High Proton Affinity Research Articles

Dihydrogen phosphate anion boosts the detection of sugars in electrospray ionization mass spectrometry: A combined experimental and computational investigation.

Sugars are key molecules of life but challenging to detect via electrospray ionization mass spectrometry (ESI-MS). Unfortunately, sugars are challenging analytes for mass spectrometric methods due to their high gas-phase deprotonation energies and low gas-phase proton affinities which make them difficult to ionize in high abundance for MS detection. Hydrogen-bond interactions in H2 PO4 - -saccharide anionic systems were studied both experimentally (via electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, ESI-FT-ICR-MS) and computationally by several sophisticated density-functional theoretical methods (DFT and DFT-D3). The H2 PO4 - dopant boosts the detection of sugars up to 51-times in the case of sucrose and up to 263-times for glucose (at 0.1 ppm concentration level). H2 PO4 - binds toward sugar molecules with noticeably more hydrogen bonds than the established dopant chloride Cl- does, with increasing binding energies in the order: Monosaccharides < Trisaccharides < Disaccharides. Analysis of a complex oak plant sample revealed that NH4 H2 PO4 specifically labeled a diverse set of sugar-type plant metabolites in the form of [M + H2 PO4 ]- complexes. We reveal the mechanism of interaction of H2 PO4 - with different sugars and glycosylated organic compounds, which significantly enhances their ionization in mass spectrometry. A computational and experimental investigation is presented. A strong correlation between the MS signal intensities of detected [M + H2 PO4 ]- anions of different saccharides and their calculated dissociation enthalpies was revealed. Thus, the variation in MS signal intensities can be very well described to a large extent by the variation in calculated saccharide affinities toward the H2 PO4 - dopant anion, showing that DFT-D3 can very well describe experimental FT-ICR-MS observations.

A new protonated molecule discovered in TMC-1: HCCNCH+

In recent years we have seen an important increase in the number of protonated molecules detected in cold dense clouds. Here we report the detection in TMC-1 of HCCNCH+, the protonated form of HCCNC, which is a metastable isomer of HC3N. This is the first protonated form of a metastable isomer detected in a cold dense cloud. The detection was based on observations carried out with the Yebes 40 m telescope and the 30 m telescope of the Institut de Radioastronomie Millimétrique (IRAM), which revealed four harmonically related lines. We derived a rotational constant B = 4664.431891 ± 0.000692 MHz and a centrifugal distortion constant D = 519.14 ± 4.14 Hz. From a high level ab initio screening of potential carriers, we confidently assigned the series of lines to the ion HCCNCH+. We derived a column density of (3.0 ± 0.5) × 1010 cm−2 for HCCNCH+, which results in a HCCNCH+/HCCNC abundance ratio of 0.010 ± 0.002. This value is well reproduced by a state-of-the-art chemical model which, however, is subject to important uncertainties regarding the chemistry of HCCNCH+. The observational and theoretical status of protonated molecules in cold dense clouds indicate that there exists a global trend in which protonated-to-neutral abundance ratios MH+/M increase with increasing proton affinity of the neutral M, although if one is restricted to species M with high proton affinities (&gt; 700 kJ mol−1), MH+/M ratios fall in the range 10−3–10−1, with no apparent correlation with the proton affinity. We suggest various protonated molecules that are good candidates for detection in cold dense clouds in the near future.

Subnanometric alkaline-earth oxide clusters for sustainable nitrate to ammonia photosynthesis

The limitation of inert N2 molecules with their high dissociation energy has ignited research interests in probing other nitrogen-containing species for ammonia synthesis. Nitrate ions, as an alternative feedstock with high solubility and proton affinity, can be facilely dissociated for sustainable ammonia production. Here we report a nitrate to ammonia photosynthesis route (NO3−RR) catalyzed by subnanometric alkaline-earth oxide clusters. The catalyst exhibits a high ammonia photosynthesis rate of 11.97 mol gmetal−1 h−1 (89.79 mmol gcat−1 h−1) with nearly 100% selectivity. A total ammonia yield of 0.78 mmol within 72 h is achieved, which exhibits a significant advantage in the area of photocatalytic NO3−RR. The investigation of the molecular-level reaction mechanism reveals that the unique active interface between the subnanometric clusters and TiO2 substrate is beneficial for the nitrate activation and dissociation, contributing to efficient and selective nitrate reduction for ammonia production with low energy input. The practical application of NO3−RR route in simulated wastewater is developed, which demonstrates great potential for its industrial application. These findings are of general knowledge for the functional development of clusters-based catalysts and could open up a path in the exploitation of advanced ammonia synthesis routes with low energy consumption and carbon emission.

