ChemPlusChem

Research and Industry for Human Health Enabled by Detergent Chemistry
Urner LH
Research and applications relevant to human health are enabled by detergent chemistry. A multifaceted overview of this field is yet missing. To close this gap, this topical collection provides an overview of recent advances in detergent chemistry covering progress in synthesis, supramolecular characterization, and application. Our collection shows that detergent chemists operate usually interdisciplinary. Connecting molecular structures of detergents with properties relevant to applications is at the center of scientific exploitation. Detergent chemists deliver solutions to research and industry that aim at securing well-being, hygiene, and new pharmaceuticals.
Evaluating the Role of Calcium Ions in the Removal of Nanoplastics ( ̴607 nm) by Flocculation-Enhanced Sedimentation using Alginate
Bastrzyk A, Gołębiowska K, Wołoszyn J, Mendrek B, Celny A, Kowalczuk A and Grządka E
The removal of nanoplastics (NPs) from aquatic environments remains a significant challenge due to their persistence and potential ecological risks. Flocculation, together with coagulation and sedimentation, is widely used as a phase-separation technique in industrial water treatment. In this study, alginate (ALG)-enhanced sedimentation of polystyrene (PS) NPs under varying CaCl concentrations was investigated via turbidimetric analysis. The destabilization mechanism was assessed through floc morphology, zeta potential measurements, attenuated total reflectance-Fourier transform infrared spectra, and scanning electron microscope/energy-dispersive X-ray spectroscopy analysis. The rheological properties of ALG solutions in the presence of CaCl were expressed as complex viscosity. To better simulate environmentally relevant conditions, we employed a novel PS-NP dispersion without commercial stabilizers. The results show that ALG effectively destabilizes the system at moderate and high coagulant ionic strengths, with an optimal dosage of 10 ppm ALG. Calcium ions can interact with ALG chains through the formation of intermolecular complexes. At the highest CaCl concentration, changes in the system's rheological properties altered floc morphology and delayed sedimentation. This study highlights the potential of natural bioflocculants such as ALG for removing PS-NPs from calcium-rich waters and reducing reliance on synthetic coagulants.
Synthesis and Luminescent Properties of Trifluoromethyl-Functionalized Biscyclometalated Gold(III) Complexes
Verma S, Neimann B, Mylvaganam K and Venkatesan K
Gold(III) complexes have gained prominence as photofunctional materials due to their tunable photophysical properties and potential in advanced optoelectronic applications. While traditionally gold(III) complexes have been known to exhibit phosphorescence emission, recent advancements have revealed that gold(III) complexes can also display thermally activated delayed fluorescence (TADF), enabling near-unity internal quantum efficiencies and full exciton utilization. However, gold(III) biscyclometalated complexes incorporating trifluoromethyl groups and displaying TADF-type emission have been lacking. We report biscyclometalated gold(III) C^N^C complexes incorporating electron-withdrawing trifluoromethyl (CF) groups with TADF-type emission. Both aryl and alkynyl ligands were employed to investigate the balance between structural stability and donor-acceptor spatial separation. Detailed photophysical studies reveal TADF-type emission behavior in these complexes with quantum yields as high as 70% in solution with high radiative rates in the order of 10 s. These complexes exhibit promising photophysical properties suitable for high-efficiency organic light-emitting diode applications, providing valuable design strategies for next-generation TADF emitters based on gold(III) scaffolds.
Electroactive Copper-Cyanurate Coordination Polymer for Thiosulfate Monitoring in Biological Fluids
Subhan M, Naeem MM, Farhan M, Atta S, Shakir I and Afzal A
The precise and noninvasive detection of thiosulfate, an essential antidote for cyanide poisoning, is critical for both clinical toxicology and environmental monitoring. In this work, the development of an electroactive copper-cyanurate (Cu-CYA) coordination polymer, engineered as a highly sensitive and selective electrochemical sensor for thiosulfate detection in biological fluids, is reported. The sensor material is synthesized via a straightforward coordination-driven self-assembly process, yielding a porous framework with abundant active sites, excellent redox properties, and superior electron transfer capability. Comprehensive physicochemical characterization confirms the structural integrity and favorable interfacial kinetics of the Cu-CYA/graphite pencil electrode (GPE) sensor. Cyclic voltammetry and differential pulse voltammetry analyses reveal a robust and linear response to thiosulfate concentrations ranging from 100 to 500 nM, with a remarkable sensitivity of 2.94 µA cm nM and an exceptionally low limit of detection of 0.32 nM. The sensor exhibits high selectivity against potential interferents and maintains 93.3% of its initial response after 30 days, underscoring its long-term functional reliability. Notably, real sample analysis using human saliva demonstrates a mean recovery of 97.5%, validating the sensor's practical applicability in complex biological matrices. This study establishes Cu-CYA as a powerful electrochemical sensing platform for thiosulfate monitoring, offering new prospects for portable diagnostics in healthcare and environmental safety.
