Single Crystal Structure Research Articles

Multifunctional bacterium induced carbonate precipitation with low nitrogen effectively remediates cadmium polluted water

Microorganism Induced Carbonate Precipitation (MICP) has emerged as an efficacious approach to address the issue of cadmium (Cd) contamination in water bodies. However, the associated production of ammonium nitrogen (NH4+-N) poses a significant challenge to the MICP. To tackle this, our research has developed a novel bacterium (UN-1), with dual MICP and NH4+-N degradation capabilities. We have elucidated the biogeochemical pathways of Cd2+ precipitation and NH4+-N degradation, characterized the micromorphology, phase composition, and crystallization of the MICP products, and identified the key factors influencing the MICP reaction. Our findings indicate that The UN-1-mediated MICP effectively removes Cd2+ at concentrations below 20 mg/L, reducing NH4+-N levels to 50 mg/L within 120 h. The predominant strains in UN-1 are Sporosarcina (24.35 %), Bacillus (31.36 %), Tumebacillus (6.89 %), Nitrospira (11.09 %), and Alkaliphilus (8.16 %). The bacterium employs urea enzymes UreA, UreB, and UreC for urea hydrolysis, thereby facilitating carbonate production, while the degradation of NH4+-N is mediated by hydroxylamine oxidase (HAO), nitrite reductase (NIR), and nitrate reductase (NAR). The resultant MICP products after Cd2+ removal are irregular spherical minerals, 200–300 nm in diameter, exhibiting well-developed single-crystal structures and high crystallinity. Their X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) patterns align with the characteristics of cadmium carbonate (CdCO3) minerals. Optimal conditions for the UN-1-led MICP reaction are identified as a pH range of 5.0 to 9.0 and a temperature range of 20 to 40 °C, the dissolved oxygen (DO) concentration in the water does not significantly impact the MICP. Furthermore, the study demonstrates that NH4+-N concentrations can be maintained at low levels under most conditions. This research introduces an innovative solution to the NH4+-N by-product challenge during Cd removal via MICP, laying a solid theoretical foundation for the development of a rapid, efficient, and eco-friendly remediation technology for Cd-contaminated waters.

Spectroscopic, quantum chemical and molecular docking studies of N-((anthracen-9-yl) methylene-2-methyl benzenamine): a potent probe to lipid bilayer systems

ABSTRACT A new synthesized Schiff base, N-((anthracen-9-yl) methylene-2-methyl benzenamine) (AMMB), was prepared from o-toluidine and 9-anthracenecarboxaldehyde. The structure of the compound was confirmed by single crystal X-ray diffraction and characterized through various analytical tools such as high resolution mass, 1H and 13C NMR, infrared, UV-vis and elemental composition analysis. The molecular geometries of AMMB were optimized by means of DFT/B3LYP/6311-G++ (d,p) basis set. The optimized geometric parameters of the compound were concordant with the single crystal structure. The optimized structure was utilized in comparison of experimental FT-IR with calculated frequency calculation. TD-DFT analysis was performed to compute the electronic absorption of the compound. SCF-GIAO was employed to compute 1H and 13C NMR, which was consistent with the experimental results. Additionally, NLO, NBO, MEP and global reactivity parameters were also computed using the same level of theory. Hirshfield surface analysis, fingerprint plot and energy frameworks were presented to explore the intermolecular interactions within the crystal. Molecular docking study was carried out to predict the probable binding site of AMMB into lipid bilayers such as DMPC, DPPC, POPC, DLPE, DOPC and POPE. The molecular docking analysis of AMMB showed complex formation with binding affinity energy ranging from −9.3 to −3.4 kcal/mol.

Semi-Preparation and X-ray Single-Crystal Structures of Sophocarpine-Based Isoxazoline Derivatives and Their Pesticidal Effects and Toxicology Study.

