Search Results (25)

In this work, we evaluate the efficiency of a DNA purification protocol from gynecological samples using locally synthesized Fe₃O₄@SiO₂ magnetic microparticles and a low-cost, guanidinium thiocyanate (GITC)-free lysis buffer. The microparticles were characterized by SEM, EDS, FTIR, and magnetic measurements, confirming the formation of compact silica-coated aggregates with suitable magnetic responsiveness for rapid and complete capture. Using this material in combination with a simple, GITC-free lysis buffer, we achieved DNA extraction yields comparable to those obtained with standard methods based on chaotropic salts. The purified DNA showed high compatibility with molecular assays for the detection of Chlamydia trachomatis, Ureaplasma urealyticum, Mycoplasma hominis, and human papilloma virus. Clinical validation demonstrated excellent diagnostic performance, with only a few discrepancies observed in samples near the detection threshold of qPCR, a limitation shared with commercial kits. Overall, the method represents a low-cost, safe, and sustainable alternative for routine clinical and epidemiological applications, compared to methods based on chaotropic salt buffers. Furthermore, it reduces reliance on imported commercial consumables and minimizes the handling of hazardous reagents. Full article

Solid polymer electrolytes (SPEs) for symmetrical supercapacitors are proposed herein with activated carbon as electrodes and optimized solid polymer electrolyte membranes, which serve as the separators and electrolytes. We propose the design of a low-cost solid polymer electrolyte consisting of guanidinium nitrate (GuN) and poly(ethylene oxide) (PEO) with poly(vinylpyrrolidone) (PVP). Using the solution casting approach, blended polymer electrolytes with varying GuN weight percentage ratios of PVP and PEO are prepared. On the blended polymer electrolytes, structural, morphological, vibrational, and ionic conductivity are investigated. The solid polymer electrolytes’ morphology and level of roughness are examined using an FESEM. The interlinking bond formation between the blended polymers and the GuN salt is verified by FTIR measurements, indicating that the ligands are chemically complex. We found that, up to 20 wt.% GuN, the conductivity value increased (1.84 × 10⁻⁶ S/cm) with an increase in mobile charge carriers. Notably, the optimized PVP/PEO/20 wt.% solid polymer electrolyte was fabricated into a solid-state symmetrical supercapacitor device, which delivered a potential window of 0 to 2 V, a superior energy density of 3.88 Wh kg⁻¹, and a power density of 1132 W kg⁻¹. Full article

As one of the most promising photovoltaic technologies, perovskite solar cells (PSCs) exhibit high absorption coefficients, tunable bandgaps, large carrier mobilities, and versatile fabrication techniques. Nevertheless, the commercialization of the technology is hindered by poor material stability, short device lifetimes and the scalability of fabrication techniques. To address these technological drawbacks, various strategies have been explored, with one particularly promising approach involving the formation of a low-dimensional layer on the surface of the three-dimensional perovskite film. In this work, we demonstrate the use of guanidinium tetrafluoroborate, CH₆BF₄N₃, (GATFB) as a post-treatment step to enhance the performance of PSCs. Compared with the control sample, the application of GATFB improves the film surface topology, reduces surface defects, suppresses non-radiative recombination, and optimizes band alignment within the device. These positive effects reduce recombination losses and enhance charge transport in the device, resulting in PSCs with an open-circuit voltage (V_OC) of 1.18 V and a power conversion efficiency (PCE) of 19.7%. The results obtained in this work exhibit the potential of integrating low-dimensional structures in PSCs as an effective approach to enhance the overall device performance, providing useful information for further advancement in this rapidly evolving field of photovoltaic technology. Full article

