Cationic Ligands Research Articles

Gold nanoparticle design for RNA compaction.

RNA-based therapeutics hold a great promise in treating a variety of diseases. However, double-stranded RNAs (dsRNAs) are inherently unstable, highly charged, and stiff macromolecules that require a delivery vehicle. Cationic ligand functionalized gold nanoparticles (AuNPs) are able to compact nucleic acids and assist in RNA delivery. Here, we use large-scale all-atom molecular dynamics simulations to show that correlations between ligand length, metal core size, and ligand excess free volume control the ability of nanoparticles to bend dsRNA far below its persistence length. The analysis of ammonium binding sites showed that longer ligands that bind deep within the major groove did not cause bending. By limiting ligand length and, thus, excess free volume, we have designed nanoparticles with controlled internal binding to RNA's major groove. NPs that are able to induce RNA bending cause a periodic variation in RNA's major groove width. Density functional theory studies on smaller models support large-scale simulations. Our results are expected to have significant implications in packaging of nucleic acids for their applications in nanotechnology and gene delivery.

Cover Feature: DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized CeIV and CeIII Cyclen‐Based Complexes and Clusters in Aqueous Solutions (Chem. Eur. J. 61/2022)

Cover Feature: DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized Ce^IV and Ce^III Cyclen‐Based Complexes and Clusters in Aqueous Solutions (Chem. Eur. J. 61/2022)

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized CeIV and CeIII Cyclen-Based Complexes and Clusters in Aqueous Solutions.

The coordination and redox chemistry of aqueous CeIV/III macrocyclic compounds were studied by using the ligands DOTA and DOTP (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetraacetic acid and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid), respectively). The hydrolysis tendency of the tetravalent cation in the presence of DOTA is shown to result in the formation of a highly ordered, fluorite-like [CeIV 6 (O)4 (OH)4 (H2 O)8 (DOTAH)4 ] oxo-hydroxo structure both in solution and in the solid state. The lifetime of the analogous species formed in the presence of DOTP was found to be much shorter. Spectroscopic measurements of the latter suggest its similarity to the former. Its gradual decomposition in solution leads to the accumulation of the in-cage complexes [CeIV DOTP] and [CeIII DOTP(H2 O)], which were crystallographically characterized in this study. The redox energetics and spectroscopic characteristics for the transition between these two in-cage complexes in aqueous solutions were studied as well. Together with the crystallographic structures of the above-mentioned species, the in-cage [CeIV DOTA(H2 O)] complex structure is presented herein for the first time. An elaborative analysis of the X-ray crystallographic structural data obtained for the in-cage complexes studied herein and similar structures published previously suggests that hard-bonding cyclen-derived ligands are, counter-intuitively, better suited for encapsulating, and perhaps kinetically stabilize softer cations than harder ones with DOTP, marked as a possible adequate chelator for the study of the aqueous properties of LnII and AcIII cations.

Thermochemical Studies of Nickel Hydride Complexes with Cationic Ligands in Aqueous and Organic Solvents

Transition metal hydride complexes are key intermediates in a variety of catalytic processes. Transfer of a hydride, hydrogen atom, or proton is defined by the thermochemical parameters of hydricity, bond dissociation free energy (BDFE), and pKa, respectively. These values have been studied primarily in organic solvents to predict or understand reactivity. Despite growing interest in the development of aqueous metal hydride catalysis, BDFE measurements of transition metal hydrides in water are rare. Herein, we report two nickel hydride complexes with one or two cationic ligands that enable the measurement of BDFE values in both aqueous and organic solvents using their reduction potential and pKa values. The Ni(I/0) reduction potentials increase anodically as more charged groups are introduced into the ligand framework and are among the most positive values measured for Ni complexes. The complex with two cationic ligands, 2-Ni(II)–H, displays exceptional stability in water with no evidence of decomposition at pH 1 for at least 2 weeks. The BDFE of the nickel hydride bond in 2-Ni(II)–H was measured to be 53.6 kcal/mol in water and between 50.9 and 56.2 kcal/mol in acetonitrile, consistent with prior work that indicates minimal solvent dependence for BDFEs of O–H and N–H bonds. These results indicate that transition metal hydride BDFEs do not change drastically in water and inform future studies on highly cationic transition metal hydride complexes.

