Thermal desorption direct analysis in real-time high-resolution mass spectrometry and machine learning allow the rapid authentication of ground black pepper and dried oregano: A proof-of-concept study

Thermal desorption direct analysis in real-time high-resolution mass spectrometry (TD-DART-HRMS) approaches have gained popularity for fast screening of a variety of samples. With rapid volatilization of the sample at increasing temperatures outside the mass spectrometer, this technique can provide a direct readout of the sample content with no sample preparation. In this study, TD-DART-HRMS's utility for establishing spice authenticity was examined. To this aim, we directly analyzed authentic (typical) and adulterated (atypical) samples of ground black pepper and dried oregano in positive and negative ion modes. We analyzed a set of authentic ground black pepper samples (n = 14) originating from Brazil, Sri Lanka, Madagascar, Ecuador, Vietnam, Costa Rica, Indonesia, Cambodia, and adulterated samples (n = 25) consisting of mixtures of ground black pepper with this spice's nonfunctional by-products (pinheads or spent) or with different exogenous materials (olive kernel, green lentils, black mustard seeds, red beans, gypsum plaster, garlic, papaya seeds, chili, green aniseed, or coriander seeds). TD-DART-HRMS facilitated the capture of informative fingerprinting of authentic dried oregano (n = 12) originating from Albania, Turkey, and Italy and those spiked (n = 12) with increasing percentages of olive leaves, sumac, strawberry tree leaves, myrtle, and rock rose. A predictive LASSO classifier was built, after merging by low-level data fusion, the positive and negative datasets for ground black pepper. Fusing multimodal data allowed retrieval of more comprehensive information from both datasets. The resultant classifier achieved on the withheld test set accuracy, sensitivity, and specificity of 100%, 75%, and 90%, respectively. On the contrary, the sole TD-(+)DART-HRMS spectra of the oregano samples allowed construction of a LASSO classifier that predicted the adulteration of the oregano with excellent statistical indicators. This classifier achieved, on the withheld test set, 100% each for accuracy, sensitivity, and specificity.     

Background-Free Detection of Spin-Exchange Dynamics at Ultra-Low Magnetic Field

Ultra-low field nuclear magnetic resonance spectroscopy (NMR) and imaging (MRI) inherently suffer from a low signal-to-noise ratio due to the small thermal polarization of nuclear spins. Transfer of polarization from a pre-polarized spin system to a thermally polarized spin system via the Spin Polarization Induced Nuclear Overhauser Effect (SPINOE) could potentially be used to overcome this limitation. SPINOE is particularly advantageous at ultra-low magnetic field, where the transferred polarization can be several orders of magnitude higher than thermal polarization. Here we demonstrate direct detection of polarization transfer from highly polarized ¹²⁹Xe gas spins to ¹H spins in solution via SPINOE. At ultra-low field, where thermal nuclear spin polarization is close to background noise levels and where different nuclei can be simultaneously detected in a single spectrum, the dynamics of the polarization transfer can be observed in real time. We show that by simply bubbling hyperpolarized ¹²⁹Xe into solution, we can enhance ¹H polarization levels by a factor of up to 151-fold. While our protocol leads to lower enhancements than those previously reported under extreme Xe gas pressures, the methodology is easily repeatable and allows for on-demand enhanced spectroscopy. SPINOE at ultra-low magnetic field could also be employed to study ¹²⁹Xe interactions in solutions.     

The thermal stability of lattice-energy minima of 5-fluorouracil: metadynamics as an aid to polymorph prediction

This paper reports a novel methodology for the free-energy minimization of crystal structures exhibiting strong, anisotropic interactions due to hydrogen bonding. The geometry of the thermally expanded cell was calculated by exploiting the dependence of the free-energy derivatives with respect to cell lengths and angles on the average pressure tensor computed in short molecular dynamics simulations. All dynamic simulations were performed with an elaborate anisotropic potential based on a distributed multipole analysis of the isolated molecule charge density. Changes in structure were monitored via simulated X-ray diffraction patterns. The methodology was used to minimize the free energy at ambient conditions of a set of experimental and hypothetical 5-fluorouracil crystal structures, generated in a search for lattice-energy minima with the same model potential. Our results demonstrate that the majority ( approximately 75%) of lattice-energy minima are thermally stable at ambient conditions, and hence, the free-energy (like the lattice-energy) surface is complex and highly undulating. Metadynamics trajectories (Laio, A.; Parrinello, M. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 12562) started from the free-energy minima only produced transitions that preserved the hydrogen-bonding motif, and thus, further developments are needed for this method to efficiently explore such free-energy surfaces. The existence of so many free-energy minima, with large barriers for the alteration of the hydrogen-bonding motif, is consistent with the range of motifs observed in crystal structures of 5-fluorouracil and other 5-substituted uracils.     