This paper reports the vapor pressure and enthalpy of vaporization for a promising phase change material (PCM) guanidinium methanesulfonate ([Gdm][OMs]), which is a typical guanidinium organomonosulfonate that displays a lamellar crystalline architecture. [Gdm][OMs] was purified by recrystallization. The elemental analysis and infrared spectrum of [Gdm][OMs] confirmed the purity and composition. Differential scanning calorimetry (DSC) also confirmed its high purity and showed a sharp and symmetrical endothermic melting peak with a melting point (T_m) of 207.6 °C and a specific latent heat of fusion of 183.0 J g⁻¹. Thermogravimetric analysis (TGA) reveals its thermal stability over a wide temperature range, and yet three thermal events at higher temperatures of 351 °C, 447 °C, and 649 °C were associated with vaporization or decomposition. The vapor pressure was measured using the isothermogravimetric method from 220 °C to 300 °C. The Antoine equation was used to describe the temperature dependence of its vapor pressure, and the substance-dependent Antoine constants were obtained by non-linear regression. The enthalpy of vaporization (Δ_vapH) was derived from the linear regression of the slopes associated with the linear temperature dependence of the rate of weight loss per unit area of vaporization. Hence, the temperature dependence of vapor pressures ln P_vap (Pa) = 10.99 − 344.58/(T (K) − 493.64) over the temperature range from 493.15 K to 573.15 K and the enthalpy of vaporization Δ_vapH = 157.10 ± 20.10 kJ mol⁻¹ at the arithmetic mean temperature of 240 °C were obtained from isothermogravimetric measurements using the Antoine equation and the Clausius–Clapeyron equation, respectively. The flammability test indicates that [Gdm][OMs] is non-flammable. Hence, [Gdm][OMs] enjoys very low volatility, high enthalpy of vaporization, and non-flammability in addition to its known advantages. This work thus offers data support, methodologies, and insights for the application of [Gdm][OMs] and other organic salts as PCMs in thermal energy storage and beyond. Full article

This work investigated the cocatalytic activity of recently prepared guanidinium salts containing an oxanorbornane subunit in an (S)-proline-catalyzed aldol reaction. The activity was interpreted by the diastereoselectivity of the reaction (anti/syn ratio) and for the most interesting polycyclic guanidinium salt, the enantioselectivity of the reaction was determined. The results indicated a negative impact on the oxanorbornane unit if present as the flexible substituent. For most of the tested aldehydes, the best cocatalysts provided enantioselectivities above 90% and above 95% at room temperature and 0 °C, respectively, culminating in >99.5% for 4–chloro– and 2–nitrobenzaldehyde as the substrate. The barriers for forming four possible enantiomers were calculated and the results for two anti–enantiomers are qualitatively consistent with the experiment. Obtained results suggest that the representatives of furfurylguanidinium and rigid polycyclic oxanorbornane-substituted guanidinium salts are good lead structures for developing new cocatalysts by tuning the chemical space around the guanidine moiety. Full article

The discrepancy between the calculated (CBS-4M/Jenkins) and experimentally determined enthalpies of formation recently reported for the 2:1 salt TKX-50 raised the important question of whether the enthalpies of formation of other 2:1 C, H, N, O salts calculated using the CBS-4M/Jenkins method are reliable values. The standard (p° = 0.1 MPa) enthalpy of formation of crystalline guanidinium 5,5′-azotetrazolate (GZT) (453.6 ± 3.2 kJ/mol) was determined experimentally using static-bomb combustion calorimetry and was found to be in good agreement with the literature’s values. However, using the CBS-4M/Jenkins method, the calculated enthalpy of formation of GZT was again in poor agreement with the experimentally determined value. The method we used recently to calculate the enthalpy of formation of TKX-50, based on the calculation of the heat of formation of the salt and of the corresponding neutral adduct, was then applied to GZT and provided excellent agreement with the experimentally determined value. Finally, in order to validate the findings, this method was also applied to predict the enthalpy of formation of a range of 1:1 and 2:1 salts (M⁺X⁻ and (M⁺)₂X²⁻ salts, respectively), and the values obtained were comparable to experimentally determined values. The agreement using this approach was generally very good for both 1:1 and 2:1 salts; therefore, this approach provides a simple and reliable method which can be applied to calculate the enthalpy of formation of energetic C, H, N, O salts with much greater accuracy than the current, commonly used method. Full article

