracutaneous irritation testing. In this work, we test the pyrogenicity of the magnetic bead implants via a lagomorph model, and we test the biocompatibility of the magnetic bead implants via a full chemical characterization and toxicological risk assessment. Further, we test the cleaning, sterilization, and dry time of the devices that are used to deploy these magnetic bead implants. We find that the magnetic bead implants are non-pyrogenic and biocompatible, with the insertion device determined to be safe to clean, sterilize, and dry in a healthcare setting. These results provide confidence for the safe use of these magnetic bead implants in humans.

Characterization of Magnetic Nanoparticles from the Shells of Freshwater Mussel L. fortunei and Marine Mussel P. perna

Magnetite (Fe3O4) nanoparticles were extracted from the shells of freshwater Limnoperna fortunei (Dunker 1857) and marine Perna perna (Linnaeus 1758) mussels, followed by full physical and chemical characterization using ICP-OES, UV–Vis, EDX, Raman, and XRD spectroscopy, VSM magnetometry, and SEM and TEM techniques. Considering their spatial distribution, the ferrimagnetic particles in the shells had low concentration and presented superparamagnetic behavior characteristics of materials of nanometric size. Transmission electron microscopy (TEM, especially HRTEM) indicated round magnetic particles around 100 nm in size, which were found to be aggregates of nanoparticles about 5 nm in size. The TEM data indicated no iron oxide particles at the periostracum layer. Nevertheless, roughly round iron (hydr)oxide nanoparticle aggregates were found in the nacre, namely, the aragonite layer. As the aragonite layer is responsible for more than 97% of the shell of L. fortunei and considering the estimated size of the magnetic nanoparticles, we infer that these particles may be distributed homogeneously throughout the shell.

Developing a novel Ti-doped ɣAl2O3 xerogel with high photocatalytic chemical and microbial removal performance: Characterization and mechanistic insights

In this work, a Ti-doped alumina (Ti-γAl2O3) xerogel (TAX) was synthesized from Al powder as a cost-effective precursor. Full physical, chemical, structural, and electrochemical characterization of the prepared materials were performed. It was shown that as-made Ti-γAl2O3 is a mesoporous nanomaterial with high specific surface area, uniform morphology, the existence of polyhedral coordinated Al3+ ions, many acidity active sites, high light absorption efficiency, and effective bandgap energy. These features made it an efficient photocatalyst for water photocatalytic treatment. In the photocatalytic process with the TAX as the catalyst irradiated by the ultraviolet A photons, around 97% of 10 mg/L Remdesivir (RDV) was degraded within 30 min (pH = 7, TAX = 100 mg/L), and elucidation of the degradation pathway was achieved; low adsorption and minimal O2·- contribution was found in the otherwise HO•-dominated photocatalytic process, as suggested by the scavenger tests. The Electron Paramagnetic Resonance spectroscopy validated the proposed species (but not 1O2), while the RDV degradation pathway towards mineralization was proposed by Liquid Chromatography–Mass Spectrometry analysis. Besides, concerning its applicability, the effect of operational parameters (pH, [TAX], [RDV], water matrix) was scrutinized and validated a notable performance over several consecutive reused cycles. Finally, almost 6.5 log E. coli inactivation was attained (in mild conditions), all indicating the high photocatalytic potential of this material.

The SARS-CoV-2 Hydra, a tiny monster from the 21st century: Thermodynamics of the BA.5.2 and BF.7 variants

SARS-CoV-2 resembles the ancient mythical creature Hydra. Just like with the Hydra, when one head is cut, it is followed by appearance of two more heads, suppression of one SARS-CoV-2 variant causes appearance of newer variants. Unlike Hydra that grows identical heads, newer SARS-CoV-2 variants are usually more infective, which can be observed as time evolution of the virus at hand, which occurs through acquisition of mutations during time. The appearance of new variants is followed by appearance of new COVID-19 pandemic waves. With the appearance of new pandemic waves and determining of sequences, in the scientific community and general public the question is always raised of whether the new variant will be more virulent and more pathogenic. The two variants characterized in this paper, BA.5.2 and BF.7, have caused a pandemic wave during the late 2022. This paper gives full chemical and thermodynamic characterization of the BA.5.2 and BF.7 variants of SARS-CoV-2. Having in mind that Gibbs energy of binding and biosynthesis represent the driving forces for the viral life cycle, based on the calculated thermodynamic properties we can conclude that the newer variants are more infective than earlier ones, but that their pathogenicity has not changed.