Two silver–containing polyoxometalate–based inorganic–organic hybrids as heterogeneous bifunctional catalysts for construction of C–C bonds and decontamination of sulfur mustard simulant

The construction of C–C bonds and degradation of chemical warfare agents (CWAs) are two central organic conversions for future sustainable development. Herein, two remarkable silver-containing polyoxomolybdates-based hybrids (Ag-POMos), [Ag(L)(H2O)2]2[HPMo12O40] (1) and [Ag2(L)2]2[HPMo10V2O40]·4DMSO (2) (L ​= ​4,6-bis(2-pyridyl)-2-aminopyrimidine) were designed and prepared by using silver cation, polyoxomolybdates and multiple N-donors ligand (L). The structure of compound 1 is constructed from an independent Ag center and a keggin-type POMs; compound 2 is composed of two independent Ag centers and a keggin-type POMs, which displays intriguing POM-incorporated 1-D chain structure with hydrogen bonding. Additionally, Ag-POMos catalysts can be severed as the efficient bifunctional catalysts for the three-component Mannich reaction to achieve the construction of C–C bonds and decontamination of sulfur mustard 2-chloroethyl ethyl sulfide (CEES). As bifunctional heterogeneous catalyst, particularly compound 2, exhibits satisfying catalytic performances in the Mannich reaction (conv. 99%; sele. 99%) and the oxidation of CEES (conv. 96%; sele. 96%). Notedly, after three runs, compound 2 maintains excellent catalytic properties, demonstrating its remarkable cycling stability.

Relevance of lipoproteins, membranes, and extracellular vesicles in understanding C-reactive protein biochemical structure and biological activities.

Early purification protocols for C-reactive protein (CRP) often involved co-isolation of lipoproteins, primarily very low-density lipoproteins (VLDLs). The interaction with lipid particles was initially attributed to CRP’s calcium-dependent binding affinity for its primary ligand—phosphocholine—the predominant hydrophilic head group expressed on phospholipids of most lipoprotein particles. Later, CRP was shown to additionally express binding affinity for apolipoprotein B (apo B), a predominant apolipoprotein of both VLDL and LDL particles. Apo B interaction with CRP was shown to be mediated by a cationic peptide sequence in apo B. Optimal apo B binding required CRP to be surface immobilized or aggregated, treatments now known to structurally change CRP from its serum soluble pentamer isoform (i.e., pCRP) into its poorly soluble, modified, monomeric isoform (i.e., mCRP). Other cationic ligands have been described for CRP which affect complement activation, histone bioactivities, and interactions with membranes. mCRP, but not pCRP, binds cholesterol and activates signaling pathways that activate pro-inflammatory bioactivities long associated with CRP as a biomarker. Hence, a key step to express CRP’s biofunctions is its conversion into its mCRP isoform. Conversion occurs when (1) pCRP binds to a membrane surface expressed ligand (often phosphocholine); (2) biochemical forces associated with binding cause relaxation/partial dissociation of secondary and tertiary structures into a swollen membrane bound intermediate (described as mCRPm or pCRP*); (3) further structural relaxation which leads to total, irreversible dissociation of the pentamer into mCRP and expression of a cholesterol/multi-ligand binding sequence that extends into the subunit core; (4) reduction of the CRP subunit intrachain disulfide bond which enhances CRP’s binding accessibility for various ligands and activates acute phase proinflammatory responses. Taken together, the biofunctions of CRP involve both lipid and protein interactions and a conformational rearrangement of higher order structure that affects its role as a mediator of inflammatory responses.

Synthesis and characterization of magnetic ionic liquids containing multiple paramagnetic lanthanide and transition metal centers and functionalized diglycolamide ligands