Proton Affinity Values of Fentanyl and Fentanyl Analogues Pertinent to Ambient Ionization and Detection.

Proton affinity is a major factor in the atmospheric pressure chemical ionization of illicit drugs. The detection of illicit drugs by mass spectrometry and ion mobility spectrometry relies on the analytes having greater proton affinities than background species. Evaluating proton affinities for fentanyl and its analogues is informative for predicting the likelihood of ionization in different environments and for optimizing the compounds' ionization and detection, such as through the addition of dopant chemicals. Herein, density functional theory was used to computationally determine the proton affinity and gas-phase basicity of 15 fentanyl compounds and several relevant molecules as a reference point. The range of proton affinities for the fentanyl compounds was from 1018 to 1078 kJ/mol. Fentanyl compounds with the higher proton affinity values appeared to form a bridge between the oxygen on the amide and the protonated nitrogen on the piperidine ring based on models and calculated bond distances. Experiments with fragmentation of proton-bound clusters using atmospheric flow tube-mass spectrometry (AFT-MS) provided estimates of relative proton affinities and showed proton affinity values of fentanyl compounds >1000 kJ/mol, which were consistent with the computational results. The high proton affinities of fentanyl compounds facilitate their detection by ambient ionization techniques in complex environments. The detection limits of the fentanyl compounds with AFT-MS are in the low femtogram range, which demonstrates the feasibility of trace vapor drug detection.

Triboionization in Discontinuous Atmospheric Pressure Inlet for a Miniature Ion Trap Mass Spectrometer.

Discontinuous atmospheric pressure interface (DAPI) consisting of a pinch valve, a silicone tube, and two metal capillaries has been widely used in miniature mass spectrometry. It is interesting that clear ion signals could be observed even when the extra ionization source was turned off. In-depth analysis suggested that this new ionization phenomenon known as triboionization is based on the surface friction on the inner surface of the silicone tube during the on/off of the pinch valve. In this study, triboionization in the DAPI of a miniature ion trap mass spectrometer was investigated. It was discovered that the signal intensity depended greatly on the material and the roughness of the silicone tube used in the DAPI. By rubbing the inner surface of the silicone tube, for example, the signal intensity can increase by nearly 20 times. Two connected pinch valves were developed to study the effects of the discharge pressure, the number, and the frequency of on/off of the pinch valve on triboionization, which were verified to have a large impact on the product ions. In addition, the humidity of the inner surface of the silicone tube impacted the signal intensity of product ions and the mass spectrum patterns, where the product ions were typically protonated ions. As the humidity increases, the signal intensity of analytes with high proton affinity increases accordingly. This triboionization source, which does not require heat, light, radiation, auxiliary gas, or solution, has been preliminarily proved to have potential for surface detection after continuous enrichment.

Novel and Polynuclear K- and Na-Based Superalkali Hydroxides as Superbases Better Than Li-Related Species and Their Enhanced Properties: An Ab Initio Exploration.

