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The two-dimensional (2D) chalcogenide WSe 2 /V 2 O 5 composite nanostructures were synthesized using the hydrothermal method and extensively characterized with various spectroscopic techniques. X-ray diffraction analysis confirmed the hexagonal crystal structure exhibiting space symmetry of P 6 3 / mmc . Scanning electron microscopy images provided insights into the irregular and nonuniform morphology. Optical spectrum analysis indicated a band gap value of 2.01 eV for 15% WSe 2 /V 2 O 5 nanostructures, as determined by the Wood and Tauc equation. Photoluminescence (PL) excitation spectra at emission wavelengths of 550 and 750 nm exhibited broad emission attributed to self-trapped excitons for V 2 O 5 and WSe 2 nanostructures. Under excitation at λ exc = 365 nm, PL emission spectra displayed distinct peaks at 550 and 750 nm, demonstrating the ability to emit vivid red light. A device optimized for photoresponsivity ( R ) of approximately 7.80 × 10 -1 A W -1 and detectivity ( D ) of around 8.65 × 10 11 Jones, and quantum efficiency of approximately 3.42 × 10 -2 A W -1 were achieved at a wavelength of 390 nm while using a lamination sheet as a substrate. These findings underscore the capability of devices for efficient photoconversion at specified wavelengths, indicating potential applications in sensing, imaging, and optical communication. The photoresponsivity of the device remained stable at 3.38 × 10 -3 A W -1 at 0° and 3.09 × 10 -3 A W -1 at 55° bending angle. This indicates the resilience of device to mechanical strain, making it ideal for flexible and wearable sensor applications. The structural, morphological, and optical characterizations confirm the suitability of luminescent WSe 2 /V 2 O 5 chalcogenide for practical optoelectronic applications, especially in display technologies.

Separating xylene isomers is a challenging task due to their similar physical and chemical properties. In this study, we developed a molecular sieve incorporating a reduced graphene oxide (rGO) membrane for the precise differentiation of xylene isomers. We fabricated GO membranes using a vacuum filtration technique followed by thermal-induced reduction to produce rGO membranes with precisely controllable interlayer spacing. Notably, we could finely tune the interlayer spacing of the rGO membrane from 8.0 to 5.0 Å by simply varying the thermal reduction temperature. We investigated the reverse osmosis separation ability of the rGO membranes for xylene isomers and found that the rGO membrane with an interlayer spacing of 6.1 Å showed a high single component permeance of 0.17 and 0.04 L m -2 h -1 bar -1 for para- and ortho -xylene, respectively, exhibiting clear permselectivity. The separation factor reached 3.4 and 2.8 when 90:10 and 50:50 feed mixtures were used, respectively, with permeance 1 order of magnitude higher than that of current state-of-the-art reverse osmosis membranes. Additionally, the membrane showed negligible permeance and selectivity decay even after continuous operation for more than 5 days, suggesting commendable membrane resistance to solvent swelling and operating pressure.

Prostate-specific antigen (PSA) is a key marker for a prostate cancer diagnosis. The low sensitivity of traditional lateral flow immunoassay (LFIA) methods makes them unsuitable for point-of-care testing. Herein, we designed a nanozyme by in situ growth of Prussian blue (PB) within the pores of dendritic mesoporous silica (DMSN). The PB was forcibly dispersed into the pores of DMSN, leading to an increase in exposed active sites. Consequently, the atom utilization is enhanced, resulting in superior peroxidase (POD)-like activity compared to that of cubic PB. Antibody-modified DMSN@PB nanozymes serve as immunological probes in an enzymatic-enhanced colorimetric and photothermal dual-signal LFIA for PSA detection. After systematic optimization, the LFIA based on DMSN@PB successfully achieves a 4-fold amplification of the colorimetric signal within 7 min through catalytic oxidation of the chromogenic substrate by POD-like activity. Moreover, DMSN@PB exhibits an excellent photothermal conversion ability under 808 nm laser irradiation. Accordingly, photothermal signals are introduced to improve the anti-interference ability and sensitivity of LFIA, exhibiting a wide linear range (1-40 ng mL -1 ) and a low PSA detection limit (0.202 ng mL -1 ), which satisfies the early detection level of prostate cancer. This research provides a more accurate and reliable visualization analysis methodology for the early diagnosis of prostate cancer.

Oral ingestion of probiotics is a promising approach to relieving inflammatory disease through regulating the gut microbiota. A newly discovered strain, Lactobacillus rhamnosus CY12 (LCY12), obtained from cattle-yak milk, displayed numerous probiotic properties. These included enhanced viability in low pH and bile environments, adhesion capabilities, and potent antimicrobial effects. The research aimed to explore the beneficial impacts of the novel LCY12 strain on colitis in mice induced by dextran sulfate sodium (DSS) and to elucidate the underlying molecular mechanisms. The results of the study showed that administration of LCY12 effectively helped to reduce the negative effects of DSS-induced body weight loss, disease activity index score, colon length shortening, loss of goblet cells, and overall histopathological scores in the intestines. Simultaneously, LCY12 administration significantly alleviated intestinal inflammation and safeguarded intestinal barrier integrity by enhancing IL-10 levels, while dampening IL-6, IL-1β, and TNF-α production. Additionally, LCY12 boosted the presence of tight junction proteins. Furthermore, LCY12 hindered the TLR4/MyD88/NF-κB signaling pathway by downregulating TLR4 and MyD88 expression, inactivating phosphorylated IκBα, and preventing translocation of NF-κB p65 from the cytoplasm to the nucleus. The LCY12 also increased specific intestinal microbial communities and short-chain fatty acid (SCFA) production. Altogether, LCY12 oral administration alleviated colitis induced with DSS in mice by improving intestinal barrier function and regulating inflammatory cytokines, SCFA production, and intestinal microbiota.