Recently, research and development of novel pesticides from natural plant products have received much attention. To accelerate the application of sophocarpine as the agrochemical candidate, a series of novel sophocarpine-based isoxazoline derivatives were prepared by the 1,3-dipolar [2 + 3] cycloaddition reaction of sophocarpine with different chloroximes. Their structures were well characterized by high-resolution mass spectra, infrared spectra, and proton/carbon-13 nuclear magnetic resonance spectra. Eight steric configurations of compounds 5a, 5e', 5f, 5g, 5h, 5i, 5r, and 5u' were further determined by X-ray single-crystallography. Against Aphis citricola Van der Goot, compounds 5n (LD50: 0.032 μg/nymph) and 5o (LD50: 0.024 μg/nymph) exhibited greater than 3.7- and 4.9-fold potent aphicidal activity compared to sophocarpine (LD50: 0.118 μg/nymph). Against Tetranychus cinnabarinus Boisduval, derivative 5g displayed the most promising acaricidal activity with the LC50 value of 0.247 mg/mL, which was 14.2-fold that of sophocarpine. Compounds 5d and 5g also exhibited good control efficacy against T. cinnabarinus. Scanning electron microscopy images indicated that compound 5g can destroy the mite cuticle layer. These results will provide the foundation for the structural modification and use of sophocarpine derivatives as agrochemicals in the future.

Oxidative stress, histopathological and genotoxicity of copper oxide nanoparticles in Biomphalaria alexandrina snail

AbstractHigher usage of copper oxide nanomaterials in industrial and biomedical fields may cause an increase of these nanoparticles in aquatic environments, which could have a detrimental ecological effect. Thus, the objective of this study was to evaluate the acute toxicity of copper oxide nanoparticles on the freshwater gastropod, Biomphalaria alexandrina. Transmission electron microscopy, x-ray diffraction analysis and UV–VIS spectrophotometer of CuO NPs revealed a typical TEM image and a single crystal structure with average crystallite size of approximately 40 nm also, a sharp absorption band was appeared. Following exposure to sub-lethal concentrations of CuO NPs (LC10, 15.6 mg/l and LC25, 27.2 mg/l), treated snails revealed a significant decrease (p < 0.05) in total antioxidant capacity, reduced glutathione contents as well as catalase, and sodium dismutase activities were significantly declined (p < 0.05) in comparison to the control group. Also, histopathological alterations were observed in the digestive gland, including ruptured and vacuolated digestive cells, and a marked increase in the number of secretory cells and the severity of the damage increased with rising concentrations. Furthermore, changes in RAPD profiles were detected in the treated snails. In conclusion, our research highlights the potential ecological impact of CuO NPs release in aquatic ecosystems and advocates for improved monitoring and regulation of CuO NPs industrial usage and disposal.

The Dialuminene AriPr8AlAlAriPr8 (AriPr8=C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2).

Careful analysis of the crystals formed in the reduction of AriPr8AlI2 (AriPr8=C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2) with sodium on sodium chloride showed them to contain the long sought-after dialuminene AriPr8AlAlAriPr8 (1) that forms alongside the previously characterized alanediyl :AlAriPr8. The single crystal X-ray structure of 1 revealed a nearly planar, trans-bent C(ipso)AlAlC(ipso) core with an Al-Al distance of 2.648(2) Å. The molecular and electronic structure of 1 are consistent with an Al-Al double dative interaction augmented with diradical character and stabilized by dispersion interactions. Density functional theory calculations showed that the reactivity of :AlAriPr8 with dihydrogen involves 1, not :AlAriPr8, as the reactive species. In contrast, the reaction of :AlAriPr8 with ethylene gave two products, the 1,4-dialuminacyclohexane AriPr8Al(C2H4)2AlAriPr8 (2) and the aluminacyclopentane AriPr8Al(C4H8) (3), that can both form from the aluminacyclopropane intermediate AriPr8Al(C2H4). Although the [2+2+2] cycloaddition of 1 with two equivalents of ethylene was also calculated to be exergonic, it is likely to be kinetically blocked by the numerous isopropyl substituents surrounding the Al-Al bond. Attempts to fine-tune the steric bulk of the terphenyl ligand to allow stronger Al-Al bonding were unsuccessful, leading to the isolation of the sodium salt of a cyclotrialuminene, Na2[AlAriPr6]3 (4), instead of AriPr6AlAlAriPr6.