High-Entropy Alloy Nano-Aggregates Enable Durable and High-Efficiency Oxygen Reduction Reaction
Chen J, Wu Z, Cao G, Yang G, Zhang Q, Liu Z and Peng F
High-entropy alloys (HEAs) have emerged as exceptional electrocatalysts due to their unique structural and electronic properties. In this work, we synthesized PtRhPdIrRu HEA nanoaggregates by precisely controlling the zeta potential during synthesis. The resulting catalyst demonstrated superior oxygen reduction reaction (ORR) activity in both acidic and alkaline electrolytes, outperforming commercial Pt/C. Remarkably, the HEA nanoaggregates exhibited outstanding stability, retaining half-wave potentials (E/) of 0.851 V after 13,000 cycles in acidic media and 0.864 V after 30,000 cycles in alkaline media. These results highlight the exceptional electrocatalytic performance and durability of HEA nanoaggregates, making them highly promising candidates for next-generation ORR catalysts.
Multianalytical Study of Amuletic and Talismanic Islamic-African Paper Manuscripts in the Slovene Ethnographic Museum
Elnaggar A, Mahgoub H, Maestro-Guijarro L, Crespo Ibáñez A, María Carmona-Quiroga P, Sánchez-Cortés S, Rehar Ž, Kos G, Ameen A, Frelih M, Strlič M, Oujja M and Castillejo M
In contrast to its European counterpart, Islamic papermaking is still little researched, especially in scientific and conservation contexts. This study presents the first in-depth material analysis of a unique collection of Islamic-African amulets and talismans from the nineteenth and twentieth centuries, held at the Slovene Ethnographic Museum. This research employed a multi-analytical approach that included pH measurements, analysis of fibrous materials, iodine test for the presence of starch, hyperspectral imaging (HSI), FTIR-ATR, Raman spectroscopy, laser-induced fluorescence (LIF), and laser-induced breakdown spectroscopy (LIBS), as well as cultural interpretations. Twelve selected manuscripts were examined to characterize paper, inks, dyes, and calligraphic features. The results showed the use of iron gall inks, plant-based dyes, and mixed paper fibers (straw and softwood pulp), suggesting a mixture of local and imported materials from the colonial period. The calligraphic and decorative styles reflect a synthesis of orthodox Qur'an and local West African Sufi traditions, often incorporating protective texts, magic squares, and regional variants of Kufic script. The findings shed light on technological aspects of Islamic manuscript production in West Africa and support the informed conservation, display, and interpretation of these culturally and spiritually significant objects. This research sets a precedent for comparative heritage studies and enhances the understanding of Islamic material culture in African contexts.
Photoinduced Formation of BODIPY Radical Cation in Meso-Methyl-BODIPY Photocage: Direct Evidence with Chemically Induced Dynamic Nuclear Polarization Technique
Polyakov N, Panfilov M, Komarovskikh A, Osik N, Moskalensky A, Vorob'ev A and Selyutina O
Light-responsive molecules that can release drugs upon light absorption have attracted significant interest in chemistry and biology. BODIPY-based photoremovable protecting groups, or photocages, have recently emerged as especially promising tools in this respect. However, the exact photorelease mechanism is still not fully understood. We study the photochemical decomposition of meso-Methyl-BODIPY-conjugated epinephrine using 1H nuclear magnetic resonance and chemically induced dynamic nuclear polarization (CIDNP) techniques. After irradiation, epinephrine was detected only in trace amounts, whereas its oxidation product, adrenochrome, was the predominant product. Surprisingly, the CIDNP study has shown that the electron transfer (ET) in this reaction does not proceed from epinephrine to the BODIPY moiety, but rather occurs between two BODIPY cores. To validate this hypothesis, we applied the CIDNP method to detect photoinduced ET between two model BODIPY molecules in solution. In addition, the radical cation of BODIPY has been detected for the first time by CIDNP under photolysis in the presence of the electron acceptor-chloranil. The hyperfine interaction (HFI) constants of the BODIPY radical cation were estimated from the CIDNP spectrum, and they are in agreement with the HFI constant predicted by density functional theory calculations. Due to high enhancement coefficients, the CIDNP technique allows for to detection of polarized BODIPY products at very low concentrations.
