Ethyl Group Research Articles

Highly Enantioselective Transportation Across Liquid Membranes Mediated by Porous Covalent Organic Frameworks

Chiral liquid membrane separation is crucial in pharmaceuticals and chemical synthesis for its simplicity and stability, yet designing membrane carriers that enable efficient enantioseparation remains a challenge. Here, we demonstrated for the first time that chiral porous materials can act as mobile carriers of bulk liquid membranes (BLMs) to enhance enantioselective transport and separation. We design and prepare three 2D chiral covalent organic frameworks (CCOFs) by imine condensations of a chiral dialdehyde with triamines containing ethyl, fluorine and/or isopropyl groups. These isostructural CCOFs feature ABC stacking, excellent water, acid and base tolerance, and chiral amine groups in 1D porous channels, promoting efficient enantioselective transportation of amino acid enantiomers. Among them, the CCOF with both ‐F and ‐iPr groups showing superior transport performance. Exfoliating the CCOF into chiral nanosheets creates flexible layers with accessible active sites, enabling nanosheet‐mediated liquid membranes to separate chiral drug enantiomers, a feat unattainable with the pristine CCOF. This work establishes CCOFs as a promising platform for chiral BLM separations and will guide the design of high‐performance BLMs using porous materials for enantioselective separation.

Highly Enantioselective Transportation Across Liquid Membranes Mediated by Porous Covalent Organic Frameworks

Chiral liquid membrane separation is crucial in pharmaceuticals and chemical synthesis for its simplicity and stability, yet designing membrane carriers that enable efficient enantioseparation remains a challenge. Here, we demonstrated for the first time that chiral porous materials can act as mobile carriers of bulk liquid membranes (BLMs) to enhance enantioselective transport and separation. We design and prepare three 2D chiral covalent organic frameworks (CCOFs) by imine condensations of a chiral dialdehyde with triamines containing ethyl, fluorine and/or isopropyl groups. These isostructural CCOFs feature ABC stacking, excellent water, acid and base tolerance, and chiral amine groups in 1D porous channels, promoting efficient enantioselective transportation of amino acid enantiomers. Among them, the CCOF with both ‐F and ‐iPr groups showing superior transport performance. Exfoliating the CCOF into chiral nanosheets creates flexible layers with accessible active sites, enabling nanosheet‐mediated liquid membranes to separate chiral drug enantiomers, a feat unattainable with the pristine CCOF. This work establishes CCOFs as a promising platform for chiral BLM separations and will guide the design of high‐performance BLMs using porous materials for enantioselective separation.

Crystal structure, Hirshfeld surface analysis, DFT and molecular docking studies of ethyl 5-amino-2-bromoisonicotinate

In the title compound, C8H9BrN2O2, the C—O—C—C torsion angle between isonicotine and the ethyl group is 180.0 (2)°. Intramolecular N—H...O and C—H...O interactions consolidate the molecular structure. In the crystal, N—H...N interaction form S(5) zigzag chains along [010]. The most significant contributions to the Hirshfeld surface arise from H...H (33.2%), Br...H/H...Br (20.9%), O...H/H...O (11.2%), C...H/H...C (11.1%) and N...H/H...N (10%) contacts. The topology of the three-dimensional energy frameworks was generated using the B3LYP/6–31 G(d,p) model to calculate the total interaction energy. The net interaction energies for the title compound are E ele = 59.2 kJ mol−1, E pol = 15.5 kJ mol−1, E dis = 140.3 kJ mol−1 and E rep = 107.2 kJ mol−1 with a total interaction energy E tot of 128.8 kJ mol−1. The molecular structure was optimized by density functional theory (DFT) at the B3LYP/6–311+G(d,p) level and the theoretical and experimentally obtained parameters were compared. The frontier molecular orbitals HOMO and LUMO were generated, giving an energy gap ΔE of 4.0931 eV. The MEP was generated to identify active sites in the molecule and molecular docking studies carried out with the title compound (ligand) and the covid-19 main protease PDB ID: 6LU7, revealing a moderate binding affinity of −5.4 kcal mol−1.

Structural mechanisms of potent lysophosphatidic acid receptor 1 activation by nonlipid basic agonists.