In the present study, a series of benzotriazole-based β-amino alcohols were efficiently synthesized in excellent yields via aminolysis of benzotriazolated epoxides under catalyst- and solvent-free conditions. Further these β-amino alcohols were successfully utilized to synthesize the corresponding benzotriazole-based oxazolidine heterocyclic derivatives. All the synthesized compounds were characterized by various spectroscopic techniques such as 1 H NMR, 13 C NMR, and mass spectroscopy for structure elucidation. The compounds were subjected to a microtiter plate-based antimicrobial assay. The antimicrobial activity results reveal that the compounds 4a , 4e , and 5f were found to be active against Staphylococcus aureus (ATCC-25923) with minimum inhibitory concentrations (MICs) of 32, 8, and 64 μM, respectively. Also, the compounds 4a , 4e , 4k , 4i , 4m , 4n , 4o , 5d , 5e , 5f , 5g , and 5h showed effective activity against Bacillus subtilis (ATCC 6633) with MICs of 64, 16, 16, 16, 64, 16, 64, 64, 32, 64, 8, and 16 μM, respectively. A biological investigation was conducted, including molecular docking of two compounds with several receptors to identify and confirm the best ligand-protein interactions. Hence, this study found a significant strategy to diversify the chemical molecules. The synthesized compounds play a potential role as an antibacterial intensifier against some pathogenic bacteria for the development of antibacterial substances., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The primary objective of this research was to identify and explore the most potent and efficacious cyclooxygenase inhibitors, utilizing indole acetic acid drugs as a lead molecule. To achieve this objective, various derivatives ( 2a-2c and 2e-2g ) of the selected lead molecule, indomethacin, were synthesized using a reflux condensation process, targeting the hydroxyl group. The synthesized analogues were subjected to different spectroscopic procedures to determine their structure and confirm their analogues. These derivatives were further screened for acute toxicity and anti-nociceptive and anti-inflammatory activity using established protocols. Docking analysis was performed to evaluate the possible protein-ligand interaction. The test compounds were found to be safe at doses of 50, 75, 100, and 200 mg/kg, i.p. The pharmacological screening revealed that test compounds 2a-2f had a superior peripheral analgesic effect at a dose of 10 mg/kg, in comparison to the parent drug indomethacin, while compound 2g exhibited slightly lower activity at the same dose. The hot plate results showed lower central analgesic activity of the test compounds compared to the standard Tramal, but it was still significant. Anti-inflammatory results were significant, comparable to Diclofenac sodium and indomethacin, except for compounds 2b , 2c , and 2e at a dose of 10 mg/kg body weight. Molecular docking analysis demonstrated that the derived compounds had augmented negative binding energies (-149.39, -146.72, -160.85, -159.34, -140.03, and -150.91 KJ/mol) compared to the parent drugs (-141.07), which supported the research's theme of producing stronger derivatives of standard drugs with significant anti-nociceptive and anti-inflammatory potential. The derived compounds exhibited significant analgesic and anti-inflammatory activities and, therefore, have the potential to be studied further as new drug candidates for pain and inflammation., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Recent advances in bandgap engineering have increased the possibility of vacancy ordered double halide perovskites (VO-DHPs), Cs 2 SnX 6 where X = Cl, Br, I with designable optoelectronic features. Doping with La 3+ ions modulates the band gap from 3.8 to 2.7 eV, allowing a steady room temperature dual emission (PL) centered at 440 and 705 nm in Cs 2 SnCl 6 . Pristine Cs 2 SnCl 6 and La:Cs 2 SnCl 6 both have a crystalline cubic structure with a space symmetry of Fm 3 m . The cubic phase correlates well with the Rietveld refinement. SEM analysis confirms anisotropic development with huge micrometer-sized (>10 μm) truncated octahedral structures. DFT investigations show that the insertion of La 3+ ions into the crystal lattice leads to the band splitting. The present study elaborates the experimental understanding of the dual PL emission properties of La:Cs 2 SnCl 6 leaving a scope for detailed theoretical study on the origin of the complex electronic transitions involving f-orbital electrons.

High-performance concrete (HPC) is increasingly used in construction due to its superior strength and durability. However, current stress block parameters used for designing normal-strength concrete cannot be safely applied to HPC. To address this issue, new stress block parameters have been proposed through experimental works, which are used for designing HPC members. In this study, the behavior of HPC was investigated using these stress block parameters. Two-span beams made of HPC were tested under five-point bending, and an idealized stress block curve was derived from the experimental stress-strain curve for grades 60, 80, and 100 MPa. Based on the stress block curve, equations for the ultimate moment of resistance, depth of the neutral axis, limiting moment of resistance, and maximum depth of the neutral axis were proposed. An idealized load-deformation curve was also developed, which identified four significant events: first cracking, yielding of reinforced steel, crushing of concrete with spalling of cover, and ultimate failure. The predicted values were found to be in good agreement with the experimental values, and the average location of the first crack was identified to be 0.270 L, measured from the central support on either side of the span. These findings provide important insights for the design of HPC structures, contributing to the development of more resilient and durable infrastructure., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