All optical half adder and subtractor using single 2D photonic crystal structure

All optical half adder and subtractor using single 2D photonic crystal structure

Efficient Deep-Blue Fluorescent OLEDs Based on a D-π-A Emitter Profiting From Intramolecular Hydrogen Bonds and a Hybridized Excited State.

High performance deep-blue emitters with a Commission International de l'Eclairage (CIE) coordinate of CIEy≤0.08 are highly desired in ultrahigh-definition displays. Herein, we designed and synthesized an efficient D-π-A deep-blue emitter, 2-(6-([1,1' : 3',1''-terphenyl]-5'-yl)pyridin-3-yl)-1-phenyl-1H-phenanthro[9,10-d] imidazole (mPTPH), using the synergistic effect of intramolecular hydrogen bond (H-bond) and hybridized excited state. Single-crystal structure analysis confirmed that there exist intra- and intermolecular H-bond interactions which could inhibit the structure vibration and increase photoluminescence efficiency. The photophysical and theoretical results show that mPTPH exhibited hybridized local and charge-transfer (HLCT) feature with strong deep-blue emission. Ultimately, the non-doped device based on mPTPH exhibited high maximum luminance of 20610 cd m-2. The doped device achieved high maximum external quantum efficiency of 5.4 % and small efficiency roll-off with deep-blue emission peak of 413 nm and CIE coordinate of (0.16, 0.08).

Modification of Lithium‐Rich Manganese Oxide Materials: Coating, Doping and Single Crystallization

AbstractThe increasing demand for portable electronics, electric vehicles and energy storage devices has spurred enormous research efforts to develop high‐energy‐density advanced lithium‐ion batteries (LIBs). Lithium‐rich manganese oxide (LRMO) is considered as one of the most promising cathode materials because of its high specific discharge capacity (>250 mAh g−1), low cost, and environmental friendliness, all of which are expected to propel the commercialization of lithium‐ion batteries. However, practical applications of LRMO are still limited by low coulombic efficiency, significant capacity and voltage decay, slow reaction kinetics, and poor rate performance. This review focus on recent advancements in the modification methods of LRMO materials, systematically summarizing surface coating with different physical properties (e. g., oxides, metal phosphates, metal fluorides, carbon, conductive polymers, lithium compound coatings, etc.), ion doping with different doping sites (Li sites, TM sites, O sites, etc.), and single crystal structures. Finally, the current states and issues, key challenges of the modification of LRMO are discussed, and the perspectives on the future development trend base on the viewpoint of the commercialization of LRMO are also provided.

Gradual spin crossover behavior encompasing room temperature in an iron(II) complex based on a heteroscorpionate ligand.

In this paper, we report the synthesis of six novel triazole-based heteroscorpionate ligands based on heterocycle metathesis reactions and their iron(II) complexes. Single crystal structure analyses were performed, the spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover-structural relationships were compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post-synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior at room temperature. The profile of the SCO curve can be explained by the presence of only relatively weak H bonds, spreading only in one dimension. Among the interesting spin transition behaviors observed for the different complexes, such stable, complete and gradual spin crossover at room temperature makes this neutral complex a good candidate for sublimation and future investigation as an active element notably for thermoreflectance-based surface microthermometry applications.

Dopant-Free Hole Transport Material Based on Non-Covalent Interaction for Efficient Perovskite Solar Cells.