Lysophosphatidic acid receptor 1 (LPA1) is one of the G protein-coupled receptors activated by the lipid mediator, lysophosphatidic acid (LPA). LPA1 is associated with a variety of diseases, and LPA1 agonists have potential therapeutic value for treating obesity and depression. Although potent nonlipid LPA1 agonists have recently been identified, the mechanisms of nonlipid molecule-mediated LPA1 activation remain unclear. Here, we report a cryo-electron microscopy structure of the human LPA1-Gi complex bound to a nonlipid basic agonist, CpY, which has 30-fold higher agonistic activity as compared with LPA. Structural comparisons of LPA1 with other lipid GPCRs revealed that the negative charge in the characteristic binding pocket of LPA1 allows the selective recognition of CpY, which lacks a polar head. In addition, our structure show that the ethyl group of CpY directly pushes W2716.48 to fix the active conformation. Endogenous LPA lacks these chemical features, which thus represent the crucial elements of nonlipid agonists that potently activate LPA1. This study provides detailed mechanistic insights into the ligand recognition and activation of LPA1 by nonlipid agonists, expanding the scope for drug development targeting the LPA receptors.

Systematic study on the hydrogen abstraction reactions from oxygenated compounds by H and HO2

AbstractTo extend the rule‐based approach for hydrogen abstraction reactions from oxygenated compounds, a systematic investigation was performed to examine the reactivity of gas‐phase hydrogen abstraction reactions from alkyl groups (methyl and ethyl groups) bound to oxygen atoms in five types of oxygenated compounds (alcohols, ethers, formate esters, acetate esters, and carbonate esters) by H atoms and HO2 radicals comprehensively considering rotational conformers. Quantum chemical calculations were conducted at the CBS‐QB3 level for stationary points. Rate constants were determined employing conventional transition state theory (TST). For hydrogen abstraction reactions by H, the rotational conformer distribution partition function was employed to approximate partition functions, owing to the similarity in vibrational energy‐level structures among conformers. In hydrogen abstraction reactions by HO2, the vibrational structures of transition‐state (TS) conformers varied significantly due to the hydrogen bonding, leading to an inappropriate evaluation of rate constants when using the lowest‐energy conformer as a representative. Therefore, the rate constants were calculated by the multi‐structural TST. It was revealed that the differences in functional groups containing O atoms mainly affect the bond dissociation energies of the C–H bonds and the activation energies of hydrogen abstraction reactions only when the C atoms are adjacent to the O atoms. Additionally, it was found that hydrogen bonds formed in the TSs show minor effect on rate parameters for the overall rate constants, apart from the reduction of the pre‐exponential factors for the H‐abstraction reactions from the methylene position of ethyl groups. The comparison with the rate constants from previous studies showed reasonable results, indicating that the rate constants in this study, which thoroughly consider rotational conformers, can be the current best estimates.

Formation of Radical-like NH Ligand from NH3 at Ambient Conditions Mediated by Dialkyl Rare-Earth Complexes.

Although intensive work on ammonia activation has been carried out in recent decades, generating nitrogen-centered radicals from NH3 under ambient conditions remains quite challenging. In the presented research, the conversion of NH3 to radical-like NH ligand has been achieved by the reactions of a series of dialkyl rare-earth (RE) complexes (1-RE, RE = Tb, Dy, Y, Ho, Er, Yb, and Lu) supported by β-diketiminate ligands with NH3 in n-hexane at room temperature, resulting in the formations of the radical-like μ3-NH ligands containing trinuclear RE complexes (2-RE). The radical-like feature of the μ3-NH ligand was revealed by electron paramagnetic resonance and magnetic measurements, radical trapping experiments, and computational spin density analysis. In addition, H2 was detected to form during the reaction of 1-RE with NH3, indicating that the radical-like μ3-NH ligand was likely to be generated via N-H bond homolysis. Moreover, the solvents and coordination pattern of β-diketiminate ligands are crucial for the formation of the radical-like μ3-NH ligand from NH3. When toluene instead of n-hexane was used in the reaction of 1-RE with NH3, an array of octaamido tetranuclear RE complexes (3-RE) was obtained. The reaction of the dialkyl yttrium complex (4-Y) bearing a modified β-diketiminate ligand, in which the two mesityl substituents are replaced by a 2,6-diisopropylphenyl group and a 2-(dimethylamino)ethyl group, with NH3 in both n-hexane and toluene only yielded a tetranuclear yttrium complex carrying the dianionic closed-shell μ3-NH ligands (5-Y).