In this research work, the mechanical properties of high-strength self-compacting concrete (HSSCC) were studied. Three mixes were selected, having compressive strengths of more than 70, 80, and 90 MPa, respectively. For these three mixes, the stress-strain characteristics were studied by casting cylinders. It was observed during the testing that the binder content and water-to-binder ratio influence the strength of HSSCC, and slow changes in stress-strain curves were seen as the strength increased. The use of HSSCC results in reduced bond cracking, leading to a more linear and steeper stress-strain curve in the ascending branches as the strength of the concrete increases. Elastic properties such as modulus of elasticity and Poisson's ratio of HSSCC were calculated using experimental data. In HSSCC, since the aggregate content is lower and the size of the aggregates is smaller, it will have a lower modulus of elasticity compared to normal vibrating concrete (NVC). Thus, an equation is proposed from the experimental results for predicting the modulus of elasticity of HSSCC. The results suggest that the proposed equation for predicting the elastic modulus of HSSCC for strengths ranging from 70 to 90 MPa is valid. It was also observed that the Poisson's ratio values for all three mixes of HSSCC were found to be lower than the typical value for NVC, indicating a higher degree of stiffness., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Plant products are widely used for health and disease management. However, besides their therapeutic effects, some plants also have potential toxic activity. Calotropis procera is a well-known laticifer plant having pharmacologically active proteins playing a therapeutically significant role in curing diseases like inflammatory disorders, respiratory diseases, infectious diseases, and cancers. The present study was aimed to investigate the antiviral activity and toxicity profile of the soluble laticifer proteins (SLPs) obtained from C. procera . Different doses of rubber free latex (RFL) and soluble laticifer protein (ranging from 0.019 to 10 mg/mL) were tested. RFL and SLPs were found to be active in a dose-dependent manner against NDV ( Newcastle disease virus ) in chicken embryos. Embryotoxicity, cytotoxicity, genotoxicity, and mutagenicity of RFL and SLP were examined on chicken embryos, BHK-21 cell lines, human lymphocytes, and Salmonella typhimurium , respectively. It was revealed that RFL and SLP possess embryotoxic, cytotoxic, genotoxic, and mutagenic activity at higher doses (i.e., 1.25-10 mg/mL), while low doses were found to be safe. It was also observed that SLP showed a rather safer profile as compared to RFL. This might be due to the filtration of some small molecular weight compounds at the time of purification of SLPs through a dialyzing membrane. We suggest that SLPs could be used therapeutically against viral disorders but the dose should be critically monitored., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The bulk and interfacial shear rheological behavior of aqueous solutions of biocompatible polymer HPC has been investigated in the presence of cationic CTAB and nonionic Tween 40 having the same chain length but different head groups. Steady-state bulk experiments depict two distinct regions in the rheogram (Newtonian followed by pseudoplastic). Dynamic experiments suggest that the stability of HPC hydrogels decreases with the increase in surfactant concentration. Interfacial steady shear tests of 2D monolayers of 1 wt % HPC and 1 wt % HPC with varying concentrations of Tween 40/CTAB show a non-Newtonian dilatant behavior at the solution-air interface. However, two distinct dilatant regions separated by a Newtonian region were observed for the same films at the solution-soya oil interface. The strength of films formed at the two interfaces decreases with the increase of surfactant concentration as observed from oscillatory interfacial tests. HPC interacts more strongly with CTAB than Tween 40 both in bulk as well as at the interfaces studied.

Methods enabling rapid and on-site detection of pathogenic bacteria are a prerequisite for public health assurance, medical diagnostics, ensuring food safety and security, and research. Many current bacteria detection technologies are inconvenient and time-consuming, making them unsuitable for field detection. New technology based on the CRISPR/Cas system has the potential to fill the existing gaps in detection. The clustered regularly interspaced short palindromic repeats (CRISPR) system is a part of the bacterial adaptive immune system to protect them from intruding bacteriophages. The immunological memory is saved by the CRISPR array of bacteria in the form of short DNA sequences (spacers) from invading viruses and incorporated with the CRISPR DNA repeats. Cas proteins are responsible for triggering and initiating the adaptive immune function of CRISPR/Cas systems. In advanced biological research, the CRISPR/Cas system has emerged as a significant tool from genome editing to pathogen detection. By considering its sensitivity and specificity, this system can become one of the leading detection methods for targeting DNA/RNA. This technique is well applied in virus detection like Dengue, ZIKA, SARS-CoV-2, etc., but for bacterial detection, this CRISPR/Cas system is limited to only a few organisms to date. In this review, we have discussed the different techniques based on the CRISPR/Cas system that have been developed for the detection of various pathogenic bacteria like L. monocytogenes , M. tuberculosis , Methicillin-resistant S. aureus , Salmonella , E. coli , P. aeruginosa , and A. baumannii ., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

This paper reports the facile one-pot synthesis of glycidol via the transesterification of glycerol with dimethyl carbonate using KNO 3 /Al 2 O 3 nanoparticles as supporting catalysts. KNO 3 /Al 2 O 3 nanoparticles were prepared by the impregnation method. XRD and FT-IR analyses indicated an interaction between KNO 3 and Al 2 O 3 that enabled the decomposition of KNO 3 during the process and resulted in the formation of KAl 5 O 8 , the Al-O-K group, and K 2 O. K 2 O was recognized as one of the active sites of the catalyst. SEM results indicated the high performance of the supporting catalyst, as the catalytic activity depended on both the number of catalytic active sites and their distribution. The yield of glycidol was 64% at the expense of 95% glycerol under moderate reaction conditions (120 min, 1 atm, and 70 °C). The nanocatalyst prepared at 800 °C with a loading amount of 30% KNO 3 was the most efficient for the synthesis of glycidol. Furthermore, the catalyst was recovered and reused without a loss of efficiency even after the fourth recycling. A plausible mechanism for the one-pot synthesis of glycidol has also been proposed., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The elucidation of the ideal coordination environment of a catalytic site has been at the heart of catalytic applications. Herein, we show that the water oxidation activities of catalytic cobalt sites in a Prussian blue (PB) structure could be tuned systematically by decorating its coordination sphere with a combination of cyanide and bidentate pyridyl groups.  K 0.1 [Co(bpy)] 2.9 [Fe(CN) 6 ] 2 ( [Cobpy-Fe] ), K 0.2 [Co(phen)] 2.8 [Fe(CN) 6 ] 2 ( [Cophen-Fe] ), {[Co(bpy) 2 ] 3 [Fe(CN) 6 ] 2 }[Fe(CN) 6 ] 1/3 ( [Cobpy2-Fe] ), and {[Co(phen) 2 ] 3 [Fe(CN) 6 ] 2 }[Fe(CN) 6 ] 1/3 Cl 0.11 ( [Cophen2-Fe] ) were prepared by introducing bidentate pyridyl groups (phen: 1,10-phenanthroline, bpy: 2,2'-bipyridine) to the common synthetic protocol of Co-Fe Prussian blue analogues. Characterization studies indicate that [Cobpy2-Fe] and [Cophen2-Fe] adopt a pentanuclear molecular structure, while [Cobpy-Fe] and [Cophen-Fe] could be described as cyanide-based coordination polymers with lower-dimensionality and less crystalline nature compared to the regular Co-Fe Prussian blue analogue (PBA), K 0.1 Co 2.9 [Fe(CN) 6 ] 2 ( [Co-Fe] ). Photocatalytic studies reveal that the activities of [Cobpy-Fe] and [Cophen-Fe] are significantly enhanced compared to those of [Co-Fe] , while molecular [Cobpy2-Fe] and [Cophen2-Fe] are inactive toward water oxidation. [Cobpy-Fe] and [Cophen-Fe] exhibit upper-bound turnover frequencies (TOFs) of 1.3 and 0.7 s -1 , respectively, which are ∼50 times higher than that of [Co-Fe] (1.8 × 10 -2 s -1 ). The complete inactivity of [Cobpy2-Fe] and [Cophen2-Fe] confirms the critical role of aqua coordination to the catalytic cobalt sites for oxygen evolution reaction (OER). Computational studies show that bidentate pyridyl groups enhance the susceptibility of the rate-determining Co(IV)-oxo species to the nucleophilic water attack during the critical O-O bond formation. This study opens a new route toward increasing the intrinsic water oxidation activity of the catalytic sites in PB coordination polymers.