Hole transport materials (HTMs) have a critical impact on the performance of perovskite solar cells (PSCs). Especially, the dopant-free HTMs could avoid the usage of hygroscopic dopants and reduce costs, which are important for device stability. Most of the current organic dopant-free HTMs are polycyclic aromatic hydrocarbons-based planar conjugated structures. Yet, the synthesis of conjugated fused heterocycles is often complicated. In this work, intramolecular non-covalent interaction is introduced to construct two organic HTMs (DCT and DTC), which can be facilely obtained through simple reactions. Compared to DTC with hexyl chain on the central benzene ring, DCT with hexyloxy chains shows better planarity in the core structure, as a result of the intramolecular non-covalent interactions between oxygen on hexyloxy and sulfur atom on the adjacent thiophene, as reflected from its single crystal structure. Moreover, DCT in a pristine state shows a decent hole mobility comparable to the doped Spiro-OMeTAD. Ultimately, conventional devices using dopant-free DCT as HTM show a high efficiency of 22.50%, with excellent long-term stability, and light and thermal stability. The results show that the noncovalent interaction is a useful and simple design strategy for dopant-free HTMs, that can effectively improve the efficiency and stability of PSCs.

5]Helicene Based π-Conjugated Macrocycles with Persistent Figure-Eight and Möbius Shapes: Efficient Synthesis, Chiral Resolution and Bright Circularly Polarized Luminescence.

π-Conjugated chiral shape-persistent molecular nanocarbons hold great potential as chiroptical materials, though their synthesis remains a considerable challenge. Here, we present a simple approach using Suzuki coupling of a [5]helicene building block with various aromatic units, enabling the one-pot synthesis of a series of chiral macrocycles with persistent figure-eight and Möbius shapes. Single-crystal structures of 7 compounds were solved, and 22 enantiomers were separated by preparative chiral HPLC. A notable pyrene-bridged figure-eight macrocycle, with its rigid, fully π-conjugated and overcrowded structure, exhibited pure excimer emission and outstanding circularly polarized luminescence (CPL) properties, including a large dissymmetric factor (|glum| = 3.8 × 10-2) and significant CPL brightness (BCPL = 710.5 M-1cm-1). This method provides a versatile synthetic platform for producing various chiral D2-symmetric figure-eight macrocycles and singly or triply twisted Möbius macrocycles with C2 and D3 symmetry, offering tunable chiroptical properties for CPL applications.

An analysis of the synthesis, crystal structure, optical, spectroscopic, mechanical, self-focusing, and third-order nonlinear optical properties of Kojic acid single crystals

A single, excellent crystal of Kojic acid (KA) was developed utilising the traditional approach of gradual evaporation in a solution-growing procedure. A variety of characterisation techniques were utilised to evaluate the characteristics of the crystals generated. Single crystal x-ray diffraction (SXRD) was utilised to identify the crystal structure. The crystalline arrangement of the KA crystal was confirmed using a powder x-ray diffraction (PXRD) analysis. Experiments with UV–vis spectrometers revealed that the KA crystal has a lower wavelength at which it blocks UV light but has outstanding light transmission throughout the visible spectrum. The KA single crystal has an energy band gap (Eg) of 2.5 eV. The Z-scan method was used to examine the third order susceptibility, nonlinear refraction, and nonlinear absorption coefficient of the synthesised KA crystal. The dielectric characteristics and AC conductivity were examined, with a particular emphasis on their connection to resistance at room temperature. The presence of appreciable levels of kojic acid was confirmed by energy-dispersive spectrometry. The crystal’s thermal behaviour was investigated using differential thermal analysis (DTA) and thermogravimetric (TG) methods. The nucleation parameters and controlled nucleation rate were calculated using normal theoretical research methods.

Design, Synthesis and Bioactivity Evaluation of Ag(I)-, Au(I)- and Au(III)-Quinoxaline-Wingtip N-Heterocyclic Carbene Complexes Against Antibiotic Resistant Bacterial Pathogens.