Non-enzymatic disposable electrochemical sensors based on CuO/Co3O4@MWCNTs nanocomposite modified screen-printed electrode for the direct determination of urea

A new electrochemical impedimetric sensor for direct detection of urea was designed and fabricated using nanostructured screen-printed electrodes (SPEs) modified with CuO/Co3O4 @MWCNTs. A facile and simple hydrothermal method was achieved for the chemical synthesis of the CuO/Co3O4 nanocomposite followed by the integration of MWCNTs to be the final platform of the urea sensor. A full physical and chemical characterization for the prepared nanomaterials were performed including Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), contact angle, scanning electron microscope (SEM) and transmission electron microscopy (TEM). Additionally, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to study the electrochemical properties the modified electrodes with the nanomaterials at different composition ratios of the CuO/Co3O4 or MWCNTs. The impedimetric measurements were optimized to reach a picomolar sensitivity and high selectivity for urea detection. From the calibration curve, the linear concentration range of 10−12–10−2 M was obtained with the regression coefficient (R2) of 0.9961 and lower detection limit of 0.223 pM (S/N = 5). The proposed sensor has been used for urea analysis in real samples. Thus, the newly developed non-enzymatic sensor represents a considerable advancement in the field for urea detection, owing to the simplicity, portability, and low cost-sensor fabrication.

First identification, chemical analysis and pharmacological characterization of N-piperidinyl etonitazene (etonitazepipne): A recent addition to the nitazene opioid subclass

A 25-year-old man visited his general practitioner with generalized muscle pain and severe abdominal pain including nausea, cramping and diarrhea, asking help for detoxification. The patient stated that his current complaints were the result of the use of high doses of N-piperidinyl etonitazene. After repeated intranasal administrations, he declared to have acquired a high tolerance for the substance. N-piperidinyl etonitazene (‘etonitazepipne’) represents a recent addition to the rapidly expanding class of 2-benzylbenzimidazole nitazene opioids. Here, we report on the full chemical and pharmacological characterization of N-piperidinyl etonitazene. A serum and a urine sample from the patient, collected at the same time, and the online-sourced N-piperidinyl etonitazene powder were available for analysis. The powder and patient samples were analyzed with a liquid chromatography - high resolution mass spectrometry (LC-HRMS) screening method using data-dependent acquisition. Additionally, an accurate HRMS method using targeted selected ion monitoring was developed for the quantification of N-piperidinyl etonitazene. A cell-based bioassay was used to determine the extent of MOR activation in both the patient samples and in the powder. Furthermore, MOR binding affinity via radioligand binding assays, in vitro pharmacological characterization and in vivo effects (in rats) were examined. Analysis of the powder via different analytical techniques (LC-HRMS, GC-MS, UHPLC-DAD, FT-IR) led to the unequivocal identification of N-piperidinyl etonitazene. The obtained concentrations in serum and urine from the patient were 1.21 and 0.51 ng/mL, respectively. Via molecular networking of the obtained HRMS data, various urinary metabolites were identified, with O-dealkylation as the primary metabolism route. Further characterization revealed that N-piperidinyl etonitazene had a high MOR binding affinity in vitro. Moreover, a high potency (EC50 = 2.49 nM; 53 and 6.7 times more potent than morphine and fentanyl, respectively) and relative efficacy (Emax = 183% versus hydromorphone; reaching 80% and 36% higher relative efficacies than morphine and fentanyl, respectively) in activating human MOR in vitro was obtained. Despite its equal efficacy, N-piperidinyl etonitazene was still less potent than etonitazene, the most potent nitazene identified to date. The compound showed characteristic opioid-mediated behavior in rats, as evidenced by catalepsy, increased hot plate latency and hypothermia. Using the bioassay, we could derive that the activity exerted by the patient's serum concentration is equivalent to that exerted by 2.5–10 ng/mL fentanyl or 10–25 ng/mL hydromorphone, which is compatible with the declared tolerance. N-piperidinyl etonitazene was identified for the first time in an online-sourced powder and in the serum and urine of a patient. Taken together, our findings indicate that etonitazepipne is a highly potent opioid with the potential to cause harm in users.