Hydroxides of superalkalis (particularly, K- and Na-related species) are shown for the first time to function as superbases. A new small series of hydroxides (XMn+1OH) is designed based on superalkali species (XMn+1) where M (K and Na) is alkali metal atoms, n is the maximal formal valence of the central atom X (F, O, and N), and n ≥ 1. To probe whether such fascinating polynuclear superalkali hydroxides (SAHs), especially the K- and Na-associated moieties are as basic as the representative alkali metal hydroxides (KOH, NaOH, and LiOH) as well as similar Li-based SAHs, a comprehensive computational exploration (in the gas phase) has been reported using the framework of an ab initio method. The ab initio calculations reveal that both the K- and Na-related SAHs consisting of larger gas-phase proton affinity (PA) and gas-phase basicity (GB) values demonstrate stronger basic character compared to the LiOH and Li-based SAHs. However, the available SAHs act as strong bases as well as superbases; among the proposed K- and Na-based SAHs, remarkably, the OK3OH moiety having the highest PA (1168.4 kJ/mol) and GB (1146.9 kJ/mol) values shows the evidence of the strongest basicity (i.e., superbase/hyperbase), which exceed enough (ΔPA: 142.1 kJ/mol and ΔGB: 146.9 kJ/mol) the IUPAC-defined superbasicity threshold values (PA: 1026.3 kJ/mol and GB: 1000 kJ/mol) of 1,8-bis(dimethylamino)naphthalene (DMAN). Furthermore, theoretical signatures have been predicted via the electronic structure calculation approach in probing the dissociation energy, ionization potential, electron affinity, HOMO–LUMO gap, and chemical hardness as well as the NCI plot and QTAIM tools are used for the bonding feature analysis and such parameters are well linked with the basicity analyzing parameters. In this study, the ab initio-based computational experiments provide some new insights into the basicity features and understanding of the structural and electronic features of a small series of designed K- and Na-related SAHs. Design and synthesis of such theoretically examined SAHs may pave alternative routes for the experimentally rewarding applications.

A DFT study on the mechanism for polymerization of δ-valerolactone initiated by N-heterocyclic carbene (NHC) catalysts

Polymerization reactions using renewable raw material as substrate (namely, δ-valerolactone) and N-heterocyclic carbenes (NHC) as organocatalysts to form polyesters were investigated by computational approaches. Two routes were investigated for the reaction, either with the NHC acting as a Brønsted base and activating an alcohol used as co-initiator or by direct nucleophilic attack of the NHC on the carbonyl carbon of the lactone, forming a zwitterionic intermediate. In agreement with previous studies, the lowest energy pathway leading to polymerization is that where the NHC activates the alcohol co-initiator, yielding a partially charged alkoxide that then performs a nucleophilic attack on the lactone. The proton affinity of the NHCs shows a high correlation with the activation enthalpy for the first reaction step. Thus, NHCs with high proton affinity stabilize the first intermediate and make the lactone ring-opening the rate-determining step for the reaction.

The influence of microwave radiation from the geocosmos on the state of a living organism

The cardinal problem of biophysics is insufficient understanding of the microwave radiation influence on a living organism. Microwave fluxes enter the biosphere from the earth’s ionosphere during solar flares and geomagnetic storms, and also from the anthropogenic background. The task of the work was to present quantum-mechanical estimates of the ionosphere influence on the biosphere. Estimates for aqueous media of an organism are made within the framework of a new concept which describes the processes of formation of polyatomic Rydberg molecules built from their parent molecules by adding a proton, which is possible due to their high affinity for protons. The resulting ions are neutralized by capturing an electron into the Rydberg orbital, which is confirmed in experiments for the gases and liquids. The enhancement of the associative properties of highly diluted biologically active solutions under the influence of microwave flows is also investigated. One of the best partners in the mechanism of increasing formation of associates with the participation of microwave fluxes are water molecules (with its high proton affinity). When the number of water molecules grows with superdilution, an increasing number of microwave quanta are involved in the associate formation of water-containing biocomponents. An interpretation of the phenomenon of sporadic “non-reproducibility” of bioexperiments and contribution of geocosmic factors to the arthritis and viral pathology are presented.

The Promoter Role of Amines in the Condensation of Silicic Acid: A First-Principles Investigation.

Though well-recognized, the molecular-level understanding of the multifunctional roles of amines in the condensation of polysilicic acids, which is one of the key processes in hydrothermal synthesis of zeolites, is still limited. Taking ethylamine as a prototype, we investigated the mechanism of polysilicic acid condensation in the existence of organic amines in aqueous solution with extensive first-principles-based calculations. Because of the high proton affinity, ethylamine exists as amine silicates and alters the subsequent condensation mechanisms from a 1-step lateral attack mechanism accompanied with simultaneous intermolecular proton transfer in neutral aqueous solution to a 2-step SN2-like mechanism. Specifically, the 5-coordinated Si species that were not observed on pathways of condensation in neutral solution are effectively stabilized by the ethylamine cations as intermediates, and the barriers for condensation of ortho-silicic acid are significantly reduced from 133 kJ/mol in neutral solution to 58 and 63 kJ/mol for formation of the 5-coordinated Si intermediate and proton transfer for water release, respectively. Similar variations of mechanisms and barriers for condensation were also observed in the formation of cyclic trimers as well as linear and cyclic tetramers of ortho-silicic acids. Based on these, it was proposed that apart from acting as structure-directing agents, pore fillers, and pH adjusters, organic amines can also function as promoters in the condensation of polysilicic acids.