Intending to homogenize the biological activities of both quinoxaline and imidazole moieties, the proligand, 1-methyl-3-quinoxaline-imidazolium hexaflurophosphate (1.HPF6), and [Ag(1)2][PF6], (2); [Au(1)2][PF6], (3); and [Au(1)Cl3], (4) NHC complexes were synthesized. All the synthesized compounds were characterized by elemental analysis, NMR, and UV-Vis spectroscopy. Finally, single crystal X-ray structures revealed a linear geometry for complex 2 whereas a square planar geometry for complex 4. The formation of complex 3 was confirmed and supported by its MS spectra. The antibacterial activities of all the synthesized complexes were investigated against gram-positive bacteria and gram-negative bacteria. The Au(III)-NHC complex, 4 showed the highest antibacterial activity with extremely low MIC values against both the bacterial strains (0.24 μg mL-1). Monitoring of zeta potential supports the higher activity of complex 4 compared to 2 and 3. ROS production by complex 4 has also been measured in vitro in the CT26 cancer cell lines, which is directly responsible for targetting and killing the bacterial pathogens. Cell cytotoxicity assay using 293T cell lines has been performed to investigate the biocompatibility nature of complex 4. Also, an excellent hemocompatibility was assigned to it from its hemolytic studies, which provide valuable insights into the design of novel antibacterial agents.

Site differentiation strategy for selective strontium uptake and elution within an all-inorganic polyoxoniobate framework

Selective uptake and elution of trace amounts of hazardous radioactive 90Sr from large-scale high-level liquid waste (HLW) is crucial for sustainable development. Here, we propose a site differentiation strategy, based on the presence of distinct selective metal capture sites (concavity site and tweezer site) within the giant polyoxoniobate (PONb) nanoclusters of an all-inorganic PONb framework (FZU-1). Through this strategy, FZU-1 can not only effectively remove 98.9% of Sr²⁺ from simulated nuclear liquid waste, performing best among the reported Sr adsorbents, but also achieve desorption of adsorbed Sr²⁺ ions by selectively loading Na⁺ ions, thus enabling the recycling of FZU-1. Based on the well-defined single-crystal structures and theoretical studies, it can be revealed that the rapid and selective uptake of Sr²⁺ is attributed to the strong binding energy between the Sr²⁺ ions and the concavity sites. The effective elution of Sr²⁺, on the other hand, stems from the preferential binding of Na⁺ ions at the tweezer sites, elevating the cluster’s electrostatic potential and indirectly facilitating the elution of Sr²⁺ ions. The exceptional stability of FZU-1, along with its rapid and selective Sr²⁺ capture and elution capabilities, positions it as a promising candidate for large-scale nuclear waste treatment and groundwater remediation applications.

An Optically Active 4‐Aryl‐3,4‐dihydroisocoumarin‐3‐carboxylate

AbstractA four step sequence for the preparation of optically active (R,R)‐ethyl 4‐phenyl‐3,4‐dihydroisocoumarin‐3‐carboxylate is reported. In the first step the first stereocenter was installed by palladium catalyzed asymmetric conjugate addition of PhB(OH)2 to indenone (88 % ee). After deprotonation, the ester moiety was introduced with Mander's reagent. The α‐hydroxylation of the resulting β‐oxoester was then achieved with cerium‐catalysis under an air atmosphere. Key transformation was the cyanide‐catalyzed ring transformation of α‐hydroxy‐β‐oxoester furnishing the δ‐lactone moiety of the target compound, which was formed as a mixture of separable cis‐ and trans‐diastereoisomers, both with 88 % ee. The cis‐isomer could be epimerized to the trans‐compound. The relative trans and the absolute (R,R)‐configuration of the target compound was established by X‐ray single crystal structure analysis.

A novel ultra-long carbon-chain salamo-like fluorescent chemosensor with good flexibility: Synthesis, crystal structure, Pb2+ ion recognition and mechanism exploration

A novel ultra-long carbon-chain salamo-like fluorescent chemical probe DMS containing ten methylene groups (DMS, 6,6′-dimethoxy-2,2′-[1,10-(decanedioxy)bis(nitromethyldyne)]diphenol), was synthesized based on the 3‑methoxy salicylaldehyde unit, and its single crystals were obtained. The single crystal structure for the probe DMS molecule was determined. Research has shown that the fluorescent probe DMS can achieve efficient and selective recognition of Pb2+ ions, with a binding constant Ka = 1.42 × 104 M-1. The detection limit is as low as LOD = 1.31 × 10–7 M, and quantification limit is as low as LOQ = 4.36 × 10–7 M The possible identification mechanism of the fluorescent chemosensor DMS to Pb2+ions was analyzed and studied through fluorescence titration test, nuclear magnetic changes and Job′s plot exprements, DFT calculation et al. The results indicated that the fluorescent chemosensor DMS forms a coordination compound with Pb2+through 1:1 coordination, enhancing its fluorescence and resulting in the coordinated fluorescence enhancement effect.