Biotoxicity Evaluation of Biodegradable Polymeric Particles: Exploring the Possible Adverse Impacts on Biological Systems

ABSTRACTThis study aimed to investigate the impact of plastic particles on cell viability and tissue toxicity. The cells were subjected to incubation with plastic particles immobilized in agar gels, resulting in minimal cell death and cytotoxicity. Furthermore, direct exposure of various cell types to suspended plastic particles showed negligible effects on cell viability, with no observed lysis or growth inhibition. Staining techniques revealed minimal plastic particle‐induced cell death, with the majority of cells remaining viable. However, histological evaluations of mouse tissues demonstrated that the nondegradable low‐density poly(ethylene) (LDPE) groups exhibited severe irritation, characterized by an excessive presence of macrophages, neutrophils, fibrosis, fat infiltration, and increased blood vessel formation in subcutaneous tissue. In contrast, biodegradable neat poly(butylene succinate) (KRICT‐PBS) and cellulose nanocrystals/PBS nanocomposite (CNC‐PBS) groups induced minimal toxicity. Interestingly, the intravenous injection of KRICT‐PBS and CNC‐PBS degradate solutions in mice exhibited mild toxicity, suggesting no significant damage to normal kidney and liver function.

(1H-Benzodiazol-2-ylmethyl)diethylamine

In the crystal of the title compound, C12H17N3, the molecules are linked by N—H...N hydrogen bonds, generating a C(4) chain extending along the c-axis direction. One of the ethyl groups is disordered over two sets of sites with a refined occupancy ratio of 0.582 (15):0.418 (15).

Icosapent ethyl by baseline small dense low-density lipoprotein cholesterol: an analysis of REDUCE-IT

Abstract Background Small dense low-density lipoprotein cholesterol (sdLDL-C) is associated with cardiovascular (CV) risk. Purpose We assessed if baseline sdLDL-C modified the effect of icosapent ethyl among patients in REDUCE-IT. Methods REDUCE-IT randomized patients to icosapent ethyl vs placebo. In this post hoc analysis, patients ≥45 years with CV disease or ≥50 years with diabetes and CV risk factors were included. Patients were required to have triglycerides of 135-499 mg/dL and low-density lipoprotein cholesterol (LDL-C) of 41-100 mg/dL. Exclusion criteria included severe heart failure, acute severe liver disease, or hemoglobin A1c >10%. Patients were stratified by baseline calculated sdLDL-C. A threshold of 46 mg/dL was chosen because sdLDL-C greater than this cutoff has predicted CV risk despite well-controlled LDL-C. The primary outcome included a composite of CV death, nonfatal myocardial infarction (MI), nonfatal stroke, coronary revascularization, or unstable angina. The key secondary composite outcome included CV death, nonfatal MI, or nonfatal stroke. Outcomes were assessed with Cox proportional hazard models and interaction analyses were conducted to assess heterogeneity in treatment effect by baseline sdLDL-C. Results REDUCE-IT included 8179 patients, with 8157 (99.7%) patients having sdLDL-C data. Among these patients, 7698 (94.4%) had sdLDL-C <46 mg/dL and 459 (5.6%) had sdLDL-C ≥46 mg/dL. Median sdLDL-C was 34.2 mg/dL (interquartile range [IQR]: 30.3, 38.4 mg/dL) in the lower sdLDL-C group and 48.4 mg/dL (IQR: 47.1, 50.6 mg/dL) in the higher sdLDL-C group (Table). The placebo group had a greater event rate in the higher sdLDL-C group compared to the lower sdLDL-C group (72.0 vs 56.4 events per 1000 p-y), though event rates in the icosapent ethyl group were similar by sdLDL-C group (44.1 vs 43.3 events per 1000 p-y, respectively). Icosapent ethyl reduced the rate of the primary outcome compared with placebo (17.2% vs 22.0%; hazard ratio [HR]: 0.75 [95% CI: 0.68, 0.83]; P<0.0001). The number needed to treat [NNT] to avoid one primary endpoint event was 21. In the lower sdLDL-C group, icosapent ethyl decreased rates of the primary outcome (43.3 events per 1000 patient-years [p-y]) compared with the placebo group (56.4 events per 1000 p-y) (17.3% vs 21.7%; HR: 0.77 [95% CI: 0.69, 0.85]; NNT: 22). Similarly, in the higher sdLDL-C group, icosapent ethyl decreased the rate of the primary outcome (44.1 events per 1000 p-y) compared with the placebo group (72.0 events per 1000 p-y) (16.6% vs 26.4%; HR: 0.58 [95% CI: 0.38, 0.88]; NNT: 10). There was no significant interaction between treatment benefit and baseline sdLDL-C for the primary (Pinteraction = 0.22) and key secondary outcome (Pinteraction = 0.82). Findings were overall similar for the other secondary outcomes (Figure). Conclusion Icosapent ethyl reduced CV outcomes in patients with high CV risk and elevated triglycerides irrespective of low or high sdLDL-C.