The Infrared Spectrum of Protonated C70

Abstract With the detection of C60, C70, and in the interstellar medium, fullerenes are currently the largest molecules identified in space. The relatively high proton affinities of C60 and C70 support the hypothesis that protonated fullerenes may also be abundant in the interstellar matter. Here, we present the first experimental vibrational spectrum of C70H+, recorded in the gas phase. The attachment of a proton to C70 causes a drastic symmetry lowering, which results in a rich vibrational spectrum. As compared to C60, where all C-atoms are equivalent due to the icosahedral symmetry, C70 belongs to the D5h point group and has five nonequivalent C-atoms, which are available as protonation sites. Combined analysis of the experimental spectrum and spectra computed at the density functional theory level enables us to evaluate the protonation isomers being formed. We compare the IR spectra of C60H+ and C70H+ to IR emission spectra from planetary nebulae, which suggests that a mixture of these fullerene analogs could contribute to their IR emission.

Alkali metal ion-induced conformation changes of methionine- and leucine enkephalin investigated by gas-phase hydrogen/deuterium exchange combined with theoretical calculations

We have investigated the effects of alkali-metal ions (G+ = K+, Rb+, or Cs+) on the conformation of leucine enkephalin (LE) and methionine enkephalin (ME) using hydrogen/deuterium exchange mass spectrometry and theoretical calculations at the molecular level. The MS result revealed a 1:1 stoichiometric ratio of the G+ coordination with LE/ME. We used [LE/ME+H]+ as the native conformation for comparison purposes, we observed different HDX behaviors following the reactivity order [LE/ME+H]+>[LE/ME+K]+>[LE/ME+Rb]+>[LE/ME+Cs]+ and [LE+G]+>[ME+G]+. Eight hydrogen atoms were HD-exchanged for [LE/ME+H]+, whereas only 4, 3, and 2 hydrogen atoms underwent HDX for [LE/ME+K]+, [LE/ME+Rb]+, and [LE/ME+Cs]+, respectively. Additionally, we obtained different dissociation processes and different fragmentations for the various complexes, and their varied HDX behaviors suggest that the alkali-metal ions K+, Rb+, and Cs+ produce effects on the LE/ME conformations that differ from those of H+. Further, we investigated the favorable conformations of the complexes by theoretical calculations, and found that K+, Rb+, and Cs+ are coordinated with three carbonyl oxygens and one deprotonated carboxylic acid of LE/ME, whereas the terminal amino group is the most stable site for protonation. We calculated the proton affinity (PA) for each active hydrogen atom on the optimized complexes, which reasonably explained the HDX results that a high PA value corresponds to low HDX reactivity. Overall, the calculations showed that alkali-metal ions can induce ME into a more rigid conformation than LE. Even the native conformation of ME is more exposed than LE, and the conformation of LE/ME is stabilized and rigid owing to the increase in the size of the complexed alkali metals.

RegioSQM20: improved prediction of the regioselectivity of electrophilic aromatic substitutions