We have designed a new class of highly potent bivalent melanocortin receptor ligands based on the nature-derived bicyclic peptide sunflower trypsin inhibitor 1 (SFTI-1). Incorporation of melanotropin pharmacophores in each of the two turn regions of SFTI-1 resulted in substantial gains in agonist activity particularly at human melanocortin receptors 1 and 3 (hMC1R/hMC3R) compared to monovalent analogues. In in vitro binding and functional assays, the most potent molecule, compound 6 , displayed low picomolar agonist activity at hMC1R (pEC 50 > 10.3; EC 50 < 50 pM; p K i : 10.16 ± 0.04; K i : 69 ± 5 pM) and is at least 30-fold more selective for this receptor than for hMC3R, hMC4R, or hMC5R. The results are discussed in the context of structural homology models of hMCRs in complex with the developed bivalent ligands.

The development of photoluminescent (PL) systems, displaying multiple stimuli-responsive emission color tuning, has been the pressing priority in the recent times due to their huge role in contemporary lighting and anticounterfeiting technologies. Acknowledging this importance, we present a simple and eco-friendly PL system showing emission color tuning in response to different stimuli, that is, the composition of the system, pH, excitation wavelength, and the temperature with the plus point of getting significantly pure white light emission (WLE). The novel system is fabricated from the aqueous mixture of three organic fluorophores, umbelliferone ( UMB ), fluorescein ( FLU ), and Rhodamine-B ( RB ). By varying the fluorophore composition in the mixture at pH 12, nearly pure WLE with a Commission Internationale d'Eclairage (CIE) 1931 profile of (0.33, 0.33) was obtained at the excitation wavelength of 365 nm, the sustainability of which was ensured by employing the micellar self-assemblies of tetradecyltrimethylammonium bromide ( TTAB ) molecules. Similar WLE was obtained under mildly acidic conditions (pH 6) but at the excitation wavelength of 330 nm. By proper tuning of pH and the wavelengths of the system to use it as a fluorescent ink, we found a remarkable and highly applicable phenomenon observed for the first time, that is, triple-mode orthogonal emission color tuning with white light ON/OFF switching. We validate the vital applicability of this phenomenon in protecting the authenticity of the document with its hard-to-counterfeit property. The applicability of this phenomenon is also explored by synthesizing PVA-based fluorescent films from the tri-fluorophore mixture. Moreover, the emission color of the PL system was explored lucidly for its temperature dependence owing to the thermal responsiveness of RB emission, where the PL system proves to be a full-color RGB system.

Mn doping in SrSnO 3 perovskite material via hydrothermal process under subcritical conditions is reported for the very first time. The present article aims to carry this perovskite suitable for blue light-emitting diodes (LEDs) and spintronic applications. The influence of various Mn doping percentages on structural, morphological, compositional, optical, photoluminescent, and magnetic properties of SrSnO 3 is demonstrated. The perovskite material is grown in an orthorhombic crystal structure having a space symmetry of Pnma along with point group of mmm as determined from the Rietveld refinement. Doping is an excellent way to modify the properties of wide-band-gap perovskite nanostructures. Incorporation of Mn is the result of exact substitution. Morphological studies indicate formation of rodlike structures with thickness in nanoscale dimensions (180-280 nm), and the thickness is a function of doping concentration. The higher doping concentration resulted in enhanced growth of the nanorods. Selected area electron diffraction (SAED) results showed the single-crystal nature of the nanorods. Thermogravimetric analysis (TGA) confirmed the high stability of the material at elevated temperatures. Also, the doped perovskite material is transparent in the visible light, active in the ultraviolet region having a band gap of ∼2.78 eV, and is tuned up to 2.25 eV as the Mn doping concentration reaches 10%. The transfer of excitonic energy from the host material to the dopant Mn 2+ ion leads to the formation of spin-forbidden [ 4 T 1 - 6 A 1 ] emission. Later on, photoluminescence study indicates an enhancement in luminescence behavior of Mn doped perovskite nanostructures. The Commission Internationale de l'éclairage (CIE) diagram drawn to find the color coordinates of the nanorods determines their suitability for blue LEDs. In addition, Mn doping results the conversion of diamagnetic SrSnO 3 into a ferromagnetic material, making the nanorods suitable for spintronic applications., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Cloth masks can be an alternative to medical masks during pandemics. Recent studies have examined the performance of fabrics under various conditions; however, the performance against violent respiratory events such as human sneezes is yet to be explored. Accordingly, we present a comprehensive experimental study using sneezes by a healthy adult and a tailored image-based flow measurement diagnostic system evaluating all dimensions of protection of commonly available fabrics and their layered combinations: the respiratory droplet blocking efficiency, water resistance, and breathing resistance. Our results reveal that a well-designed cloth mask can outperform a three-layered surgical mask for such violent respiratory events. Specifically, increasing the number of layers significantly increases the droplet blocking efficiency, on average by ∼20 times per additional fabric layer. A minimum of three layers is necessary to resemble the droplet blocking performance of surgical masks, and a combination of cotton/linen (hydrophilic inner layer)-blends (middle layer)-polyester/nylon (hydrophobic outer layer) exhibited the best performance among overall indicators tested. In an optimum three-layered design, the average thread count should be greater than 200, and the porosity should be less than 2%. Furthermore, machine washing at 60 °C did not significantly impact the performance of cloth masks. These findings inform the design of high-performing homemade cloth masks.