Investigation of Phosphazene Superbase Interactions with [PCl2N]3.

In this study, the reaction between phosphazene superbases and a chlorophosphazene trimer ([PCl2N]3) has been investigated. In this room temperature reaction, the phosphazene superbase (Me2N)3PN(Me2N)2P═NEt, commonly known as P2Et, was shown to behave as a nucleophile, displacing one of the chlorides from [PCl2N]3 and producing the tadpole-like structure 1. The reaction described herein is one of the few instances of a phosphazene superbase behaving as a nucleophile rather than a Brønsted base. Once formed, this structure contains contrasting reactivity, containing a weakly basic phosphazene head while maintaining a highly basic phosphazene tail of the tadpole. The mechanism of the reaction was explored by investigating the potential energy surface through density functional theory calculations at the B3LYP/6-311+G(d,p) level of quantum mechanical theory. It was determined that the reaction of P2Et with [PCl2N]3 followed a stepwise process beginning with the substitution of P2Et onto [PCl2N]3 with the concurrent loss of chloride. Subsequently, the chloride attacks the ethyl group of the P2Et moiety, and ethyl chloride is released, producing 1. Compound 1 was further characterized via 31P NMR spectroscopy, mass spectrometry, and X-ray crystallography.

Computational Study of Carbon Dioxide Capture by Tertiary Amines.

The reaction mechanisms and corresponding structure-activity relationships of tertiary amines with respect to CO2 capture have been investigated using density functional theory (DFT) calculations. The reaction mechanism for CO2 capture via base-catalyzed hydration to form bicarbonate is proposed to proceed in a single step involving proton transfer and the formation of a carbon-oxygen bond. Based on the height of the reaction barriers, we suggest that amines containing side chains with the ethyl group, along with a single hydroxyl group, and cyclic structures, are especially active for CO2 capture. The activation barrier is shown to be a descriptor for predicting the experimental CO2 loading values. To enhance the prediction accuracy for CO2 loading, we employ the sure-independence screening and sparsifying operator (SISSO) method, which can scan a large pool of mathematical terms stemming from combining DFT-derived descriptors to select the superior ones. Thus, we can predict the CO2 loading with acceptable accuracy from the obtained mathematical expression. Since the computational workload of applying this expression is negligible, this facilitates high-throughput screening and accelerates the design of tertiary amines for CO2 capture.

Design, synthesis, and evaluation of chalcone derivatives as xanthine oxidase inhibitors