We present RegioSQM20, a new version of RegioSQM (Chem Sci 9:660, 2018), which predicts the regioselectivities of electrophilic aromatic substitution (EAS) reactions from the calculation of proton affinities. The following improvements have been made: The open source semiempirical tight binding program xtb is used instead of the closed source MOPAC program. Any low energy tautomeric forms of the input molecule are identified and regioselectivity predictions are made for each form. Finally, RegioSQM20 offers a qualitative prediction of the reactivity of each tautomer (low, medium, or high) based on the reaction center with the highest proton affinity. The inclusion of tautomers increases the success rate from 90.7 to 92.7%. RegioSQM20 is compared to two machine learning based models: one developed by Struble et al. (React Chem Eng 5:896, 2020) specifically for regioselectivity predictions of EAS reactions (WLN) and a more generally applicable reactivity predictor (IBM RXN) developed by Schwaller et al. (ACS Cent Sci 5:1572, 2019). RegioSQM20 and WLN offers roughly the same success rates for the entire data sets (without considering tautomers), while WLN is many orders of magnitude faster. The accuracy of the more general IBM RXN approach is somewhat lower: 76.3–85.0%, depending on the data set. The code is freely available under the MIT open source license and will be made available as a webservice (regiosqm.org) in the near future.

Discovery of the acetyl cation, CH3CO+, in space and in the laboratory.

Using the Yebes 40m and IRAM 30m radiotelescopes, we detected two series of harmonically related lines in space that can be fitted to a symmetric rotor. The lines have been seen towards the cold dense cores TMC-1, L483, L1527, and L1544. High level of theory ab initio calculations indicate that the best possible candidate is the acetyl cation, CH3CO+, which is the most stable product resulting from the protonation of ketene. We have produced this species in the laboratory and observed its rotational transitions Ju = 10 up to Ju = 27. Hence, we report the discovery of CH3CO+ in space based on our observations, theoretical calculations, and laboratory experiments. The derived rotational and distortion constants allow us to predict the spectrum of CH3CO+ with high accuracy up to 500 GHz. We derive an abundance ratio N(H2CCO)/N(CH3CO+)~44. The high abundance of the protonated form of H2CCO is due to the high proton affinity of the neutral species. The other isomer, H2CCOH+, is found to be 178.9 kJ mol-1 above CH3CO+. The observed intensity ratio between the K=0 and K=1 lines, ~2.2, strongly suggests that the A and E symmetry states have suffered interconversion processes due to collisions with H and/or H2, or during their formation through the reaction of with H2CCO.

Formation of positive product ions from substances with low proton affinity in high kinetic energy ion mobility spectrometry.

RationaleIon mobility spectrometry (IMS) instruments are typically equipped with atmospheric pressure chemical ionization (APCI) sources operated at ambient pressure. However, classical APCI‐IMS suffers from a limited ionization yield for nonpolar substances with low proton affinity (PA). This is mainly due to ion clustering processes, especially those that involve water molecules, inhibiting the ionization of these substances.MethodsHigh Kinetic Energy (HiKE)‐IMS instruments are operated at decreased pressures and high reduced electric field strengths. As most clustering reactions are inhibited under these conditions, the ionization yield for nonpolar substances with low PA in HiKE‐IMS should differ from that in classical APCI‐IMS. To gain first insights into the ionization capabilities and limitations of HiKE‐IMS, we investigated the ionization of four model substances with low PA in HiKE‐IMS using HiKE‐IMS‐MS as a function of the reduced electric field strength.ResultsThe four model substances all have proton affinities between those of H2O and (H2O)2 but exhibit different ionization energies, dipole moments, and polarizabilities. As expected, the results show that the ionization yield for these substances differs considerably at low reduced electric field strengths due to ion cluster formation. In contrast, at high reduced electric field strengths, all substances can be ionized via charge and/or proton transfer in HiKE‐IMS.ConclusionsConsidering the detection of polar substances with high PAs, classical ambient pressure IMS should reach better detection limits than HiKE‐IMS. However, considering the detection of nonpolar substances with low PA that are not detected, or only difficult to detect, at ambient pressure, HiKE‐IMS would be beneficial.