The chemical kinetic (CK) method, which involves the reduction of 4-hexadecylbenzenediazonium ions (16-ArN 2 + ) by antioxidants (in the present case, TBHQ) occurring exclusively at the interface of the association colloids, was employed to establish the changes in the chemical reactivity of anionic surface-active ionic liquids (SAILs) as a function of the concentration and the composition in their mixed states. We used sodium dodecyl sulfate and different SAILs based on the dodecylsulfate surfactant containing 1-alkyl-3-methylimidazolium cations as counterions having a varying alkyl chain length of 4 (bmim), 8 (omim), and 12 (ddmim) carbon atoms. The structural transitions of aggregates of the SAILs from the micellar to vesicular form were observed as a function of concentration in single surfactant systems and as a function of composition in mixed surfactant systems. Results of the reduction kinetics of 16-ArN 2 + at the interface of such aggregates, which depends on the acid/base equilibria at the interface, gave an insight into the changes in the interfacial H + ions with the change in the hydrophobicity of the counterions of SAILs and the morphological changes from micelles to vesicles as a function of concentration or composition. These changes in the interfacial pH correlate very well with the stability of curcumin within these self-assemblies, which exclusively depends on the pH of the medium and highlights the importance of the results obtained from the CK method in selecting the appropriate medium/conditions for the stabilization of the bioactive molecules., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The mixture of the cationic surfactant, cetyltrimethylammonium bromide (CTAB), and anionic surface-active ionic liquid, 1-butyl-3-methylimidazoliumdodecyl sulfate (bmimDS), has been studied as a function of the mole fraction of CTAB, X CTAB , with the total surfactant concentration fixed at 50 mM using turbidity measurements, rheology, dynamic light scattering, differential scanning calorimetry, small-angle neutron scattering, and small-angle X-ray scattering techniques. The catanionic mixture has been found to exhibit phase transitions from vesicles to micelles as a function of temperature, with some mole fractions of CTAB showing dual transitions. Solutions of X CTAB = 0.2 to 0.5 exhibited a single transition from vesicles to cylindrical micelles at 45 °C. With an increase in the mole fraction of CTAB from 0.55 to 0.65, dual structural transitions at 30 and 45 °C were observed. The microstructural transition at 30 °C is ascribed to the vesicle aggregation process with smaller vesicles fusing into bigger ones, whereas the transition at 45 °C was evaluated to be the vesicle-to-cylindrical micelle transition. However, at higher mole fractions of CTAB, X CTAB from 0.65 to 0.90, a single transition from vesicles to small cylindrical/spherical micelles was observed in the solutions, at a lower temperature of 30 °C. To the best of our knowledge, such a microstructural transitions as a function of temperature in a single mixture of cationic and anionic surfactants without any additive has not been reported so far., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The large demand of natural gas consumption requires an effective technology to purify and store methane, the main component of natural gas. Metal-organic frameworks and gas hydrates are highly appealing materials for the efficient storage of industrially relevant gases, including methane. In this study, the methane storage capacity of the combination of methane hydrates and HKUST-1, a copper-based metal-organic framework, was studied using high pressure differential scanning calorimetry. The results show a synergistic effect, as the addition of HKUST-1 promoted hydrate growth, thus increasing the amount of water converted to hydrate from 5.9 to 87.2% and the amount of methane stored, relative to the amount of water present, from 0.55 to 8.1 mmol/g. The success of HKUST-1 as a promoter stems mainly from its large surface area, high thermal conductivity, and hydrophilicity. These distinctive properties led to a kinetically favorable decrease in hydrate growth induction period by 4.4 h upon the addition of HKUST-1. Powder X-ray diffraction and nitrogen isotherm suggests that the hydrate formation occurs primarily on the surface of HKUST-1 rather than within the pores. Remarkably, the HKUST-1 crystals show no significant changes in terms of structural integrity after many cycles of hydrate formation and dissociation, which results in the material having a long life cycle. These results confirm the beneficial role of HKUST-1 as a promoter for gas hydrate formation to increase methane gas storage capacity.

A weakly coordinating, carbonyl-assisted C-H activation of aromatic systems with α,β-unsaturated ketone and subsequent aldol condensation has been developed using a Cp*Co(CO)I 2 catalyst. The developed method is the first example of indene synthesis by cobalt-catalyzed C-H activation. In addition, the reaction requires mild reaction conditions and easily accessible starting materials, and it shows excellent functional group compatibility.