Xanthine oxidase (XO) is an important enzyme that catalyzes the oxidation of hypoxanthine to xanthine and xanthine to uric acid in the catabolism of purines in humans. This makes XO a well-recognized target in alleviating hyperuricemia. The present study adapted a structure-based drug discovery approach to develop potent and low-toxicity XO inhibitors with the chalcone skeleton. We introduced a carboxyl group and a hydroxyl group to the B ring and modified the A ring. 35 chalcone derivatives were designed and synthesized. All the 35 derivatives exhibited higher XO inhibition activities (IC50=0.064-0.559μM) compared with allopurinol (IC50=2.588μM). Their high affinity was attributed to strong hydrogen bond interactions formed between the introduced carboxyl and hydroxyl groups with key amino acid residues in XO. SAR analysis disclosed that carboxyl, hydroxyl, ethyl (12c), methylamino (12h), dimethylamino (12i), indolin (13k), and indol (13l) groups played important roles in improving the whole molecules' inhibition potency against XO. ADME predictions and cytotoxicity assays suggested their pharmacokinetic characteristics and biocompatibility were desirable. Additionally, 12c exhibited a significant hypouricemic effect on potassium oxonate-induced hyperuricemia rats after orally administrated at a dose range of 10-40mg/kg, representing a promising anti-hyperuricemia potential for further optimization and development.

Sulfur Fluoride Exchange Enabled Polysufate Adsorbents: Flexible Group Embedded in Polymer Backbone Regulation Strategy for Organic Solvent Removal from Water.

Removal of organic solvents (such as chloroform, toluene, etc.) in trace amounts using adsorbents from water is a challenge due to their low removal efficiencies and poor selectivities. Herein, four polysulfates (P1-P4) with different flexible group embedded backbones were synthesized via a sulfur fluoride exchange (SuFEx) reaction, and their swelling behaviors in organic solvents were investigated. P1 with a flexible ethyl group on its backbone can selectively swell in aprotic organic solvents with medium and high polarities about 30-fold its original weight, which is much higher than that of P4 with rigid benzene on its backbone. Moreover, molecular dynamic (MD) simulation results showed that the swelling mechanism could be put down to the electrostatic and van der Waals forces between the polysulfates and organic solvents. Surprisingly, the polysulfates can be used to remove chloroform and toluene from water with removal efficiencies of up to 99.26 and 99.42%, respectively. Furthermore, the polysulfates also exhibited high selectivities and anti-interference performances toward chloroform in the presence of other pollutants and different acid/base environments. Our work provides a strategy to construct adsorbents with high efficiencies for removal of low concentrations of organic solvents from water.

Molecularly Woven Cationic Covalent Organic Frameworks for Highly Selective Electrocatalytic Conversion of CO2 to CO.

Coupling carbon capture with electrocatalytic carbon dioxide reduction (CO2R) to yield high-value chemicals presents an appealing avenue for combating climate change, yet achieving highly selective electrocatalysts remains a significant challenge. Herein, two molecularly woven covalent organic frameworks (COFs) are designed, namely CuCOF and CuCOF+, with copper(I)-bisphenanthroline complexes as building blocks. The metal-organic helical structure unit made the CuCOF and CuCOF+ present woven patterns, and their ordered pore structures and cationic properties enhanced their CO2 adsorption and good conductivity, which is confirmed by gas adsorption and electrochemical analysis. In the electrocatalytic CO2R measurements, CuCOF+ decorated with extra ethyl groups exhibit a main CO product with selectivity of 57.81%, outperforming the CuCOF with 42.92% CO at the same applied potential of 0.8 VRHE. After loading Pd nanoparticles, CuCOF-Pd and CuCOF+-Pd performed increased CO selectivity up to 84.97% and 95.45%, respectively. Combining the DFT theoretical calculations and experimental measurements, it is assumed that the molecularly woven cationic COF provides a catalytic microenvironment for CO2R and ensures efficient charge transfer from the electrode to the catalytic center, thereby achieving high electrocatalytic activity and selectivity. The present work significantly advances the practice of cationic COFs in real-time CO2 capture and highly selective conversion to value-added chemicals.

