Water-soluble Molecules Research Articles

Progress on clay swelling inhibitors: a comprehensive review

Relevance. It is known that swelling of a well wall due to the presence of water negatively affects drilling operations, causing a significant increase in their material costs. The use of various inhibitors prevents this effect and the drilling mud reacting on wellbore narrowing. In this sense, the problems of developing polymer, amino-, ionic liquid and shale inhibitors of surfactants considered in the article are very relevant and of practical interest to oil engineers in terms of the prospects for fundamental and applied researches of these issues. Aim. To study the possibilities of existing approaches and methods that determine the characteristics of the main clay swelling inhibitors, the regularities of changes in the properties of traditional and non-traditional clay materials, as well as the mechanisms of clay swelling with the identification of the most characteristic group of these inhibitors. Object. Processes of minimizing the effect of wall narrowing as a result of exposure to inhibitors. Methods. Systematic, critical and comprehensive analysis of modern data on clay swelling inhibition in the field of drilling muds. Results. The authors have carried out the detailed analysis of clay swelling. The paper discusses the characteristics of inhibitors required to prevent swelling, in the structure of which nitrogen and ionic liquids are contained. It is noted that a high-quality clay swelling inhibitor should include in its base a water-soluble bulk molecule with a distinct hydrophobic and hydrophilic structure; have characteristics, which allow replacing the hydrated cations of the intermediate layer with some hydrophobic cations, such as ammonium ions instead of sodium ions; differ in the ability to disperse multiple cations well. It was found that functional groups that support inhibitor binding to the siloxane groups of the clay are able to significantly expand clay swelling.

Peptide programming of supramolecular vinylidene fluoride ferroelectric phases.

Ferroelectric structures have spontaneous macroscopic polarization that can be inverted using external electric fields and have potential applications including information storage, energy transduction, ultralow-power nanoelectronics1,2 and biomedical devices3. These functions would benefit from nanoscale control of ferroelectric structure, the ability to switch polarization with lower applied fields (low coercive field) and biocompatibility. Soft ferroelectrics based on poly(vinylidene fluoride) (PVDF)4-6 have a thermodynamically unstable ferroelectric phase in the homopolymer, complex semi-crystalline structures, and high coercive fields. Here we report on ferroelectric materials formed by water-soluble molecules containing only six VDF repeating units covalently conjugated to a tetrapeptide, with the propensity to assemble into the β-sheet structures that are ubiquitous in proteins. This led to the discovery of ribbon-shaped ferroelectric supramolecular assemblies that are thermodynamically stable with their long axes parallel to both the preferred hydrogen-bonding direction of β-sheets and the bistable polar axes of VDF hexamers. Relative to a commonly used ferroelectric copolymer, the biomolecular assemblies exhibit a coercive field that is two orders of magnitude lower, as the result of supramolecular dynamics, and a similar level of remnant polarization, despite having a peptide content of 49 wt%. Furthermore, the Curie temperature of the assemblies is about 40 °C higher than that of a copolymer containing a similar amount of VDF. This supramolecular system was created using a biologically inspired strategy that is attractive in terms of sustainability and that could lead to new functions for soft ferroelectrics.

Water-soluble AIE photosensitizer in short-wave infrared region for albumin-enhanced and self-reporting phototheranostics

Organic photosensitizers (PSs) play important roles in phototheranostics, and contribute to the fast development of precision medicine. However, water-soluble and highly emissive organic PSs, especially those emitting in the short-wave infrared region (SWIR), are still challenging. Also, it's difficult to prepare self-reporting PSs for visualizing the treatment via stimulated emission depletion (STED) nanoscopy. Thus, in this work, a water-soluble molecule of DTPAP-TBZ-I with aggregation-induced emission features is designed for the self-reporting photodynamic therapy (PDT) in an ultra-high resolution. In contrast to single molecule, its complex (DTPAP-TBZ-I@BSA) shows much enhanced fluorescence properties and reactive oxygen species (ROS) generation in SWIR window. Their photoluminescence quantum yield is determined to be ∼20.6 % and the enhancement of ROS generation is ∼18-fold. During the PDT, immigration of the complex from cytoplasm to nucleus is also observed via STED nanoscopy with a resolution of 66.11 nm, which allows self-report in the PDT treatment. DTPAP-TBZ-I@BSA is finally utilized for the imaging-guided PDT in vivo with a tumor inhibition rate of 84 %. This is the first work in albumin-enhanced water-soluble organic PSs in SWIR window for self-reporting phototheranostics at ultra-high resolutions, providing an ideal solution for the next generation of photosensitizers for precise medicine.