Magnetic ionic liquids (MILs) containing paramagnetic centers have gained widespread recognition as sustainable solvents due to their ability to respond to an external magnetic field. The physico-chemical properties of MILs are dependent on the choice of anion/cation ligands and metal centers; the search for highly tunable ligands and precursors that can confer favorable characteristics, such as low viscosity, is ongoing. Diglycolamides employed as cationic ligands have been previously shown to form hydrophobic MILs that can simultaneously incorporate multiple lanthanide metal centers in both the anion/cation. Despite their enhanced magnetic susceptibility, the effect of diglycolamide chemical structure modifications on the physico-chemical properties of MILs has not been thoroughly studied. Additionally, the possibility of forming diglycolamide-based MILs with popularly employed transition metals has not been investigated and combinations that can simultaneously embed two different types of metal centers in both the anion/cation have not been explored. In this study, thirty (30) MILs comprised of lanthanide and transition metals were synthesized by examining their chelation to both straight-chained and branched diglycolamides. Transition metal-based MILs were found to possess high thermal stabilities up to 235 °C compared to 192 °C for those comprised of lanthanides. While MILs comprised of rare-earth metal centers exhibited the lowest viscosities, substituting lanthanides with transition metals in just the anion or cation resulted in enhanced thermal stability and reduced viscosity. The effective magnetic moment for these MILs varied between 4.71 and 21.08 µB and was much higher compared to all previous classes of MILs prepared using the same metals. Results from this study explore all possible modifications that can be made to these MILs in an effort to demonstrate their structural tunability, which is often highly desirable in various applications, including organic synthesis and chemical separations.

Solution-processable copper(I) iodide-based inorganic-organic hybrid semiconductors composed of both coordinate and ionic bonds

Three new one-dimensional (1D) All-In-One (AIO) type CuI-based hybrid semiconductors with both dative and ionic bonds between the inorganic and organic components have been successfully designed and synthesized by using the ligands containing both cationic center and coordination available sites. Structural analysis confirms that all compounds share the same formula of Cu4I6(L)2 (L ​= ​ligand) and are composed of 1D-Cu4I62− anionic chains that coordinate to cationic ligands. These materials demonstrate high stability towards heat and moisture and excellent solution processability due to their unique bonding nature. They emit low energy light ranging from green to orange color (530–590 ​nm). The origin and mechanism of their emissions were studied by both experimental and theoretical methods. More importantly, all compounds can be easily fabricated into films by solution process, a desired but rare feature for most of CuI-based hybrids built of extended networks.

Exploratory and machine learning analysis of the stability constants of HgII- triazene ligands complexes

Knowing stability constants for the complexes HgII with extracting ligands is very important from environmental and therapeutic standpoints. Since the selectivity of ligands can be stated by the stability constants of cation–ligand complexes, quantitative structure–property relationship (QSPR) investigations on binding constant of HgII complexes were done. Experimental data of the stability constants in ML2 complexation of HgII and synthesized triazene ligands were used to construct and develop QSPR models. Support vector machine (SVM) and multiple linear regression (MLR) have been employed to create the QSPR models. The final model showed squared correlation coefficient of 0.917 and the standard error of calibration (SEC) value of 0.141 log K units. The proposed model presented accurate prediction with the Leave-One-Out cross validation ( Q LOO 2 = 0.756) and validated using Y-randomization and external test set. Statistical results demonstrated that the proposed models had suitable goodness of fit, predictive ability, and robustness. The results revealed the importance of charge effects and topological properties of ligand in HgII - triazene complexation.

Research Progress in the Relationship Between P2X7R and Cervical Cancer.

Cervical cancer is one of the most common and serious tumors in women. Finding new biomarkers and therapeutic targets plays an important role in the diagnosis, prognosis, and treatment of cervical cancer. Purinergic ligand-gated ion channel 7 receptor (P2X7R) is a purine ligand cation channel, activated by adenosine triphosphate (ATP). Studies have shown that P2X7R plays an important role in a variety of diseases and cancers. More and more studies have shown that P2X7R is also closely related to cervical cancer; therefore, the role of P2X7R in the development of cervical cancer deserves further discussion. The expression level of P2X7R in uterine epithelial cancer tissues was lower than that of the corresponding normal tissues. P2X7R plays an important role in the apoptotic process of cervical cancer through various mechanisms of action, and both antagonists and agonists of P2X7R can inhibit the proliferation of cervical cancer cells, while P2X7R is involved in the antitumor effect of Atr-I on cervical cancer cells. This review evaluates the current role of P2X7R in cervical cancer in order to develop more specific therapies for cervical cancer. In conclusion, P2X7R may become a biomarker for cervical cancer screening, and even a new target for clinical treatment of cervical cancer.