Application of precursor with ultra-small particle size and uniform particle distribution for ultra-high nickel single-crystal cathode materials by coprecipitation method

Ultra-high nickel single-crystal cathode materials have become the most promising for lithium-ion batteries. However, the preparation of ultra-high nickel single-crystal precursors by a continuous coprecipitation method has the disadvantages of large particle size, wide distribution, poor morphology. The extent of the inhomogeneous reactions can be more severe in single-crystal cathodes with larger particle size. Herein, the coprecipitation method with a solid concentrator was adopted, and citrate sodium was used as a complexing agent to improve the physical properties of precursors and electrochemical performance of single-crystal cathode materials. By analyzing the morphology and agglomeration mechanism of the precursor nucleuses under different pH values, it was found that hexagonal nanosheets grew along the 101 direction, and the primary particles showed thicker at pH of 11.4. The hexagonal nanosheets grew along the 001 direction, and the primary particles showed finer at pH of 12.2. The morphology and particle size uniformity of the secondary particles formed by agglomeration at these two pH values showed poor. However, hexagonal nanosheets grew synergistically along the 001 and 101 directions at pH of 11.8, so the primary particles with uniform particle size gradually agglomerated, and then the secondary particles with ultra-small particle size and uniform distribution obtained. Compared to materials prepared by the traditional continuous coprecipitation method, the precursor displays a smaller particle size(D50 = 1.8 µm), higher sphericity, uniformity and denser internal structure. In order to evaluate the performance of Ni0.94Co0.04Mn0.02(OH)2 with ultra-small particle size, the sintering conditions of LiNi0.94Co0.04Mn0.02O2 need to be explored. It was found that the LiNi0.94Co0.04Mn0.02O2 cathode material prepared at 790 °C exhibited higher discharge capacity, cycle and rate performance, compared to materials prepared at 760 °C and 820 °C. We further utilized TEM, EPMA, and XPS to test the internal structure and valence state of LiNi0.94Co0.04Mn0.02O2 cathode material. The results show that the LiNi0.94Co0.04Mn0.02O2 calcined at 790 °C has a good single crystal structure. The LiNi0.94Co0.04Mn0.02O2 cathode materials inherited the structure and particle size of Ni0.94Co0.04Mn0.02(OH)2 precursors, and displayed discharge capacity of 194.7 mAh/g and capacity retention rate of 89.8 % after 100 cycles at 1 C. The microstructure and phase transition of the as-prepared cathode material are well-maintained after long-term cycling, without obvious inter-crystalline micro-crack. The results indicate that its electrochemical performance is better than that of cathode materials with precursors prepared by a continuous coprecipitation method. This work provides new insights for the preparation of small-particle-size precursor and single-crystal cathode materials.

Room temperature phase transition and luminescence behavior of a novel metal‐free ionic crystal [C7H16NO][ClO4

Metal‐free ionic crystals have attracted tremendous attention for their environmental friendliness, biocompatibility, easy fabrication and structural variability. Herein, a metal‐free ionic crystal [C7H16NO][ClO4] ([C7H16NO] = 1‐methyl‐4‐piperidinemethanol) with a dielectric transition at room temperature was designed and constructed. Differential scanning calorimetry (DSC) proved that there exists a reversible phase transition near room temperature at 304 K, accompanied with switchable dielectric behaviors between the low and high dielectric states. The single crystal structure show that the mechanism of such structural phase transition mainly results from the dynamic motion of perchlorate anions. The compound is further shown to exhibit remarkable luminescent properties, characterized by a prolonged lifetime of 18.6 ns. This work offers valuable insights into the construction of room temperature phase‐transition ionic crystals involved with dielectric switching and blue luminescence properties.