Substituent effect on the chemical and biological properties of diisatin dihydrazone Schiff bases: DFT and docking studies

According to the considered role of lipophilicity-hydrophobicity on organic Schiff base hydrazones, different substituents of phenyl, ethyl, and methyl groups were inserted in the synthetic strategy of diisatin dihydrazones (L1–4). The biochemical enhancement was evaluated depending on their inhibitive potential of the growth power of three human tumor cells, fungi, and bacteria. The biochemical assays assigned the effected role of different substituents of phenyl, ethyl, and methyl groups on the effectiveness of their diisatin dihydrazone reagents. The interacting modes with calf thymus DNA (i.e. Ct-DNA) were studied via viscometric and spectrophotometric titration.The organo-reagent L1 with the oxalic derivative assigned a performed inhibitive action for the examined microbes and the human tumor cell lines growing up over the terephthalic (L4) > malonic (L2) > succinic (L3) ones. From Kb = binding constant, and ∆Gb≠ = Gibb’s free energy values, the binding of interaction within Ct-DNA was evaluated for all compounds (L1–4), in which L1, L3, and L4 assigned the highest reactivity referring to the covalent/non-covalent modes of interaction, as given for (L1–4), 14.32, 13.28, 10.87, and 12.41 × 107 mol−1 dm3, and −45.17, −43.24, −43.75, and −44.05 kJ mol−1, respectively. DFT and docking studies were achieved to support the current work.

Fluorogenic Chemical Probe Strategy for Precise Tracking of Mitochondrial Polarity.

Mitochondrial polarity is a critical indicator of numerous pathological and biological processes; thus, the development of fluorescent probes capable of targeting mitochondria and visually monitoring its polarity is of great significance. In this study, fluorescent probes were designed with a N, N-dialkylamino rhodol scaffold as the fluorophore sensitive to polarity environments, in which the alkyl chain length was adjusted rationally to obtain distinct polarity recognition modes. By integrating mitochondria targeting groups, three fluorogenic chemical probes ROML-1, ROML-2, and ROML-3 have been obtained, featuring the capability to target mitochondria and monitor its polarity precisely, dynamically and visually. The probes displayed a distinctive response to the alterations in polarity. ROML-1 and ROML-2 followed a turn-on pattern while ROML-3 was ratiometric. It has been demonstrated that the hypersensitivity to polarity and ratio fluorescence property of ROML-3 was attributed to methyl groups rather than ethyl or butyl groups. The introduction of short methyl chains made the dihedral angle between the dialkylamino substituent and fluorophore of ROML-3 (spirocyclic form) rotatable and enlarged the energy gap between the ground state and excited state, which has been validated by the results of density functional theory (DFT) calculations. Furthermore, ROML-3 was used to monitor mitochondrial polarity via confocal microscopy imaging, which revealed that compared to healthy cells the polarity of mitochondria in cancer cells was enhanced; meanwhile, the polarity of mitochondria in senescent cells was higher in contrast with young cells. The present probe ROML-3 has been proven to be an efficient tool to monitor mitochondrial polarity dynamics, which demonstrated potential significance in biomedical research and disease diagnosis.

Cytotoxic and Anti-HSV-1 Effects of Caulerpin Derivatives.

Marine organisms represent a potential source of secondary metabolites with various therapeutic properties. However, the pharmaceutical industry still needs to explore the algological resource. The species Caulerpa lamouroux Forssk presents confirmed biological activities associated with its major compound caulerpin, such as antinociceptive, spasmolytic, antiviral, antimicrobial, insecticidal, and cytotoxic. Considering that caulerpin is still limited, such as low solubility or chemical instability, it was subjected to a structural modifications test to establish which molecular regions could accept structural modification and to elucidate the cytotoxic bioactive structure in Vero cells (African green monkey kidney cells, Cercopithecus aethiops; ATCC, Manassas, VA, USA) and antiviral to Herpes simplex virus type 1. Substitution reactions in the N-indolic position with mono- and di-substituted alkyl, benzyl, allyl, propargyl, and ethyl acetate groups were performed, in addition to conversion to their acidic derivatives. The obtained analogs were submitted to cytotoxicity and antiviral activity screening against Herpes simplex virus type 1 by the tetrazolium microculture method. From the semi-synthesis, 14 analogs were obtained, and 12 are new. The cytotoxicity assay showed that caulerpin acid and N-ethyl-substituted acid presented cytotoxic concentrations referring to 50% of the maximum effect of 1035.0 µM and 1004.0 µM, respectively, values significantly higher than caulerpin. The antiviral screening of the analogs revealed that the N-substituted acids with methyl and ethyl groups inhibited Herpes simplex virus type 1-induced cytotoxicity by levels similar to the positive control acyclovir.