In contrast to the well-studied canonical regulatory mechanisms, the way by which the recently discovered Src N-terminal regulatory element (SNRE) modulates Src activity is not yet well understood. Phosphorylation of serine and threonine residues modulates the charge distribution along the disordered region of the SNRE and may affect a fuzzy complex with the SH3 domain that is believed to act as an information transduction element. The pre-existing positively charged sites can interact with the newly introduced phosphate groups by modulating their acidity, introducing local conformational restrictions, or by coupling various phosphosites into a functional unit. In this paper, we use pH-dependent NMR measurements combined with single point mutations to identify the interactions of basic residues with physiologically important phosphorylated residues and to characterize the effect of these interactions in neighbor residues, thus providing insight into the electrostatic network in the isolated disordered regions and in the entire SNRE. From a methodological point of view, the linear relationships observed between the mutation-induced pKa changes of the phosphate groups of phosphoserine and phosphothreonine and the pH-induced chemical shifts of the NH groups of these residues provide a very convenient alternative to identify interacting phosphate groups without the need to introduce point mutations on specific basic residues. Full article

The synthesis and characterization of six new substituted guanidium tetrahydroxidohexaoxidopentaborate(1-) salts are reported: [C(NH₂)₂(NHMe)][B₅O₆(OH)₄]·H₂O (1), [C(NH₂)₂(NH{NH₂})][B₅O₆(OH)₄] (2), [C(NH₂)₂(NMe₂)][B₅O₆(OH)₄] (3), [C(NH₂)(NMe₂)₂][B₅O₆(OH)₄] (4), [C(NHMe)(NMe₂)₂][B₅O₆(OH)₄]·B(OH)₃ (5), and [TBDH][B₅O₆(OH)₄] (6) (TBD = 1,5,7-triazabicyclo [4.4.0]dec-5-ene). Compounds 1–6 were prepared as crystalline salts from basic aqueous solution via self-assembly processes from B(OH)₃ and the appropriate substituted cation. Compounds 1–6 were characterized by spectroscopic (NMR and IR) and by single-crystal XRD studies. A thermal (TGA) analysis on compounds 1–3 and 6 demonstrated that they thermally decomposed via a multistage process to B₂O₃ at >650 °C. The low temperature stage (<250 °C) was endothermic and corresponded to a loss of H₂O. Reactant stoichiometry, solid-state packing, and H-bonding interactions are all important in assembling these structures. An analysis of H-bonding motifs in known unsubstituted guanidinium salts [C(NH₂)₃]₂[B₄O₅(OH)₄]·2H₂O, [C(NH₂)₃][B₅O₆(OH)₄]·H₂O, and [C(NH₂)₃]₃[B₉O₁₂(OH)₆] and in compounds 1–6 revealed that two important H-bonding R₂²(8) motifs competed to stabilize the observed structures. The guanidinium cation formed charge-assisted pincer cation–anion H-bonded rings as a major motif in [C(NH₂)₃]₂[B₄O₅(OH)₄]·2H₂O and [C(NH₂)₃]₃[B₉O₁₂(OH)₆], whereas the anion–anion ring motif was dominant in [C(NH₂)₃][B₅O₆(OH)₄]·H₂O and in compounds 1–6. This behaviour was consistent with the stoichiometry of the salt and packing effects also strongly influencing their solid-state structures. Full article