Tunable Coassembly of Octaarginine with Thiazolyl Benzenesulfonamides Exerts Variable Antibacterial Activity.

The cationic peptide octaarginine (R8) is a prominent cell-penetrating peptide and has been extensively researched as a carrier of diverse cell-destined cargo. In this work, we describe the coassembly of R8 with small molecule thiazolyl benzenesulfonamide (TBS) derivatives. Physical complexation of R8 with three TBS derivatives across a range of weight ratios results in the formation of a distinctive set of nano- and microstructures. A detailed structural characterization of the R8:TBS-derivative coassemblies has been performed by a combination of FTIR, XRD, SEM, and DSC. The major functional groups that facilitate coassembly include sulfonamide SO2 and NH groups of the TBS derivatives, and the guanidinium of R8, via a combination of cation-π and hydrogen-bonding interactions. The R8:4F-TBS coassembly displays singular topological features compared to R8:4Br-TBS and R8:4CH3-TBS complexes. These differences are attributed to the changes in the preferred orientation of the guanidino groups of R8 with respect to the π-surface of TBS derivatives. The modulation of forces of interaction across the R8:TBS-derivative coassemblies aligns with their respective thermal stabilities. The single-crystal structure of bare 4F-TBS has been subjected to Hirshfeld and 2D fingerprinting analysis and indicates notable variations from the crystal packing of the R8:4F-TBS coassembly. The structural differences among the R8:TBS-derivative coassemblies correlate with distinctive profiles of antibacterial activity in each case. The coassembled structures exert a variable extent of bacterial membrane disruption and damage based on the unique disposition of R8 and the potency of small molecule in each case. The aqueous suspension of R8:4F-TBS displays significant outer membrane disruption and bacterial killing compared with the other complexes. This work successfully demonstrates the hitherto unreported potential for coassembly of cell-penetrating peptides with other entities. The coassembly of R8 with small molecules highlights an attractive strategy for tuning the functional properties of each component.

Group VA Aromatic Thiosemicarbazone Complexes: Synthesis, Characterization, Biological Activity, and Topological Studies.

The antiproliferative and antibacterial activities of thiosemicarbazones increase markedly with the presence of metal ions. One of the factors determining the activity of metal thiosemicarbazone complexes is the coordination structure. In this study, the biological effects of new antimony (III) and bismuth (III) thiosemicarbazone complexes with different binding modes and geometrical structures were demonstrated. Three new complexes, with the formulae {[SbCl3(µ2-S-Hacptsc)(η1-S-Hacptsc)], 2/3H2O,1/3CH2Cl2}, {[SbCl3(κ2-S,N-Hacpmtsc)(η1-S-Hacpmtsc)2CH2Cl2]}, and{[BiCl3(η1-S-Hbzmtsc)3]·C2H5OH}, where Hacptsc: acetophenone thiosemicarbazone, Hacpmtsc: acetophenone-N-methyl thiosemicarbazone, Hbzmtsc: benzaldehyde-N-methyl thiosemicarbazone) were elucidated by different methods and deeply analyzed in accordance with their structure by X-ray structure analysis and Atoms-In-Molecules topological analysis. This analysis provided a deeper understanding of the coordination spheres of the Sb/Bi complexes. For instance, the first reported two binding modes of the same ligand are observed in a single crystal structure of antimony (III) halide complexes. Additionally, in one of the complexes, a solid-to-solid phase transition was detected and analyzed in detail. Those complexes, very unique in terms of their geometry, have also been tested for their in vitro cytotoxic activity against human adenocarcinoma cervical cancer (HeLa) cells, whereas antimony (III) complex 1is the most active complex of this study. Further, the antibacterial activity of the complexes has been screened against two Gram-negative (Pseudomonas aeruginosa and Escherichia coli) and two Gram-positive (Staphylococcus epidermidis and Staphylococcus aureus) pathogenic bacteria. From the results, it is found that all the complexes exhibited significant activity against the Gram-negative pathogenic bacteria.