Gas-phase study of adduct and exchange complexation reactions between two and tridimensional macrocyclic ligands using ion mobility spectrometry and mass spectrometry

A gas-phase study concerning the interaction between macrocyclic ligands and different molecular ion guests (H3O+, NH4+, CH3NH3+) was performed using ion mobility spectrometry and mass spectrometry. 18-crown-6 (18C6), diaza18-crown-6 (DA18C6) and cryptand [222] (C222) ligands were selected for the investigation of structural properties on the nature of complexes formed. Characterization of complexes was performed by ESI-TWIM-TOFMS. In this study, the importance of the type of donating atom in the ring on complex formation was investigated by comparison of the ion mobility spectra of 18C6 and DA18C6 at various temperatures. Different complexation behaviors of ligands showed that the nature of species formed strongly depends on the structural features of the host. DA18C6 does not demonstrate the adduct formation that is observed for 18C6. This is attributed to the high proton affinity of DA18C6, which serves to preferentially remove a proton from any reactant ion upon introduction to the gas phase. In the case of C222 with a three-dimensional cavity, due to the existence of an inclusive site, an interesting behavior was observed. In C222–H3O+ and C222–CH3NH3+ systems, only proton exchange reaction and an inclusion complex formation (C222.H+) are found, while for C222–NH4+ happens inclusive ammonium complex C222·NH4+ in addition to proton exchange reaction and C222.H+ formation. Encapsulation of ammonium ion in the cage of C222 was attributed to size match between ammonium and host cavity that depends on temperature. The exchange constant, enthalpy and entropy of C222·NH4+ complex formation in the gas phase have been determined.

Tricyclo[2.1.0.02,5]pent-3-ylidene: Stereoelectronic Control of Bridge-Flapping within a Nonclassical Nucleophilic Carbene.

Tricyclo[2.1.0.02,5]pent-3-ylidene is a carbene foreseen to rearrange to pyramidane (c-C4H4)C, a highly strained molecule featuring an inverted C atom. Modeling of the carbene, using the (U)MPWB1K/cc-pVTZ//(U)MPWB1K/6-311G(d) theoretical model, indicated a large singlet–triplet energy gap (ΔES–T = −45 kcal/mol), a high gas-phase proton affinity (PA = 258 kcal/mol), and a preference for electron-poor alkenes. These properties are consistent with those of nucleophilic carbenes. Structural differences between the Cs-symmetric singlet (ωflap = ±44 deg) and C2v-symmetric triplet (ωflap = 0 deg) stem from nonclassical electron delocalization in the former and the lack thereof in the latter. Degenerate bridge-flapping of the singlet’s main bridge, which comprises the reactive divalent C3 atom, is computed to be slow due to a high activation barrier of the C2v-symmetric transition state (TS) (Ea = 17 kcal/mol). The position of the conformeric equilibrium is subject to stereoelectronic control. 1-Substituted derivatives of the carbene (R ≠ H) are sensitive to σ inductive effects. A proximal conformation is preferred when R is electron-donating and a distal one is favored when R is electron-withdrawing. Finally, carbene rearrangements via 1,2-C atom shift or enyne fragmentation were computed. The C2v-symmetric bridge-flapping TS has the proper geometry to initiate enyne fragmentation.

Ion-Molecular Derivatization Reactions of Alcohols in a “Direct Analysis in Real Time” (DART) Mass Spectrometer: 4-N,N-Dimethylaminopyridine as a New Efficient Reagent

Gas-phase on-line derivatization in the ion source of a DART mass spectrometer is a new approach to the efficient detection of alcohols in complex matrices. It does not require any special sample handling; it is based just on mixing an alcohol with a nitrogen-containing compound with high proton affinity. The resulting N-alkyl-derivatized cations appear in DART spectra as very characteristic and highly intense signals. In addition to the earlier used pyridine and quinoline, we propose a new reagent, 4-N,N-dimethylaminopyridine (4-DMAP), having a higher proton affinity. It is shown that DART mass spectra recorded for alcohols in the presence of an equimolar mixture of pyridine and 4-DMAP reveal peaks that are mainly due to the 4-DMAP quaternization cation. This indicates a highly competitive ability of this reagent to get protonated and then predominantly participate in ion-molecular reactions with alcohols under study. It is suggested that 4-DMAP provides high sensitivity in the analysis of aliphatic and alicyclic primary and secondary alcohols.