New chemistry of olefin complexes of platinum(II) unravelled by basic conditions: synthesis and properties of elusive cationic species

The evolution in basic medium ([RO-] = 1 M in methanol, R = H or Me) of five-coordinate platinum(II) compounds, [PtCl2(eta2-C2H4)(N-N)], 2a-c, (N-N = N,N,N',N'-tetramethyl-1,2-ethanediamine, a; 2,2'-bipyridyl, b; 1,10-phenanthroline, c) leads to the formation of [PtCl(eta1-CH2CH2-OCH3)(N-N)], 5a-c. The analogous compound 5d (N-N = 2,9-dimethyl-1,10-phenanthroline, d) can also be prepared, but not via transformation of the five-coordinate species 2d in basic medium where it is quite stable. 5d can instead be prepared by reaction of d with a strongly basic methanol solution of Zeise's anion [PtCl3(eta2-C2H4)](-), 1. In such a medium the di-anionic trans-[PtCl2(OR)(eta1-CH2CH2-OCH3)](2-) species (1") reacts with to form exclusively 5d. Hydrolysis of with acids bearing weakly coordinating anions leads to [PtCl(eta2-C2H4)(N-N)]+, 3a-c, as stable cations; upon the same treatment 5d does not generate 3d, but it reacts with HCl to give 2d in almost quantitative yield. Cationic complexes 3b, 3c, here reported for the first time, were reacted with some nucleophiles and their behaviour compared with that of the already known 3a. In 3b, 3c the metal centre competes with the coordinated ethene for binding to nucleophiles; therefore the acetylacetonate anion can either add to the olefin (affording compounds 6b, 6c ) or to the metal ion replacing the ethene ligand (yielding compounds 7b, 7c). Under similar conditions, 3a gives exclusively 6a. Secondary amines readily add to ethene in 3b, 3c, affording the addition products 8b, 8c, which undergo a ready cyclization to an azaplatinacyclobutane ring (9b, 9c). The remarkable ease of the four-membered ring formation has been related to the high electrophilic character of the metal core in 3b, 3c.     

DFT research on the dehydroxylation reaction of pyrophyllite 1. First-principle molecular dynamics simulations

The dehydroxylation of pyrophyllite involves the reaction of OH groups and elimination of water molecules through two possible mechanisms, one involving the bridging hydroxyl groups of an octahedral Al (3+) pair and the other two hydroxyl groups reacting across the dioctahedral vacancy. First-principles molecular dynamics simulations at the density functional theory level are used together with the metadynamics algorithm to explore the free-energy surface (FES) of the initial step of the dehydroxylation. We observe that the two possible dehydroxylation mechanisms yield similar activation energies at 0 K, but at high temperatures, the cross mechanism has lower free energy than that of the on-site one. The dehydroxylation process produces different semidehydroxylated intermediates that should be taken into account. The role of the temperature in favoring a dehydroxylation nonconcerted chain mechanism over another is here elucidated, and a novel competitive mechanism, which is assisted by the structural apical oxygens in the high-temperature regime, is proposed.     

Evaluation of Detector Position and Light Fluence Distribution Using an Infrared Navigation System during Pleural Photodynamic Therapy†

Photodynamic therapy (PDT) has been used to treat malignant pleural mesothelioma. Current practice involves delivering light to a prescribed light fluence with a point source, monitored by eight isotropic detectors inside the pleural cavity. An infrared (IR) navigation system was used to track the location of the point source throughout the treatment. The recorded data were used to reconstruct the pleural cavity and calculate the light fluence to the whole cavity. An automatic algorithm was developed recently to calculate the detector positions based on recorded data within an hour. This algorithm was applied to patient case studies and the calculated results were compared to the measured positions, with an average difference of 2.5 cm. Calculated light fluence at calculated positions were compared to measured values. The differences between the calculated and measured light fluence were within 14% for all cases, with a fixed scattering constant and a dual correction method. Fluence-surface histogram (FSH) was calculated for photofrin-mediated PDT to be able to cover 80% of pleural surface area to 50 J cm⁻²(83.3% of 60 J cm⁻²). The study demonstrates that it will be possible to eliminate the manual measurement of the detector positions, reducing the patient's time under anesthesia.     

Superhydrophobicity due to the hierarchical scale roughness of PDMS surfaces

Wettability control has been widely investigated in the last decades for technological applications such as microfluidic devices and self-cleaning surfaces by modifying both the chemical composition and the geometric structure of the surfaces. Inspired by the typical morphology of superhydrophobic leaves (such as lotus leaves), we have developed a dual-scale roughness, micro- and nanosized, on polydimethylsiloxane (PDMS) surfaces. By combining different geometric parameters and plasma treatment conditions, the structures were controlled hierarchically, at different independent length scales. Both the microsized replicated pillars and the nanosized etched posts tuned the wettability of the PDMS surfaces in a very simple way, up to contact angles of 170 degrees . Furthermore, changes in the influence of micro- and nanoscale geometrical structures were investigated. Hysteresis and contact angles of water droplets are evaluated as a combined effect of micropillars and a superimposed roughness, resulting in high advancing contact angles and low sliding angles.     

Joziknipholones A and B: the first dimeric phenylanthraquinones, from the roots of Bulbine frutescens

From the roots of the African plant Bulbine frutescens (Asphodelaceae), two unprecedented novel dimeric phenylanthraquinones, named joziknipholones A and B, possessing axial and centrochirality, were isolated, together with six known compounds. Structural elucidation of the new metabolites was achieved by spectroscopic and chiroptical methods, by reductive cleavage of the central bond between the monomeric phenylanthraquinone and -anthrone portions with sodium dithionite, and by quantum chemical CD calculations. Based on the recently revised absolute axial configuration of the parent phenylanthraquinones, knipholone and knipholone anthrone, the new dimers were attributed to possess the P-configuration (i.e., with the acetyl portions below the anthraquinone plane) at both axes in the case of joziknipholone A, whereas in joziknipholone B, the knipholone part was found to be M-configured. Joziknipholones A and B are active against the chloroquine resistant strain K1 of the malaria pathogen, Plasmodium falciparum, and show moderate activity against murine leukemic lymphoma L5178y cells.