Cobalt-Based Metal-Organic Framework Nanoparticles with Peroxidase-like Catalytic Activity for Sensitive Colorimetric Detection of Phosphate

Appropriate addition of phosphate salt in food can improve the food quality and taste. However, extensive intake of phosphate salt may lead to some human diseases such as hyperphosphatemia and renal insufficiency. Thus, it is essential to establish a cost-effective, convenient, sensitive, and selective method for monitoring phosphate ion (Pi) to ensure food quality control. In this work, a Co-based metal-organic frameworks (Co-MOF) nanomaterial with dual functions (peroxidase-like activity and specific recognition) was designed for acting as a catalytic chromogenic platform for sensitive detection of Pi. The Co2+ nodes not only provide high enzyme-like activity to catalyze the 3,3′,5,5′--tetramethylbenzidine (TMB) substrate to blue oxTMB (652 nm) but also act as selective sites for Pi recognition. The use of cationic organic ligands (2-methylimidazole) and cationic metal ions (Co2+) endows the Co-MOF with a strong positive surface charge, which is beneficial to the capture of negative-charged Pi and the dramatically suppressed TMB oxidation. When Pi exists, it specifically adsorbs onto the Co-MOF through the Co-O-P bond and the strong electrostatic interaction, leading to the change of surface charge on Co-MOF. The peroxidase-like catalytic activity of Co-MOF is thus restrained, causing a different catalytic effect on TMB oxidation from that without Pi. Based on this principle, a colorimetric assay was established for rapid and sensitive detection of Pi. A good linear relationship was obtained between Pi concentration and the absorbance at 652 nm, with a linear range of 0.009–0.144 mg/L and a detection limit of 5.4 μg/L. The proposed assay was applied to the determination of Pi in actual food samples with recoveries of 92.2–108% and relative standard deviations (RSDs) of 2.7–7.3%, illustrating the promising practicality for actual samples analysis.

Catalyst Engineering Empowers the Creation of Biomass-Derived Polyesters and Polycarbonates.

The introduction of circular principles in chemical manufacturing will drastically change the way everyday plastics are produced, thereby affecting several aspects of the respective value chains in terms of raw feedstock, recyclability, and cost. The ultimate aim is to ensure a paradigm shift toward plastic-based (consumer) materials that overall can offer a more attractive and sustainable carbon footprint, which is an important requisite from a societal, political, and eventually economical point of view. To realize this important milestone, it is vitally important to control the polymerization processes associated with the creation of novel sustainable materials. In this respect, we realized that expanding the portfolio of biomass-derived monomers may indeed create an impetus for atom circularity; however, the often sterically congested nature of biomass-derived monomers minimizes the ability of previously developed catalysts to activate and transform these precursors. Our motivation was thus spurred by an apparent lack of catalysts suitable for addressing the conversion of such biomonomers, as we realized the potential that new catalytic processes could have to advance and contribute to the development of sustainable materials produced from polycarbonates and polyesters. These two classes of polymers represent crucial ingredients of important and large-scale consumer products and are therefore ideal fits for implementing new catalytic protocols that enable a gradual transition to plastic materials with an improved carbon footprint.When we started our research expedition, the field was dominated by metal catalysts that incorporated preferred, and in some cases even privileged, ligand backbones (such as salens) able to mediate both ring-opening and ring-opening copolymerization manifolds. One major drawback of these aforementioned catalysts is their rather rigid nature, a feature that reduces their ability to act as adaptive systems, especially in cases where bulky monomers are involved. While our initial focus was on the utilization of sustainable metal salen complexes (M = Zn, Fe) for the activation of small cyclic ethers, which are privileged monomers for polyester and polycarbonate production, we were rapidly confronted with severe limitations related to their inability to activate a wider range of complex epoxides and oxetanes, which was imparted by the planar coordination geometry of the salen ligand in most of its applied metal complexes. In our quest to find a catalytically more effective metal complex with the ability to electronically and sterically tune its substrate-binding and substrate-activation potential, we identified aminotriphenolates as structurally versatile, easily accessible, and scalable ligands for various earth-abundant metal cations. Moreover, the ligand backbone allows for switchable coordination environments around the metal centers, thus offering the necessary adaptation in substrate activation events.This Account describes how Al(III)- and Fe(III)-centered aminotriphenolates have conquered a prominent position as catalyst components in the synthesis of new biobased polyester and polycarbonate architectures, thereby changing the landscape of previously difficult to convert biomonomers, and expanding the chemical space of biobased functional polymers. With the ever-increasing influence of legislation and the restrictions placed on the use of fossil-fuel-based feedstock, the polymer industry needs viable alternatives to design materials that are greener, cost-effective, and allow for the exploration and optimization of their recycling and properties.