Structural investigations, quantum mechanical studies on proton and metal affinity and biological activity predictions of selpercatinib

Cancer of the lungs and thyroid is particularly difficult to manage and treat. Notably, selpercatinib has recently been suggested as an effective drug to combat these diseases. The entire world is currently tackling the pandemic caused by the SARS-CoV-19 virus. Numerous pharmaceuticals have been evaluated for the management of the disease caused by SARS-CoV-19 (i.e., COVID-19). In this study, selpercatinib was proposed as a potential inhibitor of different SARS-CoV-19 proteins. Several intriguing effects of the molecule were found during the conducted computational investigations. Selpercatinib could effectively act as a proton sponge and exhibited high proton affinity in solution. Moreover, it was able to form complexes with metal ions in aqueous solutions. Specifically, the compound displayed high affinity towards zinc ions, which are important for the prevention of virus multiplication inside human cells. However, due to their charge, zinc ions are not able to pass the lipid bilayer and enter the cell. Thus, it was determined that selpercatinib could act as an ionophore, effectively transporting active zinc ions into cells. Furthermore, various quantum mechanical analyses, including energy studies, evaluation of the reactivity parameters, examination of the electron localisation and delocalisation properties, as well as assessment of the nonlinear optical (NLO) properties and information entropy, were conducted herein. The performed docking studies (docking scores −9.3169, −9.1002, −8.1853 and −8.1222 kcal mol−1) demonstrated that selpercatinib strongly bound with four isolated SARS-CoV-2 proteins.

Role of the amine and phosphine groups in oleylamine and trioctylphosphine in the synthesis of copper chalcogenide nanoparticles

The effect of the functional groups of capping agents was investigated in the synthesis of copper selenide, copper sulphide and copper oxide nanoparticles using oleylamine (OLA) and trioctylphosphine (TOP). These capping molecules have demonstrated their ability to act as reducing agents, surfactants, solvents and enhancement of colloidal stabilization. They also offer electron donating abilities from the two group 5A elements, P and N. Nitrogen atom in an amine group possess stronger surface interactions and higher basicity than P atom in the phosphines. Copper chalcogenide nanoparticles were prepared using Hot-injection method and characterized using UV/Vis spectroscopy, TEM and XRD. The optical and structural properties of the yielded nanoparticles showed dependence on the type of capping interactions from the two agents. Nanoparticles synthesized using TOP produced two phases whereas a single phase was observed from OLA as confirmed by XRD. Although TOP and OLA exhibit similar features, but their affinity to metals differs resulting to significant different morphology and crystallinity of the produced nanoparticles. Amine group has higher affinity for protons than phosphine due to the lone pair of electrons it possesses which it easily donates to H+ compared to phosphine. The high proton affinity of oleylamine makes it interact faster than trioctylphosphine. OLA in overall produced larger particle sizes compared to TOP but generated a wider variety of shapes.

Protonation of Planar and Nonplanar Porphyrins: A Calorimetric and Computational Study.

Herein, we report the first calorimetric study of the protonation of planar and nonplanar free-base porphyrins: H2OETPP (strongly saddled by its substituents), H2T(tBu)P (strongly ruffled by its substituents), and the nominally planar porphyrins (npPs) H2OEP, H2TPP, H2T(nPe)P, and H2T(iPr)P. The observed enthalpies of protonation in solution (ΔHprotsoln) for formation of the dications in 1,1,2,2-tetrachloroethane with 2% trifluoroacetic acid are -45 ± 1 kcal mol-1 for the npPs, -52.0 kcal mol-1 for H2T(tBu)P, and -70.9 kcal mol-1 for H2OETPP. The corresponding enthalpies of protonation (ΔHDFT) obtained from DFT calculations (-27 ± 5, -42, and -63 kcal mol-1, respectively) reproduce this trend. The much more negative enthalpy of protonation seen for H2OETPP is consistent with this molecule being pre-deformed into the saddle structure favored by porphyrin dications. Except for OETPP, the calculated enthalpies of the first protonations (ΔH1) are significantly more positive than the enthalpies of the second protonations (ΔH2). In addition, the structural strain energies for the first protonations (ΔEst(1)) are also significantly more positive than ΔEst(2). According to the calculations, the monocations thus have higher proton affinities than the corresponding free-base porphyrins due to a structural strain effect, which is consistent with the generally elusive nature of the porphyrin monocation. The recent observations of monocations for free-base porphyrins with a high degree of saddling can be rationalized in terms of ΔH1 and ΔH2 being similar; so, the monocation is no longer an unstable intermediate.