Multi-Peak Redox Strategy for Ultrasensitive Adsorptive Stripping Voltammetric Detection of 5-Hydroxyindole Acetic Acid on a Thermally Oxidized Graphite Felt
Liu S, Wang L, Wang Z, Meng J, Liu T, Hou Y, Guo H and Jiang H
The precise determination of 5-hydroxyindole acetic acid (5-HIAA), an essential biomarker for neuroendocrine tumors and neurological diseases, is of paramount importance. Herein, we develop a sensitive electrochemical sensor based on an oxidized graphite felt (OGF) electrode, functionalized with oxygen-containing groups via facile thermal oxidation. The synergistic integration of these moieties with the inherent 3D porous structure facilitates hydrogen-bonding interactions, enabling efficient capture of a crucial oxidative intermediate of 5-HIAA: its cationic free radical. This unique molecular recognition mechanism generates a distinctive six-peak voltammetric signature in cyclic voltammetry, providing deeper insights into the complex oxidation pathway of 5-HIAA. Utilizing adsorptive stripping square wave voltammetry, the OGF sensor achieves a wide linear range of 0.35-26.5 μmol/L and a low limit of detection of 0.094 μmol/L (S/N = 3). The enhanced analytical performance is directly linked to the superior intermediate-trapping capability of OGF, highlighting its potential for reliable biosensing applications.
Bioderived Reduced Graphene Oxide from Sterculia foetida for Efficient Adsorptive Dye Removal and Electrochemical Characterization
Shamil O M, Safeer Naduvil Kovilakath M, Yoosuf S, Tharayil SB, Shibile M, Ashraf M T S, Maharoof M, M Muhammed N, P P and V S
Pervasive use of dyes in industries leads to contamination of water, which results in potential hazards to humans and the environment. In contrast to photodegradation method, adsorption-based dye removal is considered an efficient and cost-effective way with no secondary environmental hazardous by-product. In the present study, environmentally benign method was used for preparation of reduced graphene oxide (rGO), an efficient adsorbent. A low-cost and facile method starting from biochar of Sterculia foetida was used for obtaining rGO nanosheet. Morphological, vibrational and structural transformation suggest possible transformation of biochar to rGO. Adsorption capacity studies of rGO using methylene blue (MB) reveal that rGO is a promising adsorbent. 0.2 mg mL of rGO marks 94.04% dye removal of 2.5 ppm MB solution. It follows pseudo-second-order kinetics depicting both physisorption and chemisorption. Further studies were also performed to investigate the electrochemical behavior of rGO for supercapacitor applications. The double-layer capacitance obtained for rGO (2.08 × 10 mF cm) is ∼1.5 times higher as compared to that of bare glassy carbon electrode (GCE: 1.37 × 10 mF cm). The higher adsorption of ions is the main reason for the enhanced double-layer capacitance of rGO.
Mechanochemistry: A Transformative Technique for the Synthesis of Polar Organometallics from Zero-Valent Metals
Nallaparaju JV, Aav R and Kananovich D
The generation and synthetic applications of polar organometallic reagents have traditionally relied on organic solvents. Recently, mechanochemistry has emerged as a conceptually new approach in the field, using mechanical forces for the activation of bulk zero-valent metals and enabling a solvent-free or solvent-minimized synthesis of polar organometallics. This transformative approach brings several advantages over traditional methods, such as eliminating the need for strictly anhydrous conditions and inert atmospheres, removing solvent compatibility issues, and improving the reactivity profiles of polar organometallic reagents, thereby addressing long-standing challenges in the field. This concept article brings into focus the key developments in the mechanochemical generation of polar organometallics (derivatives of zinc, magnesium, calcium, barium, and lithium), highlighting the main advantages of this approach and emphasizing the current challenges.