A broad spectrum tunable photoluminescent material with dual encryption based on a two-step fluorescence resonance energy transfer (FRET) between pyrene ( Py ), coumarin 480 ( Cou480 ), and rhodamine 6G ( R6G ) in micelles of SDS and bmimDS is presented. The phenomenon is achievable due to the encapsulation of the fluorophores within these micelles. The transfer of energy as FRET between the pair Py and Cou480 showed ON at 336 nm and OFF at 402 nm in contrast to the FRET observed between the pair Cou480 and R6G that showed ON at 402 nm and OFF at 336 nm. However, the transfer of energy as FRET occurs from Py to R6G in the presence of Cou480 when excited at 336 nm, thereby making it a chain of three fluorophores with Cou480 acting as a relay fluorophore receiving energy from Py and transferring it to R6G . The different FRET scenarios between the three fluorophores in micelles provide a window for the generation of a matrix of colors, which occupies a significant 2D area in the chromaticity diagram, having potential applications in security printing. The different fluorophoric ratios generate different colors based on their individual photonic emissions and the FRET processes taking place between them. Writing tests were carried out using varied ratios of the fluorophores in the micellar systems producing different colored outputs under the UV light with insignificant visibility under the white light. We envision that this as-discovered three fluorophoric FRET system could form the basis for the future development of multi-FRET light-harvesting devices and anti-counterfeiting security inks based on much simpler non-covalent interaction aided encapsulation of the fluorophores within the self-assembled soft systems.

We report a new approach to building hierarchical superstructures using a shape-persistent porous organic cage, which acts as a premade secondary building unit, and coordination chemistry. To illustrate the principle, a zinc-metalated porphyrin box (Zn-PB), a corner-truncated cubic porous cage, was connected by suitable dipyridyl terminated bridging ligands to construct PB-based hierarchical superstructures (PSSs). The PSSs were stabilized not only by the coordination bonds between Zn ions and bipyridyl-terminated ligands but also by π-π interactions between the corners of the Zn-PB units. By varying the length of the linker, we identified an optimum range of the linker length for construction of PSSs. The PSSs have large void volumes and an extrinsic surface area compared to the parent PBs, which can be exploited for the selective encapsulation and interior functionalization of the PSSs for various applications, including catalysis. We observed that singlet oxygen induced synthesis of the natural product, juglone, is more efficiently catalyzed by PSS-1 than its constituent component Zn-PB.

The effect of lavender oil on aggregation characteristics of P123 in aqueous-ethanolic solutions is investigated systematically by DLS, SANS, and rheology. The solubilization capacity of the P123 based formulations toward Lavender oil increased by increasing P123 concentration. The study unveiled the importance of the short chain alcohol-ethanol, as solubilization enhancer. The apparent hydrodynamic radius (R h ) increased significantly with an increase in lavender oil concentration up to maximum oil solubilization capacity of the copolymer at a particular ethanol concentration. DLS measurements on 5, 10, and 15 wt% P123 in the presence of 25% ethanol revealed the presence of large-sized micellar clusters in addition to the oil swollen micelles. The core size (R C ), radius of hard sphere (R HS ), and aggregation number (N) obtained from SANS profiles showed considerable enhancement with the addition of lavender oil confirming penetration of oil inside the copolymer. Rheological studies showed that viscosity also increased significantly with the addition of lavender oil near the maximum loading limit of the P123 concentration. Quite interestingly, the sol-gel transition temperature displayed a strong dependence on both P123 as well as oil concentration and decreased almost linearly by increasing oil concentration. This study demonstrates the use of a biocompatible and temperature sensitive self-assembled P123 based formulation for lavender oil solubilization that can be beneficial in the cosmetic industry wherein controlled release of fragrances and so forth is demanded.

Solubilization of structurally varied coumarins, viz., Warfarin (WF; a 4-hydroxy coumarin) and Coumarin30 (C30, a 7-amino coumarin) individually and in mixed states (cosolubilization) within the aqueous surfactant self-assemblies of varying architectures has been explored, exploiting steady-state, time-resolved fluorimetric, and spectrophotometric techniques. Cosolubilization studies within micelles, which have rarely been done in the literature, were specifically undertaken with the aim of understanding the effect of micelles on their photophysical phenomena when simultaneously present within these nanocarriers and assess their prospective use as an efficient FRET pair. WF solubilizes within CTAB micelles, whereas little or no solubilization is observed in Brij30 and SDS micelles. On the other hand, C30 solubilizes deep into the palisade layer of CTAB micelles, between negatively charged head groups in SDS micelles and between OE groups in Brij30 micelles. C30 and WF maintain their solubilization sites during cosolubilization. In SDS and Brij30 micelles, an increase in WF causes fluorescence quenching of C30 molecules, while in CTAB, an increase in WF causes an increase in fluorescence of C30 by excited WF molecules indicating FRET between the two molecules.

Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures-separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with increasing alkyl chain length of a particular AO. We conclude with perspectives and prospects.

Captive bubbles on a superhydrophobic (SH) surface have been shown to increase in volume via injection of air through the surrounding plastron. The experimental contact diameter against volume trends were found to follow that predicted by the Surface Evolver simulation generally but corresponded with the simulated data at contact angle (CA) = 158° when the volume was 20 μL but that at CA = 170° when the volume was increased to 180 μL. In this regime, there was a simultaneous outward movement of the contact line as well as a small reduction in the slope that the liquid-air interface makes with the horizontal as air was injected. At volumes higher than 180 μL, air injection caused the diameter to reduce progressively until detachment. The inward movement of the contact line in this regime allowed the bubble body to undergo shape deformations to stay attached onto the substrate with larger volumes (300 μL) than predicted (220 μL at CA = 170°) using simulation. In experiments to investigate the effect of translating the SH surface, movement of captive bubbles was possible with 280 μL volume but not with 80 μL volume. This pointed to the possibility of transporting gas-phase samples on SH surfaces using larger captive bubble volumes.