Optimization of carrier transfer kinetics of BiOIO3 using TFA·/TFA- reversible redox pairs of TFA molecules as co-catalysts for efficient photoelectrochemical water splitting system

Co-catalyst loading on photoelectrodes is considered to be an effective way to accelerate charge transfer. However, the bonding between most of the co-catalysts and photoelectrodes tends to be weak, which severely limits the role of co-catalysts in the catalytic system. Based on the above problems, we introduced trifluoroacetic acid (TFA) as a homogeneous molecular co-catalyst in the layered BiOIO3 catalytic system for the first time. The BiOIO3-TFA photoelectrode exhibited excellent photoelectrochemical performance under light and applied bias voltage. The photocurrent density reached up to 0.228 μA cm−2, which was 2.11 times higher than that before modification, while the overpotential was negatively shifted by 183 mV. The results showed that the photogenerated electron-hole pairs in BiOIO3 are excited and transferred to the TFA causing the CO double bond to break to form a TFA radical (TFA·), which is then reduced to TFA-. This cyclic redox reaction accompanied by fast hole transfer can greatly reduce the recombination behavior during carrier transport. This work demonstrates a new form of co-catalyst for photoelectrochemical water splitting. Highly water-soluble molecules and TFA·/TFA- reversible reactions have considerable potential for the development of new co-catalysts. It also provides ideas for the establishment of new, efficient catalytic systems for inhibiting carrier recombination.

Synthesis of a MOF derived porous graphene and pyrolytic carbon supported zinc stannate nanohybrid electrode with enhanced lithium-ion storage performances

Compositing nano-sized zinc stannate (Zn2SnO4) with supportive carbon skeleton usually brings in improved lithium-ion storage performances. One of the most challenging tasks is to effectively stabilize Zn2SnO4 nanocrystals via simplified preparation routes from eco-friendly raw materials. In this work, the water-soluble natural molecule gallic acid (GA) is directly employed to coordinate with Zn2+/Sn2+ ions, and the corresponding metal-organic framework (MOF) precursor samples of pure Zn-GA MOF and bimetallic ZnSn-GA MOF can be synthesized. The Zn-GA MOF and ZnSn-GA MOF precursors are further converted to a three-dimensional (3D) porous graphene sample (ZMG) and a pyrolytic carbon domain supported Zn2SnO4 nanocomposite (Zn2SnO4@C), respectively, by taking the advantages of the unique micro-structures and compositions of MOF materials. By rationally mixing the ZMG and Zn2SnO4@C in electrode fabrication, the finally obtained Zn2SnO4@C/ZMG nanohybrid electrode exhibits a high reversible capacity of 1117 mAh·g−1 after 500 cycles at a current density of 1000 mA g−1 in half-cells as well as inspiring full-cell performance. The favorable synergistic effect in lithium-ion storage for the Zn2SnO4@C/ZMG electrode has been investigated. The MOF derived samples and involved sustainable synthesis protocols can be further developed for wider applications.

Antifungal Activity of Disalt of Epipyrone A from Epicoccum nigrum Likely via Disrupted Fatty Acid Elongation and Sphingolipid Biosynthesis.

Multidrug-resistant fungal pathogens and antifungal drug toxicity have challenged our current ability to fight fungal infections. Therefore, there is a strong global demand for novel antifungal molecules with the distinct mode of action and specificity to service the medical and agricultural sectors. Polyenes are a class of antifungal drugs with the broadest spectrum of activity among the current antifungal drugs. Epipyrone A, a water-soluble antifungal molecule with a unique, linear polyene structure, was isolated from the fungus Epiccocum nigrum. Since small changes in a compound structure can significantly alter its cell target and mode of action, we present here a study on the antifungal mode of action of the disalt of epipyrone A (DEA) using chemical-genetic profiling, fluorescence microscopy, and metabolomics. Our results suggest the disruption of sphingolipid/fatty acid biosynthesis to be the primary mode of action of DEA, followed by the intracellular accumulation of toxic phenolic compounds, in particular p-toluic acid (4-methylbenzoic acid). Although membrane ergosterol is known to be the main cell target for polyene antifungal drugs, we found little evidence to support that is the case for DEA. Sphingolipids, on the other hand, are known for their important roles in fungal cell physiology, and their biosynthesis has been recognized as a potential fungal-specific cell target for the development of new antifungal drugs.