A proposed mechanism of the reaction of guanidinium chlorides with dimethyl acetylenedicarboxylate in a tandem aza-Michael addition reaction/intramolecular cyclization was investigated by DFT M06-2X and B3LYP computational approaches. The energies of the products were compared against the G3, M08-HX, M11, and wB97xD data or experimentally obtained product ratios. The structural diversity of the products was interpreted by the concurrent formation of different tautomers formed in situ upon deprotonation with a 2-chlorofumarate anion. A comparison of relative energies of the characteristic stationary points along the examined reaction paths indicated that the initial nucleophilic addition is energetically the most demanding process. The overall reaction is strongly exergonic, as predicted by both methods, which is primarily due to methanol elimination during the intramolecular cyclization step producing cyclic amide structures. Formation of a five-membered ring upon intramolecular cyclization is highly favored for the acyclic guanidine, while optimal product structure for the cyclic guanidines is based on a 1,5,7-triaza [4.3.0]-bicyclononane skeleton. Relative stabilities of the possible products calculated by the employed DFT methods were compared against the experimental product ratio. The best agreement was obtained for the M08-HX approach while the B3LYP approach provided somewhat better results than the M06-2X and M11 methods. Full article

The cycloaddition of simple alkyl-substituted guanidine derivatives is an interesting approach toward polycyclic superbases and guanidine-based organocatalysts. Due to the high nucleophilicity of guanidines, an aza-Michael reaction with dienophiles is more common and presents a huge obstacle in achieving the desired synthetic goal. Our preliminary investigations indicated that the proton could act as a suitable protecting group to regulate the directionality of the reaction. To investigate the role of the protonation state and type of anion, the reactivity of furfuryl guanidines with dimethyl acetylenedicarboxylate was explored. Furfuryl guanidines showed a strong reaction dependence on the nucleophilicity of the counterion and the structure of guanidine. While the reaction of DMAD with the guanidinium halides provided products of an aza-Michael addition, Diels–Alder cycloaddition occurred if non-nucleophilic hexafluorophosphate salts were used. Depending on the structure and the reaction conditions, oxanorbornadiene products underwent subsequent intramolecular cyclization. A tendency toward intramolecular cyclization was interpreted in terms of the pK_a of different positions of the guanidine functionality in oxanorbornadienes. New polycyclic guanidines had a slightly decreased pK_a in acetonitrile and well-defined geometry suitable for the buildup of selective sensors. Full article

Amidinium salts have been utilized in perovskite precursor solutions as additives to improve the quality of perovskite films. The design of hydrophilic or hydrophobic groups in amidinium salts is of great importance to photovoltaic device performance and stability in particular. Here we report a contrast study of a guanidinium iodide (GUI) additive with a hydrophilic NH₂ group, and a N,1–diiodoformamidine (DIFA) additive with a hydrophobic C–I group, to investigate the group effect. The addition of GUI or DIFA was beneficial to achieve high quality perovskite film and superior photovoltaic device performance. Compared with GUI, the addition of the DIFA in a perovskite precursor solution enhanced the crystal quality, reduced the defect density, and protected the water penetration into perovskite film. The perovskite solar cell (PSC) devices showed the best power conversion efficiency (PCE) of 21.19% for those modified with DIFA, as compared to 18.85% for the control, and 20.85% for those modified with GUI. In benefit to the hydrophobic C–I group, the DIFA–modified perovskite films and PSC exhibited the best light stability, thermal stability, and humidity stability in comparison to the control films and GUI–modified films. Overall, the introduction of a hydrophobic group in the amidinium salts additive was demonstrated to be an efficient approach to achieve high quality and stable perovskite film and PSC devices. Full article

The use of ionic liquid and organic salts as additives for electrolyte systems in dye-sensitized solar cells have been widely described in recent years. The tunability of their physical-chemical properties according to the cation–anion selection contributes toward their high efficiencies. For this purpose, several iodide-based organic salts including imidazolium, picolinium, guanidinium and alkylammonium cations were tested using acetonitrile/valeronitrile electrolytes and their photovoltaic parameters were compared. A best efficiency of 4.48% (4.15% for the reference) was found for 1-ethyl-2,3-dimethylimidazolium iodide ([C2DMIM]I) containing electrolyte, reaffirming the effectiveness of these additives. 4-tertbutylpyridine was included into the formulation to further improve the performance while determining which iodide salts demonstrate the highest synergy with this additive. [C2DMIM]I once again proved to be the superior additive, achieving an efficiency of 6.48% (6% for the reference). Electrochemical impedance spectroscopy was employed to elucidate the effects of the various additives, demonstrating the relevance of the counter electrode resistance on device performance. Finally, several computational descriptors for the cationic structures were calculated and correlated with the photovoltaic and resistance parameters, showing that properties related to polarity, namely relative positive charge, molecular polarizability and partition coefficient are in good agreement with the counter-electrode resistance. Full article