Charge Transfer Complexes of Thienyl-Substituted Diazadiphosphapentalenes with 1,2,4,5-Tetracyanobenzene: Synthesis, Structure, and Photoconductivity
Grishin M, Sushev V, Zolotareva N, Khristolyubova A, Rumyantcev R, Fukin G, Luk'yanov A, Travkin V, Nazarov A and Kornev A
3a, 6a-Diaza-1,4-diphosphapentalenes (RR'DDP) containing thienyl and alkyl peripheral substituents were synthesized (R, R' = {(5-ethylthienyl-2), Me} (6), {(thienyl-2), n-Bu} (7)). Interaction of 1,2,4,5-tetracyanobenzene (TCNB) with DDP 6 in any stoichiometry produces sandwich complex of the composition DDP-TCNB-DDP. Estimation of the HOMO-LUMO gap from the onset of optical absorption gives value of 1.34 eV. The study of the electron density topology showed that each TCNB molecule is an acceptor of 0.44e in the crystal while each DDP molecule in stack is charged + 0.22e. The energy of intermolecular interactions between the donor and acceptor molecules is 8.2 kcal/mol. We demonstrate for the first time the photoconductivity of a representative of a new class of charge-transfer complexes based on diazadiphosphapentalenes. Electrical measurements of single crystals of the (RR'DDP)/TCNB complex (R, R' = {(thienyl-2), Me} showed that the photocurrent under 1 Sun-irradiation is close to 1.5 nA, and the photosensitivity reaches 70. Complexation of TCNB with diazadiphosphapentalene 7 containing n-butyl peripheral substituents does not result in the formation of a stable complex. Analysis of ten representatives of diazadiphosphapentalenes showed that steric effects and the flexibility of peripheral substituents play a decisive role in complexation with TCNB.
CF-Driven Regioselectivity in C Hydrogenation
Malkin NA, Brotsman VA, Lukonina NS, Belov NM, Eliseev AA and Goryunkov AA
We report the theoretical modeling of the reductive hydrogenation of [6,6]-closed, [6,6]-open, and near-equatorial [5,6]-open C(CF)-I-III as well as the regioselective synthesis of three novel C(CF)H isomers I-III, their spectral characterization using mass spectrometry, UV/Vis, FTIR, Raman, and NMR spectroscopy. We have shown that regardless of the configuration of CF moiety and its position at the fullerene cage, the bridgehead carbon atoms are activated in the anionic state and undergone protonation in the presence of water. The regioselectivity of the formation of C(CF)H isomers, as well as unexpected features of suppression of the C hydrogenation in the presence of C(CF), and the high reactivity of near-equatorial [5,6]-open C(CF) to polyhydrogenation are discussed from kinetic and thermodynamic aspects.
On the Photophysics and Contrasting Cavitand Binding of a Fluorescent Amphiphilic Benzothiazole
Bera A, Ketkar RN, Sadhukhan N and Dutta Choudhury S
Benzothiazoles, including the cationic thioflavin T and its variants, are of immense interest because of their therapeutic potential and applications as biomolecular fluorescence probes. This study investigates the photophysics of an interesting benzothiazole derivative, TEG-BTA-2, that combines a neutral thioflavin T type of moiety (BTA-2) with a tetraethylene glycol chain (TEG). Unlike thioflavin T, TEG-BTA-2 is highly fluorescent and shows multiple prototropic transformations. Monoprotonated TEG-BTA-2 is found to exist in two isomeric forms, each having characteristic absorption, emission, and fluorescence lifetimes. Furthermore, TEG-BTA-2 shows strong affinity toward the cavitands α-, β-, and γ-cyclodextrins (CDs). The binding constants of TEG-BTA-2 with the cavitands are considerably higher than that of thioflavin T, which is attributed to its neutral charge and favorable hydrophobic/H-bonding interactions provided by the TEG chain. Interestingly, it is found that the size of the macrocyclic cavity plays a pivotal role in controlling the fluorescence response of TEG-BTA-2 due to formation of complexes with different stoichiometries. In contrast to the fluorescence enhancement observed with αCD and βCD, the interaction of TEG-BTA-2 with γCD leads to fluorescence quenching. These results provide valuable insights for development of thioflavin T-inspired benzothiazole molecules as fluorescent markers and diagnostic agents.