Cascade Hydroxyl Radical-Generating and Ferroptosis-Inducing Nanofiber System for the Therapy of Oral Squamous Cell Carcinoma.

Nanofiber (NF) membrane systems that can provide cascade catalytic reaction and ferroptosis induction were developed for oral cancer therapy. Glucose oxidase (GOx) and aminoferrocene (AF) were introduced into the NF system for glucose deprivation/H2O2 generation and OH radical generation, respectively. GOx offers starvation therapy and AF (including iron) provides chemodynamic therapy/ferroptosis for combating oral cancer. GOx (water-soluble) and AF (poorly water-soluble) molecules were successfully entrapped in the NF membrane via an electrospinning process. GOx and AF were incorporated into the polyvinyl alcohol (PVA)-based NF, resulting in PVA/GOx/AF NF with fast disintegration and immediate drug-release properties. In oral squamous cell carcinoma (YD-9 cells), the PVA/GOx/AF NF group exhibited higher cytotoxicity, antiproliferation potential, cellular ROS level, apoptosis induction, lipid ROS level, and malondialdehyde level compared to the other NF groups. The electrospun PVA/GOx/AF NF can be directly applied to oral cancer without causing pain, offering starvation/chemodynamic therapy and ferroptosis induction.

Direct Water-Soluble Molecules Transfer from Transplanted Bone Marrow Mononuclear Cell to Hippocampal Neural Stem Cells.

Intravascularly transplanted bone marrow cells, including bone marrow mononuclear cells (BM-MNC) and mesenchymal stem cells, transfer water-soluble molecules to cerebral endothelial cells via gap junctions. After transplantation of BM-MNC, this fosters hippocampal neurogenesis and enhancement of neuronal function. Herein, we report the impact of transplanted BM-MNC on neural stem cells (NSC) in the brain. Surprisingly, direct transfer of water-soluble molecules from transplanted BM-MNC and peripheral mononuclear cells to NSC in the hippocampus was observed already 10 min after cell transplantation, and transfer from BM-MNC to GFAP-positive cortical astrocytes was also observed. In vitro investigations revealed that BM-MNC abolish the expression of hypoxia-inducible factor-1α in astrocytes. We suggest that the transient and direct transfer of water-soluble molecules between cells in circulation and NSC in the brain may be one of the biological mechanisms underlying the repair of brain function.

Pegylated Viologen Derivatives to Improve Performance of Aqueous Organic Redox Flow Battery

Renewable energy sources like wind and solar power are great alternatives for a clean way to produce electricity but have the inconvenience to fluctuate1. To address this issue and promote the implementation of renewables sources, scientists are developing new ways to store energy while production is at a maximum for a subsequent release when there is demand. Redox flow batteries (RFBs) are the most appropriate solution and are increasingly gaining attention for stationary, large scale electrochemical energy storage2,3. One variation of RFBs are aqueous organic redox flow batteries (AORFBs), where water-soluble organic molecules are use as the redox couple. Viologen type molecules are particularly well-suited as a negative potential species to develop cheaper and better AORFBs with great scalability, reversibility and long-term stability4.In this study, viologen derivatives were synthesized with various N-functional groups to explore the impact of the substituent on their solubility, viscosity and redox potential. We showed that the use of short chains of poly(ethylene glycol) improved the solubility of the viologens derivatives which could lead to batteries with higher capacity. The symmetric viologen (with two identical substituents) provided a great solubility in water and the formal potential was unaffected by the chemical nature of the substituents. We demonstrated that the 1,1’-(bisethylene glycol)-4,4’-bipyridium (PEG2-V-PEG2) showed the most promising properties with a high solubility (2.3 M in 1M KCl) and low viscosity (3.01 mPa*s at 1M). As such, this derivative was selected for further evaluation in an asymmetrical labs-scale RFB prototype cell versus bis(trimethylamoniumpropyl)ferrocene (BTMAP-Fc). The compound was studied at various concentrations to assess the maximum energy density that can be reached and the effect of concentration on cycling life by achieving a comparison to the symmetrical 1,1’-bis(3-sulfonatopropyl)-4,4’-bipyridium (SPr-V-SPr) at 0.5 M. Figure 1: Redox flow battery scheme using Viologen derivative as the negolyte and BTMAP-Fc as the posolyte Reference Shi, X., Qian, Y. and Yang, S. Fluctuation analysis of a complementary wind–solar energy system and integration for large scale hydrogen production. ACS Sustainable Chemistry & Engineering, 8(18), pp.7097-7110. (2020)Sánchez-Díez, E.; Ventosa, E.; Guarnieri, M.; Trovò, A.; Flox, C.; Marcilla, R.; Soavi, F.;Mazur, P.; Aranzabe, E.; Ferret, R., Redox flow batteries: Status and perspective towards sustainable stationary energy storage. Journal of Power Sources, 481, 1-23. (2021)Poullikkas, A., A comparative overview of large-scale battery systems for electricity storage. Renewable and Sustainable energy reviews, 27, pp.778-788. (2013)Gentil, S., Reynard, D. and Girault, H.H. Aqueous organic and redox-mediated redox flow batteries: a review. Current Opinion in Electrochemistry, 21, pp.7-13. (2020) Figure 1