Chemical properties, sources and size-resolved hygroscopicity of submicron black-carbon-containing aerosols in urban Shanghai

Abstract. Refractory black carbon (rBC) aerosols play an important role in air quality and climate change, yet highly time-resolved and detailed investigations on the physicochemical properties of rBC and its associated coating are still scarce. In this work, we used a laser-only Aerodyne soot particle aerosol mass spectrometer (SP-AMS) to exclusively measure rBC-containing (rBCc) particles, and we compared their properties with those of the total nonrefractory submicron particles (NR-PM1) measured in parallel by a high-resolution AMS (HR-AMS) in Shanghai. Observations showed that, overall, rBC was thickly coated, with an average mass ratio of coating to rBC core (RBC) of ∼5.0 (±1.7). However, the ratio of the mass of the rBC-coating species to the mass of those species in NR-PM1 was only 19.1 (±4.9) %; sulfate tended to condense preferentially on non-rBC particles, so the ratio of the sulfate on rBC to the NR-PM1 sulfate was only 7.4 (±2.2) %, while the majority (72.7±21.0 %) of the primary organic aerosols (POA) were associated with rBC. Positive matrix factorization revealed that organics emitted from cooking did not coat rBC, and a portion of the organics that coated rBC was from biomass burning; such organics were unidentifiable in NR-PM1. Small rBCc particles were predominantly from traffic, while large-sized ones were often mixed with secondary components and typically had a thick coating. Sulfate and secondary organic aerosol (SOA) species were generated mainly through daytime photochemical oxidation (SOA formation, likely associated with in situ chemical conversion of traffic-related POA to SOA), while nocturnal heterogeneous formation was dominant for nitrate; we also estimated an average time of 5–19 h for those secondary species to coat rBC. During a short period that was affected by ship emissions, particles were characterized as having a high vanadium concentration (on average 6.3±3.1 ng m−3) and a mean vanadium/nickel mass ratio of 2.0 (±0.6). Furthermore, the size-resolved hygroscopicity parameter (κrBCc) of rBCc particles was obtained based on their full chemical characterization, and was parameterized as κrBCc(x)=0.29–0.14 × exp⁡(-0.006×x) (where x ranges from 150 to 1000 nm). Under critical supersaturations (SSC) of 0.1 % and 0.2 %, the D50 values were 166 (±16) and 110 (±5) nm, respectively, and 16 (±3) % and 59 (±4) %, respectively, of the rBCc particles by number could be activated into cloud condensation nuclei (CCN). Our findings are valuable for advancing the understanding of BC chemistry as well as the effective control of atmospheric BC pollution.

Metal-Organic Enzyme Nanogels as Nanointegrated Self-Reporting Chemobiosensors.

A fluorometric glucose biosensor based on fine-tuned chemoenzymatic nanohybrids is herein proposed. The successful integration of an engineered glucose oxidase enzyme and an optically responsive polymeric nanogel in a single entity has led to the fabrication of a highly efficient glucose chemobiosensor. The optical responsiveness has been achieved by the loading of preactivated polymeric hydrogel with fluorescent lanthanide, i.e., cerium (III), cations. A comprehensive investigation of the responsiveness of the biomaterial revealed the interplay between the oxidation state of the cerium lanthanide and the fluorescence emission of the polymer. Finally, a full structural, chemical, and biochemical characterization of the reported system supports the chemobiosensors as robust, specific, and sensitive materials that could be utilized to faithfully quantify the amount of glucose in tear fluids.

Materials synthesis at terapascal static pressures

Theoretical modelling predicts very unusual structures and properties of materials at extreme pressure and temperature conditions1,2. Hitherto, their synthesis and investigation above 200 gigapascals have been hindered both by the technical complexity of ultrahigh-pressure experiments and by the absence of relevant in situ methods of materials analysis. Here we report on a methodology developed to enable experiments at static compression in the terapascal regime with laser heating. We apply this method to realize pressures of about 600 and 900 gigapascals in a laser-heated double-stage diamond anvil cell3, producing a rhenium–nitrogen alloy and achieving the synthesis of rhenium nitride Re7N3—which, as our theoretical analysis shows, is only stable under extreme compression. Full chemical and structural characterization of the materials, realized using synchrotron single-crystal X-ray diffraction on microcrystals in situ, demonstrates the capabilities of the methodology to extend high-pressure crystallography to the terapascal regime.