Improved method for the obtaining DTTA-appended 2,2’-bipyridine ligands for lanthanide cations

The composition of the reaction mixture after DTTA tert-butyl ester alkylation with 6'-halomethyl-5-phenyl-2,2'-bipyridines was studied. In addition to the target product, DTTA-appended 2,2’-bipyridine, the corresponding 6'-hydroxymethyl-substituted 2,2’-bipyridine and (5'-phenyl-[2,2'-bipyridin]-6-yl)methyl formate were isolated as by-products in some cases. Finally, an improved procedure for the DTTA tert-butyl ester alkylation with 6'-halomethyl-5-phenyl-2,2'-bipyridines by using Finkelstein reaction was developed.

Impact of Cation–Ligand Interactions on the Permselectivity of Ligand-Functionalized Polymer Membranes in Single and Mixed Salt Systems

We conduct molecular dynamics simulations to study the effects of cation–ligand interactions on salt permeation in ligand-functionalized polymer membranes. Our results indicate that salt partitioning into the membrane increases while the salt diffusivity decreases with enhancement in the cation–ligand interaction strength. Moreover, the increase in partitioning dominates the decline in salt diffusivity, leading to a net enhancement in salt permeation at higher cation–ligand interaction strengths. Equimolar binary mixed salt systems (having a common anion) generally exhibit much more selective partitioning of salts into the membrane as compared to their single salt counterparts. However, single salt systems exhibit much higher ratio of salt diffusivities than their mixed salt analogues. The permselectivity data closely resemble the trends in selective partitioning for both single and mixed salt systems, indicating that salt diffusivity selectivity plays a weaker role than salt partitioning selectivity in dictating the selective permeation of salts across the membrane.

Cationic Axial Ligand Effects on Sulfur-Substituted Subphthalocyanines.

Herein, we report the synthesis of sulfur-substituted boron(III) subphthalocyanines (SubPcs) with cationic axial ligands. Subphthalocyanines were synthesized by a condensation reaction using the corresponding phthalonitriles and boron trichloride as a template. An aminoalkyl group was introduced on the central boron atom; this process was followed by N-methylation to introduce a cationic axial ligand. The peripheral sulfur groups shifted the Q band of SubPcs to a longer wavelength. The cationic axial ligands increased the polarity and enhanced the hydrophilicity of SubPcs. The effect of axial ligands on absorption and fluorescence properties is generally small. However, a further red shift was observed by introducing cationic axial ligands into the sulfur-substituted SubPcs. This change is similar to that in sulfur-substituted silicon(IV) phthalocyanines. The unique effect of the cationic axial ligand was extensively investigated by theoretical calculations and electrochemistry. In particular, the precise oxidation potential was determined using ionization potential measurements. Thus, the results of the present study provide a novel strategy for developing functional dyes and pigments based on SubPcs.

Synergistic and antagonistic effects during solvent extraction of Gd(III) ion in ionic liquids

Study of the liquid–liquid extraction of Gd(III) ion with a series of phosphorus-containing calix[4]arenes by the well-known method of slope analysis and determination of the process parameters are presented employing three ionic liquids, ([C1Cnim+]/[C1C4pyr+][Tf2N−], n = 4, 10) as diluents. The solvent extraction of Gd(III) ion with a chelating compound, 4-benzoyl-3-phenyl-5-isoxazolone (HPBI) has been investigated as well, plus various synergistic solvent systems. Enhanced extraction (synergism) and complete destruction of it by addition of excess of the two ligands are demonstrated. This antisynergistic effect or antagonism is shown to be greater than the negative effect due to the chemical nature of the IL’s cation connected with the water content of the organic phase. The ligand effect on the complexation properties of Gd(III) ion is quantitatively assessed. The synergistic effect in an IL media, [C1C10im+][Tf2N−] is further evaluated and discussed. The organic extracts are examined by EPR and 31P NMR approaches in order to viewing the cation coordination and ligands’ binding mode in the organic phase solution. Several conclusions are given highlighting the role of the ionic diluent in complexation processes and selectivity with an employment of the stronger chelating agent HPBI for various metal s-, p-, d- and f-cations.