The interaction of xanthine oxidase (XO), a key enzyme in purine metabolism, with cetyltrimethylammonium bromide (CTAB) and bis(cetyldimethylammonium)butane dibromide (C16C4C16Br2) has been studied using tensiometry, spectrofluorometry, spectrophotometry, and circular dichroism at pH 7.4 and 25 °C. The tensiometric profiles of CTAB and C16C4C16Br2 in the presence of XO exhibit a single break at a lower surfactant concentration termed as C1 compared to their CMC in the buffered solution and show the existence of interaction between the surfactants and the enzyme. The results of the multitechnique approach showed that, although both CTAB as well as C16C4C16Br2 interact with the XO, C16C4C16Br2 interacts more strongly than its conventional single chain counterpart. Fluorescence and absorption measurements revealed that, compared to CTAB, C16C4C16Br2 is more effective in unfolding the enzyme. Change in XO activity by the surfactants was in concurrence with the structural alterations monitored by circular dichroism and showed structural stabilization of XO at higher surfactant concentrations, consistent with the aggregation results. This stabilization has been explained in light of strong tendency of C16C4C16Br2 for micellar growth and membrane/water stabilization of proteins by membrane-like fragments provided by higher concentrations of C16C4C16Br2 . The results are related to the stronger electrostatic and hydrophobic forces in C16C4C16Br2, owing to the presence of two charged headgroups and two hydrophobic tails.

Deficiency of the sulfide metabolizing protein ETHE1 is the cause of ethylmalonic encephalopathy (EE), an inherited and severe metabolic disorder. To study the molecular effects of EE, we performed a proteomics study on mitochondria from cultured patient fibroblast cells. Samples from six patients were analyzed and revealed seven differentially regulated proteins compared with healthy controls. Two proteins involved in pathways of detoxification and oxidative/reductive stress were underrepresented in EE patient samples: mitochondrial superoxide dismutase (SOD2) and aldehyde dehydrogenase X (ALDH1B). Sulfide:quinone oxidoreductase (SQRDL), which takes part in the same sulfide pathway as ETHE1, was also underrepresented in EE patients. The other differentially regulated proteins were apoptosis inducing factor (AIFM1), lactate dehydrogenase (LDHB), chloride intracellular channel (CLIC4) and dimethylarginine dimethylaminohydrolase 1 (DDAH1). These proteins have been reported to be involved in encephalopathy, energy metabolism, ion transport, and nitric oxide regulation, respectively. Interestingly, oxidoreductase activity was overrepresented among the regulated proteins indicating that redox perturbation plays an important role in the molecular mechanism of EE. This observation may explain the wide range of symptoms associated with the disease, and highlights the potency of the novel gaseous mediator sulfide.

The interaction between cationic gemini hexanediyl-1,6-bis(dimethylcetylammonium bromide) (16-6-16, abbreviated as G6) with conventional cationic cetylpyridinium chloride (CPC), anionic sodium bis(2-ethyl hexyl)sulfosuccinate (AOT) and nonionic polyoxyethylene 10 cetyl ether (Brij56) in aqueous medium has been investigated at 25 degrees C. Different physicochemical properties such as critical micelle concentration (cmc), surface excess concentration (Gamma(max)), minimum area per molecule (A(min)), and interaction parameters (beta(m), beta(sigma)) as well as other thermodynamic and micellar properties have been determined. The interfacial and bulk behaviors were explored using theoretical models of Clint, Rubingh, Rosen, Motomura, and Maeda for justification and comparison of results of different binary combinations with the geminis of alkanediyl-alpha,omega-bis(dimethylcetylammonium bromide) series. Synergism was observed in all the binary combinations in the micelle and at interface with lowering of packing parameter due to slight expansion of A(min). The results of the present study could be of interest for selection of surfactant mixtures for surfactant-enhanced remediation (SER) of soils and aquifers contaminated by hydrophobic organic compounds (HOCs).

The interaction of hexadecyltrimethylammonium bromide (HTAB) and methylcellulose (MC) has been investigated in aqueous medium employing rheological and fluorescence probing experiments. The associated physicochemical properties of the polymer-surfactant mixed system such as critical aggregation concentration (cac), critical micelle concentration (cmc), micellar aggregation number (N), micellar micropolarity index (pyrene I(1)/I(3) values), and viscosity curve are studied as a function of HTAB concentration. The effects of sodium benzoate (NaBz), sodium hexanoate (NaHx) and sodium chloride (NaCl) on the behavior of the polymer-surfactant solution have been followed systematically. The obtained experimental findings unfold significant information with respect to the effects of the salts on the solution behavior of the mixed system in addition to gelation characteristics.

The interaction of bovine serum albumin (BSA) with cetyltrimethylammonium bromide (CTAB), C(16)C(4)C(16)Br(2), Brij58, and their binary mixtures has been studied using tensiometry, spectrofluorometry, and circular dichroism at physiological pH and 25 degrees C. The tensiometric profiles of CTAB and C(16)C(4)C(16)Br(2) in the presence of BSA exhibit a single break at a lower surfactant concentration termed as C(1) (concentration corresponding to saturation of the interface) compared to their critical micelle concentration (CMC) in the buffered solution. However, for Brij58, CTAB+Brij58, and C(16)C(4)C(16)Br(2)+Brij58, two breaks were observed, first at the critical aggregation concentration (CAC), corresponding to onset of interaction with BSA and the second at C(1) corresponding to saturation of the interface. The interaction of CTAB+Brij58 and C(16)C(4)C(16)Br(2)+Brij58 mixtures with the BSA solution is discussed in terms of competition between surfactant-surfactant and surfactant-BSA interactions. CTAB+Brij58 and C(16)C(4)C(16)Br(2)+Brij58 mixtures show nonideality with respect to mixed micelle formation, which is reflected in their interaction with the BSA. The interaction of CTAB+Brij58 with BSA decreases with increase in the mole fraction of CTAB in the mixture, whereas in C(16)C(4)C(16)Br(2)+Brij58 the reverse is the case. The results of the present study may prove fruitful in optimizing the properties of surfactant-protein mixtures relevant for many formulations.