Thiocarbamoylimidates as Precursors of New 5-Amino-1,2,4-Triazole and Oxadiazole Derivatives In Silico Prediction of Absorption, Distribution, Metabolism, and Excretion Parameters
Gatri O, Roisnel T, Cordier M, Dorcet V, Efrit ML and Fischmeister C
A series of 23 heterocyclic derivatives incorporating 1,2,4-triazole and oxadiazole motifs are synthesized via cyclization of thiocarbamoylimidates with hydrazine salts. Reaction parameters including solvent, base, and temperature are systematically optimized and very good results are obtained in the environmentally friendly reaction media composed of water and ethanol, under mild conditions of temperature (40 °C). The reaction is very versatile and allows for the introduction of a wide variety of functional groups. All the new compounds are submitted to in silico evaluation of their drug potential using the SWISS-ADME tool. Several compounds of both families did not violate any drug likeness rules, making them potential candidates for further evaluation of their biological activity and structural optimization.
A pH-Responsive Synthetic Receptor for Switchable Binding of Carbohydrates
Milanesi F, Corti G, Baldi A, Roelens S and Francesconi O
Stimuli-responsive, water-soluble synthetic receptors are key to advancing dynamic molecular recognition in aqueous environments, with implications for self-assembly, molecular machines, and biomedical systems. Herein, a macrocyclic receptor is reported that exhibits pH-dependent binding properties toward saccharides in water, in that it displays markedly different affinities between alkaline and neutral conditions. Spectroscopic and binding studies reveal that the degree of protonation of the solubilizing groups modulates the receptor self-association phenomena, together with concomitant substantial loss of binding ability. This work highlights a rare example of a pH-switchable carbohydrate receptor operating in water and underscores the potentials of such system in the design of smart, responsive molecular architectures.
Via Performance to Degradation: Oxidation Mechanism of Biodegradable Polyalphaolefin Base Oil for Electric Drive Systems
Distler E, Albrecht J, Holderied K, Güney DC, Kiefel M and Weber K
An additive-free, low-viscosity polyalphaolefin (PAO) has been oxidized under pure oxygen at elevated pressure and temperature. This biodegradable PAO base oil is a promising candidate for use as a motor-gear lubricant in electrical drive systems. The oxidation behavior is systematically investigated to evaluate its thermal stability and long-term performance. Rheological measurements are performed to assess viscosity, water content is quantified, tribological tests determine the coefficient of friction, and Fourier-transform infrared spectroscopy is used to monitor chemical changes during oxidation. All analytical methods consistently revealed a two-step oxidative degradation process. It is proposed that the first stage involves the formation of carbonyl compounds and water without compromising lubrication properties, while the second stage-triggered by hydrolysis of oxidation products-leads to chain scission and initiates the desired degradation. This two-stage mechanism is discussed in the context of technological functionality and sustainability requirements for next-generation electric drive lubricants.
Machine Learning Approaches in Soft Matter Molecular Simulation and Materials Characterization: Challenges and Perspectives
Vergadou N and Constantoudis V
Machine learning (ML) techniques are currently investigated for their potential applicability in a wide range of disciplines and scientific domains as a powerful extension to existing state-of-the-art experimental and computational methods. The diverse scientific areas within the materials science field can largely benefit from the development of data-driven methods in the present era of advanced ML computational algorithms, efficient, and optimized hardware and large amounts of produced information. In this perspective, basic concepts are introduced and representative advances are showcased from the standpoint of materials characterization and soft matter molecular simulation. Prerequisites and challenges are discussed toward the construction of sound and efficient ML-aided approaches that can contribute via new auxiliary routes to fundamental understanding and thus facilitate scientific discovery and technological applications.