Comprehensive phytochemical characterization of Raphanus raphanistrum L.: In vitro antioxidant and antihyperglycemic evaluation

Raphanus raphanistrum L. is an edible flowering plant that belongs to the Brassicaceae family and is also known as wild radish. Recently, it was reported as a sustainable source of bioactive compounds and nutrients. For comprehensive metabolites profiling of R. raphanistrum whole plant, three types of extracts; aqueous ethanol (AEE), dichloromethane (DCME), and defatted aqueous ethanol (DAEE), were prepared. DCME was investigated by GC/MS analysis and led to the characterization of twenty-nine compounds from the unsaponifiable fraction and fourteen compounds from the saponifiable one. Likewise, the HPLC-MS/MS analysis of AEE aided with the molecular networking via the GNPS platform, resulting in the annotation of 99 metabolites belonging to different chemical classes. Besides, seven compounds were isolated from the DAEE, five of them are reported for the first time from R. raphanistrum. In parallel, the antioxidant evaluation revealed that DCME has the most potent activity using DPPH· and NO· scavenging assays with IC50 (117.68 & 162.31 µg/mL), compared to ascorbic acid (244.85 & 117.12 µg/mL) and BHT (90.82 & 76.69 µg/mL), respectively. DCME also gave the highest α-amylase and α-glucosidase inhibitory activities with an IC50 (µg/mL) of 150.72 and 123.16, respectively. Among the tested compounds, isorhamnetin 3-O-rutinoside showed the highest activity with an IC50 (µg/mL) 274.68 and 195.87, respectively on the same investigated enzymes. As far as we can tell, the current work is considered the full chemical characterization and first antihyperglycemic evaluation of the wild radish.

Feasibility of iron‐based sorbents for arsenic removal from groundwater

AbstractBACKGROUNDArsenic is one of the most serious drinking water contaminants around the world. The development of iron oxide materials, including nanoparticles, as sorbents for arsenic remediation has shown promising results in recent years. Some of these materials are already used as commercial‐grade arsenic sorbents. However, the use of iron‐oxide nanoparticles (IONPs) has barely been used in real‐world conditions. This work compares commercial IONPs with three proven arsenic sorbents.RESULTSThe full chemical characterization includes electron microscopy, X‐ray diffraction and X‐ray photon spectroscopy to determine morphology, crystalline structure and elemental analysis, respectively. Arsenic remediation studies also were conducted in both batch and column set‐ups with real water samples from Salamanca, Mexico. The conditions (pH 8, high concentration of silica and presence of other interferences) found in this site are outside the recommended parameters of operations for most of the arsenic sorbents. All of the materials observed a negative effect because of silica presence. However, the effects observed in batch did not correlate directly to the column tests. This is important when evaluating the viability of using sorbents in specific conditions.CONCLUSIONSA feasibility analysis revealed that some commercial sorbents can treat water with the conditions presented in the selected site, but the cost of treatment is not viable for developing countries. In addition, the generated waste by using these sorbents would be substantial. These challenges could be diminished by using nanoparticles, yet the commercially‐available IONPs do not fill this gap. Better designed nanomaterials are still needed for arsenic removal. © 2022 Society of Chemical Industry (SCI).

Wildfire atmospheric chemistry: climate and air quality impacts

Wildfire atmospheric chemistry: climate and air quality impacts

Structure Elucidation and Mitigation of Endogenous Interferences in LC-MS-Based Metabolic Profiling of Urine.