Mixed surfactants may improve the performance of surfactant-enhanced solubilization of drugs and thus can serve as the tool for increased bioavalaibility, controlled drug release, and targeted delivery. Solubilization of Naproxen by micellar solutions at 25 degrees C using single and mixed surfactant systems was measured and compared. Solubilization capacity determined with spectrophotometry and tensiometry has been quantified in terms of molar solubilization ratio, micelle-water partition coefficient, and locus of solubilization. Cationic surfactants exhibited higher solubilization capacity than nonionics and anionics, the efficiency increasing with chain length. Mixing effect of surfactants on mixed micelle formation and solubilization efficiency has been discussed in light of regular solution approximation (RSA). Equimolar cationic-nonionic surfactant combinations showed better solubilization capacity than pure cationics or nonionics, which, in general, increased with increase in hydrophobic chain length. Equimolar cationic-nonionic-nonionic ternary surfactant systems exhibited intermediate solubilization efficiency between their single and binary counterparts. Use of RSA has been extended, with fair success, to predict the partition coefficient of ternary surfactant systems using data from binary mixtures. The theoretical micelle-water partition coefficients calculated from the geometric mean equation compared well with experimental values. Locus of solubilization of NAP in different micellar solutions was probed by UV-visible spectroscopy.

To improve the sensitivity of antibody microarray assays, we developed ENSAM (Europium Nanoparticles for Signal enhancement of Antibody Microarrays). ENSAM is based on two nanomaterials. The first is polystyrene nanoparticles incorporated with europium chelate (beta-diketone) and coated with streptavidin. The multiple fluorophores incorporated into each nanoparticle should increase signal obtained from a single binding event. The second nanomaterial is array surfaces of nanoporous silicon, which creates high capacity for antibody adsorption. Two antibody microarray assays were compared: ENSAM and use of streptavidin labeled with a nine-dentate europium chelate. Analyzing biotinylated prostate-specific antigen (PSA) spiked into human female serum, ENSAM yielded a 10-fold signal enhancement compared to the streptavidin-europium chelate. Similarly, we observed around 1 order of magnitude greater sensitivity for the ENSAM assay (limit of detection < or = 0.14 ng/mL, dynamic range > 10(5)) compared to the streptavidin-europium chelate assay (limit of detection < or = 0.7 ng/mL, dynamic range > 10(4)). Analysis of a titration series showed strong linearity of ENSAM ( R2 = 0.99 by linear regression). This work demonstrates the novel utility of nanoparticles with time-resolved fluorescence for signal enhancement of antibody microarrays, requiring as low as 100-200 zmol biotinylated PSA per microarray spot. In addition, proof of principle was shown for analyzing PSA in plasma obtained from patients undergoing clinical PSA-testing.

In this paper, we are reporting the influence of addition of aromatic acids (anthranilic and benzoic acid) and their sodium salts on the micellar morphological changes in three cationic gemini surfactant solutions, viz. 5 mM tetramethylene-1,4-bis(N-hexadecyl-N,N-dimethylammonium bromide), 10 mM pentamethylene-1,5-bis(N-hexadecyl-N,N-dimethylammonium bromide), and 10 mM hexamethylene-1,6-bis(N,-hexadecyl-N,N-dimethylammonium bromide). The solubilization site of the counterions (obtained from the additives) near the micellar surface are inferred by 1H NMR. The behavior is explained in the light of binding of counterions to the micelle as well as the nature of the functional group attached to the additive.

Water solubility enhancements of polycyclic aromatic hydrocarbons (PAHs), viz., naphthalene, anthracene and pyrene, by micellar solutions at 25 degrees C using two series of surfactants, each involving two cationic and one nonionic surfactant in their single as well as equimolar binary and ternary mixed states, were measured and compared. The first series was composed of three surfactants, benzylhexadecyldimethylammonium chloride (C16BzCl), hexadecyltrimethylammonium bromide (C16Br), and polyoxyethylene(20)mono-n-hexadecyl ether (Brij-58) with a 16-carbon (C16) hydrophobic chain; the second series consisted of dodecyltrimethylammonium bromide (C12Br), dodecylethyldimethylammonium bromide (C12EBr), and polyoxyethylene(4)mono-n-dodecyl ether (Brij-30) with a 12-carbon (C12) chain. Solubilization capacity has been quantified in terms of the molar solubilization ratio, the micelle-water partition coefficient, the first stepwise association constant between solubilizate monomer and vacant micelle, and the average number of solubilizate molecules per micelle, determined employing spectrophoto-, tensio-, and flourimetric techniques. Cationic surfactants exhibited lesser solubilization capacity than nonionics in each series of surfactants with higher efficiency in the C16 series compared to the C12 series. Increase in hydrophobicity of head groups of cationics by incorporation of ethyl or benzyl groups enhanced their solubilization capacity. The mixing effect of surfactants on mixed micelle formation and solubilization efficiency has been discussed in light of the regular solution approximation (RSA). Cationic-nonionic binary combinations showed better solubilization capacity than pure cationics, nonionics, or cationic-cationic mixtures, which, in general, showed increase with increased hydrophobicity of PAHs. Equimolar cationic-cationic-nonionic ternary surfactant systems showed lower solubilization efficiency than their binary cationic-nonionic counterparts but higher than cationic-cationic ones. In addition, use of RSA has been extended, with fair success, to predict partition coefficients of ternary surfactant systems using data of binary surfactants systems. Mixed surfactants may improve the performance of surfactant-enhanced remediation of soils and sediments by decreasing the applied surfactant level and thus remediation cost.