Blue and Second Near-Infrared Transmissive Electrochromic Polymers based on ProDOT and Triphenylamine Derivatives
Jiang J, Ma F, Ming S, Zhen S, Lin K and Li M
Electrochromic materials have recently aroused extreme attention due to their exceptional application potential in display screens, architectural glass, and coating stealth materials, etc. Developing electrochromic polymers synchronously sharing blue and second near-infrared (NIR-II) transmissive is urgently in demand but extremely scarce. Herein, three kinds of electrochromic polymers featuring redox electrochemical and electrochromic properties are obtained through electrochemical polymerization of three monomers, ProDOT-TPA, ProDOT-TPPA, and ProDOT-2TPA, which are constructed based on 3,4-ethylenedioxythiophene (ProDOT) and triphenylamine (TPA) derivatives. Electrochemical studies reveal that ProDOT-TPA exhibits low initial oxidation potential of 0.59 V, possessing significant advantages for obtaining high-quality polymers. The optimized polymers [P(ProDOT-TPA)] show significant properties in electrochromic devices with optical contrast of 14.38% at 400 nm and 49.55% at 1100 nm, along with coloration efficiency of 123 cmC and response times of 0.5 s.
Recent Advances in the Stereoselective Polymerization of Epoxides and Applications of Stereocontrolled Polyethers
Borst T and Naumann S
The stereoselective polymerization of racemic epoxides represents an increasingly powerful route to materials with tailored properties. Progress in this field is closely connected to advanced catalyst design and a growing understanding of polymerization mechanisms. This review briefly summarizes the historical development of the field and then focuses on research covering the past 10 years. Polyethers, already widely employed both for the mass market and for highly specialized applications, can be expected to gain further functionality and applicability based on these advances. A succinct final chapter provides an outlook, highlighting where stereocontrolled polyethers, in particular isotactic polymers, have already found fruitful application.
Continuous Flow Catalytic Reductive Amination of Carbonyl Compounds to Primary Amines with Carbon-Coated Co@CS Catalyst under Mild Conditions
Mi S, Lei Y, Liu J and Pyo SH
Reductive amination is crucial for synthesizing amines in pharmaceutical and industry, yet selectively producing primary amines on a large scale remains challenging. This work presents a continuous-flow reductive amination process using benzaldehyde with NH and H as the nitrogen sources and reductant. A cobalt catalyst supported on nitrogen-doped carbon derived from chitosan (Co@CS) was developed. After optimization, a primary amine yield exceeding 99% was achieved under mild reaction conditions. The catalyst demonstrated excellent stability in long-term tests and with various substrates, including the biomass lignin-derived vanillin. Compared to batch reactors, theflow reactor provided superior selectivity. This catalytic flow process minimizes waste, enhances atom economy, avoids hazardous chemical, and improves energy efficiency. The use of a renewable chitosan feedstock and a safer process aligns with multiple principles of green chemistry. The exceptional heat and mass transfer in the Flow system offers an effective strategy for the large-scale production of primary amines from biomass platform compounds.
Metal Meets Nucleobase: A Cd(II)-Adenine Complex with Bridging Supramolecular Architectures and Antibacterial Activity
Nath S, Sen T, Deb VK, Shahnowaz T, Mukherjee S, Kaminsky W, Roy S, Shukla R and Adhikari S
A mononuclear Cd(II) complex, [Cd(9BuA)(HO)(DMF)NO]NO (1) derived from 9-butyladenine (9BuA) has been synthesized and characterized using elemental analysis, Fourier transform infrared H NMR, and single-crystal X-ray diffraction analysis. Crystallographic analysis reveals a distorted octahedral coordination environment around the Cd(II) center, where two 9BuA ligands, two water molecules, a DMF molecule, and a nitrate ion coordinate through N and O atoms. The complex exists as a monocation stabilized by an additional noncoordinated nitrate counterion. Hirshfeld surface analysis and electrostatic potential mapping highlight the dominance of hydrogen-bonding interactions (CH…O, NH…O, OH…O, etc.), which collectively stabilize the 3D crystal packing. Energy framework analysis identifies 18 dimeric interactions, with the most stable dimers stabilized by strong Coulombic forces, resulting in total interaction energies between -145.3 and -376.3 kJ mol. The photophysical investigation shows chelation-enhanced fluorescence due to ligand rigidification upon coordination. In vitro antibacterial assays of complex 1 against six bacterial strains-three Gram-positive (Mammaliicoccus lentus, Staphylococcus cohnii, Bacillus cereus) and three Gram-negative (Enterobacter cloacae, Klebsiella pneumoniae, Shigella sonnei)-reveal selective and potent activity. To the best of current knowledge, this study presents the first structurally and biologically characterized Cd(II) complex of a modified adenine derivative, integrating detailed supramolecular and photophysical analyses with antibacterial evaluation.