Liquid chromatography-mass spectrometry (LC-MS) is the main workhorse of metabolomics owing to its high degree of analytical sensitivity and specificity when measuring diverse chemistry in complex biological samples. LC-MS-based metabolic profiling of human urine, a biofluid of primary interest for clinical and biobank studies, is not widely considered to be compromised by the presence of endogenous interferences and is often accomplished using a simple "dilute-and-shoot" approach. Yet, it is our experience that broad obscuring signals are routinely observed in LC-MS metabolic profiles and represent interferences that lack consideration in the relevant metabolomics literature. In this work, we chromatographically isolated the interfering metabolites from human urine and unambiguously identified them via de novo structure elucidation as two separate proline-containing dipeptides: N,N,N-trimethyl-l-alanine-l-proline betaine (l,l-TMAP) and N,N-dimethyl-l-proline-l-proline betaine (l,l-DMPP), the latter reported here for the first time. Offline LC-MS/MS, magnetic resonance mass spectrometry (MRMS), and nuclear magnetic resonance (NMR) spectroscopy were essential components of this workflow for the full chemical and spectroscopic characterization of these metabolites and for establishing the coexistence of cis and trans isomers of both dipeptides in solution. Analysis of these definitive structures highlighted intramolecular ionic interactions as responsible for slow interconversion between these isomeric forms resulting in their unusually broad elution profiles. Proposed mitigation strategies, aimed at increasing the quality of LC-MS-based urine metabolomics data, include modification of column temperature and mobile-phase pH to reduce the chromatographic footprint of these dipeptides, thereby reducing their interfering effect on the underlying metabolic profiles. Alternatively, sample dilution and internal standardization methods may be employed to reduce or account for the observed effects of ionization suppression on the metabolic profile.

Zoisite-(Pb), a New Orthorhombic Epidote-Related Mineral from the Jakobsberg Mine, Värmland, Sweden, and Its Relationships with Hancockite

The new mineral zoisite-(Pb), ideally CaPbAl3(SiO4)(Si2O7)O(OH), was discovered in a sample from the Jakobsberg manganese-iron oxide deposit, Värmland, Sweden. Zoisite-(Pb) is found as pale pink subhedral prisms elongated on [010], up to 0.3 mm in size, associated with calcite, celsian, diopside, grossular, hancockite, hyalophane, native lead, phlogopite, and vesuvianite. Associated feldspars show one of the highest PbO contents (~7–8 wt%) found in nature. Electron-microprobe analysis of zoisite-(Pb) point to the empirical formula (Ca1.09Pb0.86Mn2+0.01Na0.01)∑1.97(Al2.88Fe3+0.10Mn3+0.04)∑3.02Si3.00O12(OH)1.00. The eight strongest diffraction lines [dobs, Iobs, (hkl)] are 8.63 s (101), 8.11 mw (200), 4.895 m (011), 4.210 m (211), 3.660 s (112, 311), 3.097 mw (312), 2.900 s (013), and 2.725 m (511). Zoisite-(Pb) is isostructural with zoisite and its crystal structure was refined up to R1 = 0.0213 for 2013 reflections with Fo > 4σ(Fo). Pb shows a stereochemically active lone pair leading to a lopsided distribution of its coordinating oxygens. A full chemical and Raman characterization of zoisite-(Pb) and of the Pb-bearing epidote hancockite is reported, together with an improved crystal structural model of hancockite, refined up to R1 = 0.0254 for 2041 reflections with Fo > 4σ(Fo). The effects of the incorporation of Pb in the crystal structure of zoisite-(Pb), hancockite, and related synthetic and natural phases are described and discussed.

ISOLATION AND IDENTIFICATION OF A NEW ANTIPROLIFERATIVE INDOLOCARBAZOLE ALKALOID DERIVATIVE EXTRACTED FROM FARMED SHRIMP (Litopenaeus vannamei) MUSCLE

Farmed shrimp Litopenaeus vannamei, one of the most consumed seafood in the planet, is a source of antiproliferative extracts still to be fully characterized. This study the isolation and identification of these antiproliferative compounds. From a chloroform-soluble extract from shrimp muscle, hexane- and methanol-soluble fractions were obtained and tested for antiproliferative activity (MTT), a bioassay that guided the fractionation and isolation of bioactive fractions using open column chromatography. MeOH-soluble fraction resulted bioactive and was subjected to further fractionation from which one subfraction outstand for being highly active against prostate cancer cell line. Antiproliferative effects were evaluated using colorimetric assays and cell morphology observations. Further chromatographic procedures resulted in sub-fractions from which one was effective in causing DNA damage and F-actin polymerization, which suggests cellular collapse and apoptosis. According to the structural chemical characterization carried out, dioctyl phthalate, eicosapentaenoic acid, and an indolocarbazole alkaloid type of compound were identified. This last compound, which resulted majorly responsible for the bioactivity, was not found reported in the available databases. Pure EPA control was used to compare it with the subfraction, observing greater activity in the subfraction than when EPA was used, suggesting that another compound different from EPA is providing the highest activity; but, more investigation is needed for a full chemical and structural characterization.