Zinc(II) and cobalt(II) complexes with unusual coordination of mixed imidazole-1,2,4-triazole ligand in a protonated cationic form

Zinc(II) and cobalt(II) molecular coordination compounds with the mixed-donor 1-(4-(1H-imidazol-1-yl)benzyl)-1H-1,2,4-triazole were prepared and their crystal structure was determined by single crystal X-ray diffraction analysis. Both metal cations are in a slightly distorted tetrahedral arrangement, the heterocyclic ligand is coordinated via 1,2,4-triazole nitrogen atoms at position 4 of the ring, consistent with the localization of a negative charge at this atom, according to DFT calculations. Upon coordination, the ligand undergoes protonation with the formation of rare examples of transition metal coordination compounds with the cationic ligands. Zinc(II) complex demonstrated ligand-centered photoluminescence with the maximum near 302 nm upon excitation at 264 nm.

Real-Space Image of Charged Patches in Tunable-Size Nanocrystals.

The remarkable dual nature of faceted-charge patchy metal fluoride nanocrystals arises from the spontaneous selective coordination of anionic and cationic ligands on the different facets of the nanocrystals. In previous studies, the identification and origin of the charge at the patches were obtained by combining computer simulations with indirect experimental evidence. Taking a step further, we report herein the first direct real-space identification by Kelvin probe force microscopy of the predicted faceted-charge patchy behavior, allowing the image of the dual faceted-charge surfaces. High-resolution transmission electron microscopy reveals the detailed nanocrystal faceting and allows unambiguously inferring the hydrophilic or hydrophobic role of each facet from the identification of the surface atoms exposed at the respective crystallographic planes. The success of the study lies in a foresighted synthesis methodology designed to tune the nanocrystal size to be suitable for microscopy studies and demanding applications.

A New Concept of Radiation Detection Based on a Fluorochromic and Piezochromic Nanocluster.

Developing materials that possess colorimetric responses to external stimuli is a promising strategy for addressing the current challenges in radiation dosimetry. Currently, colorimetric ionizing-radiation-responsive materials remain underexplored, and those with multistimuli response are rare. Herein, the integration of thorium cation and photoresponsive terpyridine carboxylate ligand gives rise to a thorium nanocluster, Th-101, which displays the second case of fluorochromic response and unprecedented piezochromic behavior among all actinide materials. The emission color of Th-101 exhibits a gradual transition from blue to cyan to green upon irradiation with accumulated dose, which renders colorimetric dosimetry of ionizing radiation based on a red-green-blue (RGB) concept. Further fabricating Th-101 into a custom-built optoelectronic device allows for on-site quantification of radiation dose with merits of ease of operation, rapid readout, and cost-effectiveness.

Cationic ligands between σ-donation and hydrogen-bridge-bond-stabilisation of ancillary ligands in coinage metal complexes with protonated carbodiphosphoranes.

A series of copper(I) and silver(I) complexes is reported containing the PCP-type tridentate ligand [(dppm)2CH]+ with a protonated carbodiphosphorane (CDPH) as cationic central donor group (dppm = 1,1-bis(diphenylphosphino)methane). In comparison to the previously reported gold complex [({dppm}2CH)AuCl]+ [Reitsamer et al., J. Organomet. Chem., 2017, 830, 150], the corresponding silver and copper complexes exhibit a κC-coordinated CDPH-group, which is absent in case of gold. For the series of silver complexes, we demonstrate that the κC-coordination of the CDPH-group is dependant on the ancillary ligand and that hydrogen bonding of the CDPH-group to the ancillary ligand can be competitive. The ability for such hydrogen bonding is a unique characteristic of protonated CDPs in comparison to other cationic ligands, which might offer benefits for applications in homogeneous catalysis by hemilability and substrate activation with this group.