Exploring the conformational landscape through rotational spectroscopy and computational modelling: The tunneling dynamics in 2,6-diethylphenol

Phenol and some of its derivatives exhibit interesting tunneling motions consisting of two groups of transitions separated by a few hundred MHz. Recently, one of its derivatives, 2,6-di-tert-butylphenol, has shown additional hyperfine tunneling components, the origin of which remains unclear. In this work, another member of the family, 2,6-diethylphenol, has been investigated through its rotational spectrum. The jet-cooled broadband chirped-pulse Fourier transform microwave spectra in the 2–8 GHz frequency region revealed the presence of two conformers. The comparison with the equilibrium structure obtained by computational calculations at the B3LYP-D3(BJ)/Def2-TZVP level validates the structural determination and the orientation of the lateral ethyl groups. Additional observation of all the singly-substituted 13C isotopologues for the most stable ones allowed the determination of the substitution structure by means of the Kraitchman equations. Both conformers exhibited tunneling that was reproduced using an advanced 1D model, which provides an estimate of the barrier height for both conformers.

Controlling curcumin/acrylic polymer interactions for tailored delivery systems

In this work, we investigate the interaction between curcumin and biocompatible polymethacrylates (methyl, ethyl, and n-butyl side groups). Blend samples were produced using the salt leaching technique to increase the contact area in the ionic medium with pH 2.0, 5.0, 7.4, and 8.0. Using curcumin photoluminescence (PL) spectra to determine release profiles, we found a 6-fold higher quantity and a 3-fold higher release ratio for poly(n-butyl methacrylate) (PnBMA). Changes in the ionic form of curcumin were observed with PL blue shift and decrease in the characteristic time, from ca. 435 min at pH 2.0 and 5.0 to 192 min at pH 7.4 for PnBMA. The relative importance of curcumin interactions with the side and main polymer chains could be determined by interpreting the release profiles. With curcumin interaction controlled by pH and the length of the polymer side chain, one may envisage tailored drug delivery systems focusing on prolonged release.

Exploration of Synthesis and Coordination Chemistry of Thiazole-Containing Calix[3]Pyrroles

Calix[n]pyrroles have been used as powerful and specific receptors and as extractants for anions and ion pairs over the past 20 years. In the recent past, calix[4]pyrroles have been used as systems that can move ions and ion pairs over lipophilic membranes [1]. Unfortunately, the coordination chemistry of calix[n]pyrroles hardly explored. The ring-contracted analog of calix[n]pyrrole, calix[3]pyrrole, was synthesized and recently published [2]. The structure of calix[3]pyrrole and its analogues is strained, and they show an appealing strain-induced ring expansion response. On the other hand, the synthesis of calix[3]pyrrole requires multistep reactions including cyclization of hexaketone precursor and Paar–Knorr synthesis with the total yield of 4%. Extended use of calix[3]pyrrole analogues necessitates further refinement of the synthesis process.Here, we demonstrate the synthesis of new calix[3]pyrroles analogue, calix[1]pyrrole[2]thiazole (3). Direct macrocyclization between bis(α-bromoketone) and 2,2-dimethylpropane (bis-thioamide) produced the calix[1]furan[2]thiazole (1), with 60% yield. The furan unit of 1 was converted into pyrrole to give calix[1]pyrrole[2]thiazole 3 (Figure 1).Single-crystal X-ray analysis revealed a cone-shaped conformation of calix[1]pyrrole[2]thiazole 3, with all three heterocycles pointing in the same direction through strong intramolecular hydrogen bonding. However, unlike calix[3]pyrrole, calix[1]pyrrole[2]thiazole was completely stable under acidic conditions, which may be due to the basic nature of the thiazolimine units.Metal coordination of calix[1]pyrrole[2]thiazole was attempted and its Zn(II), Ag(I) and Pd(II) complexes were obtained by appropriate metalation procedures. The central metal ion of the Zn(II) complex is coordinated by a conical 3 and an axial ethyl group to behave as a monoanionic tridentate ligand. In contrast, it acts as a bidentate neutral ligand for Pd(II) or Ag(I) complexation. The synthesis of meso-aza calix[1]pyrrole[2]thiazole is in progress. Figure 1