Guanidinium (Gdm) undergoes interactions with both hydrophilic and hydrophobic groups and, thus, is a highly potent denaturant of biomolecular structure. However, our molecular understanding of the interaction of Gdm with proteins and DNA is still rather limited. Here, we investigated the denaturation of DNA origami nanostructures by three Gdm salts, i.e., guanidinium chloride (GdmCl), guanidinium sulfate (Gdm₂SO₄), and guanidinium thiocyanate (GdmSCN), at different temperatures and in dependence of incubation time. Using DNA origami nanostructures as sensors that translate small molecular transitions into nanostructural changes, the denaturing effects of the Gdm salts were directly visualized by atomic force microscopy. GdmSCN was the most potent DNA denaturant, which caused complete DNA origami denaturation at 50 °C already at a concentration of 2 M. Under such harsh conditions, denaturation occurred within the first 15 min of Gdm exposure, whereas much slower kinetics were observed for the more weakly denaturing salt Gdm₂SO₄ at 25 °C. Lastly, we observed a novel non-monotonous temperature dependence of DNA origami denaturation in Gdm₂SO₄ with the fraction of intact nanostructures having an intermediate minimum at about 40 °C. Our results, thus, provide further insights into the highly complex Gdm–DNA interaction and underscore the importance of the counteranion species. Full article

Hydrogen/deuterium (H/D) exchange combined with two-dimensional (2D) NMR spectroscopy has been widely used for studying the structure, stability, and dynamics of proteins. When we apply the H/D-exchange method to investigate non-native states of proteins such as equilibrium and kinetic folding intermediates, H/D-exchange quenching techniques are indispensable, because the exchange reaction is usually too fast to follow by 2D NMR. In this article, we will describe the dimethylsulfoxide (DMSO)-quenched H/D-exchange method and its applications in protein science. In this method, the H/D-exchange buffer is replaced by an aprotic DMSO solution, which quenches the exchange reaction. We have improved the DMSO-quenched method by using spin desalting columns, which are used for medium exchange from the H/D-exchange buffer to the DMSO solution. This improvement has allowed us to monitor the H/D exchange of proteins at a high concentration of salts or denaturants. We describe methodological details of the improved DMSO-quenched method and present a case study using the improved method on the H/D-exchange behavior of unfolded human ubiquitin in 6 M guanidinium chloride. Full article

The development of methodologies to sense glyphosate has gained momentum due to its toxicological and ecotoxicological effects. In this work, a red-emitting and polymerizable guanidinium benzoxadiazole probe was developed for the fluorescence detection of glyphosate. The interaction of the fluorescent probe and the tetrabutylammonium salt of glyphosate was studied via UV/vis absorption and fluorescence spectroscopy in chloroform and acetonitrile. The selective recognition of glyphosate was achieved by preparing molecularly imprinted polymers, able to discriminate against other common herbicides such as 2,4-dichlorophenoxyacetic acid (2,4-D) and 3,6-dichloro-2-methoxybenzoic acid (dicamba), as thin layers on submicron silica particles. The limits of detection of 4.8 µM and 0.6 µM were obtained for the sensing of glyphosate in chloroform and acetonitrile, respectively. The reported system shows promise for future application in the sensing of glyphosate through further optimization of the dye and the implementation of a biphasic assay with water/organic solvent mixtures for sensing in aqueous environmental samples. Full article