A comprehensive review on current technologies for removal of endocrine disrupting chemicals from wastewaters

In the recent years, endocrine disrupting compounds (EDCs) has received increasing attention due to their significant toxic effects on human beings and wildlife by affecting their endocrine systems. As an important group of emerging pollutant, EDCs have been detected in various aquatic environments, including surface waters, groundwater, wastewater, runoff, and landfill leachates. Their removal from water resources has also been an emerging concern considering growing population as well as reducing access to fresh water resources. EDC removal from wastewaters is highly dependent on physicochemical properties of the given EDCs present in each wastewater types as well as various aquatic environments. Due to chemical, physical and physicochemical diversities in these parameters, variety of technologies consisting of physical, biological, electrochemical, and chemical processes have been developed for their removal. This review highlights that the effectiveness of EDC removal is highly dependent of selecting the appropriate technology; which decision is made upon a full wastewater chemical characterization. This review aims to provide a comprehensive perspective about all the current technologies used for EDCs removal from various aquatic matrices along with rising challenges such as the antimicrobial resistance gene transfer during EDC treatment.

Analytical characterization of "etonitazepyne," a new pyrrolidinyl-containing 2-benzylbenzimidazole opioid sold online.

This paper reports on the identification and full chemical characterization of the substance colloquially called "etonitazepyne" or "N-pyrrolidino etonitazene" (2-(4-ethoxybenzyl)-5-nitro-1-(2-(pyrrolidin-1-yl)ethyl)-1H-benzo[d]imidazole), a potent NPS opioid of the 5-nitrobenzimidazole class. Identification of etonitazepyne was performed, on a sample purchased during routine monitoring of the drug market, using GC-MS, HRAM LC-MS/MS, 1 H NMR, and FTIR. The chromatographic data, together with the FTIR data, indicated the presence of a highly pure compound and already indicated a benzimidazole structure. The specific benzimidazole regio-isomer was confirmed using 1 H NMR spectroscopy, resulting in the unambiguous identification of etonitazepyne.

Synthesis and structural characterization of bio-based bis(cyclic carbonate)s for the preparation of non-isocyanate polyurethanes

Full chemical structure characterization of cyclic carbonates from diepoxides synthesized using sustainable bio-based polyols with different molecular weights and carbon dioxide.

First Report on Brorphine: The Next Opioid on the Deadly New Psychoactive Substance Horizon?

New psychoactive substances continue to appear on the drug market. Until recently, new synthetic opioids, which are among the most dangerous new psychoactive substances, primarily encompassed analogs of the potent analgesic fentanyl. Lately, also other new synthetic opioids have increasingly started to surface. This is the first report on the identification and full chemical characterization of brorphine, a novel potent synthetic opioid with a piperidine benzimidazolone structure. A powder, identified as brorphine, was obtained from a patient seeking medical help for detoxification. Brorphine was also found in a serum sample of the patient. Liquid chromatography-high-resolution mass spectrometry (LC-HRMS) identified an exact mass of m/z 400.1020 and 402.1005 for the compound, corresponding to both bromine isotopes. Further chemical characterization was performed by gas chromatography-mass spectrometry, liquid chromatography-diode array detection and Fourier-transform infrared spectroscopy analyses. Finally, the structure was confirmed by performing 1H-NMR and 13C-NMR spectroscopy. In vitro biological activity of brorphine was determined by a cell-based µ-opioid receptor activation assay, resulting in an EC50 of 30.9 nM (13.5 ng/mL) and an Emax of 209% relative to hydromorphone, confirming the high potency and efficacy of this compound. In a serum sample of the patient, brorphine and a hydroxy-metabolite were found using the LC-HRMS screening method. The presence of opioid activity in the serum was also confirmed via the activity-based opioid screening assay. The occurrence of brorphine is yet another example of how the illicit drug market is continuously evolving in an attempt to escape international legislation. Its high potency poses a serious and imminent health threat for any user.