(Invited) Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Heterogeneous catalysts consisting of iron cations incorporated into nitrogen-doped carbon (“Fe-N-C”) have received extensive attention as leading alternatives to Pt for the electrochemical oxygen reduction reaction (ORR). Fe-N-C catalysts host mononuclear nitrogen-ligated active centers, FeNx, that frequently coexist with agglomerated Fe species. Although FeNx are the dominant active centers for ORR and other electrocatalytic reactions, the relative accuracies of methods to quantify them are still debated. Here, we develop a kinetic probe-reaction approach to quantify FeNx centers and compare it with spectroscopic and molecular probe methods.Model Fe-N-C catalysts were synthesized to contain mononuclear FeNx species at low loadings (0.1–0.4 wt% bulk Fe) on solvent-accessible surfaces using a postsynthetic metalation approach and their Fe speciation was confirmed by low-temperature 57Fe Mössbauer spectroscopy. The initial rate of oxidation of a water-soluble hydroquinone molecule (per gcatalyst) catalyzed by these model materials correlates linearly with their density of FeNx centers, reflecting their intrinsic turnover frequency (TOF) for this reaction. This TOF, in turn, enables the estimation of the active-site density on any other Fe-N-C catalyst through a simple rate measurement. Kinetically determined FeNx site densities are measured on a suite of fourteen Fe-N-C catalysts with diverse synthetic origins and Fe speciation (0.3–8.4 wt% bulk Fe) and are compared with those estimated by low-temperature 57Fe Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical stripping of NO derived from NO2 −. Kinetic quantifications of FeNx centers correlate well with those obtained from the CO pulse chemisorption method and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification method. The kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and standard analytical instrumentation, offering an attractive complementary approach. Figure 1

Anthropogenic sources and liquid water drive secondary organic aerosol formation over the eastern Himalaya

Atmospheric aerosols have a serious impact on altering the radiation balance of the vulnerable Himalayan atmosphere. Organic aerosol (OA), one of the least resolved aerosol fractions in the Himalayas, constrain our competence to assess their climate impacts on the region. Here we investigate water-soluble OA molecules in PM10 samples collected from March to May 2019 at Lachung (27.4°N and 88.4°E), a high-altitude location (2700 m a.s.l.) in the eastern Himalaya, to elucidate their origin and formation process. The dominance of oxalic acid (C2) reveals that water-soluble OA in the eastern Himalaya are atmospherically processed. Backward air mass trajectories and mass concentration ratios of organic tracers as well as relationships with inorganic species (K+, SO42−, NH4+) suggest an anthropogenic origin of water-soluble OA with significant atmospheric processing during long-range transport to the eastern Himalayan region. We used the thermodynamic prediction of aerosol liquid water (ALW) to examine the formation mechanism of secondary OA (SOA) such as oxalic acid. Correlations of ALW with SO42− and water-soluble organic matter show that ALW is sensitive to both anthropogenic sulfate and water-soluble organic compounds in Himalayan aerosols. A strong positive relationship of C2 acid with predicted ALW provides evidence of extensive SOA formation from precursors via aqueous phase photochemical processes. This inference is supported by positive correlations of C2 acid relative abundance with diagnostic mass concentration ratios of C2 acid to precursor molecules. Our findings underscore the importance of anthropogenic sources and ALW in SOA formation through aqueous phase processes in the eastern Himalaya.

Co-crystallization of Hesperidin with different co-formers to enhance solubility, antioxidant and anti-inflammatory activities

Hesperidin (HSP) is a natural flavonoid glycoside with very low aqueous solubility and a slow dissolution rate, limiting its effectiveness. This study aims to address these issues by creating co-crystals of hesperidin with water-soluble small molecules (co-formers) such as L-arginine, glutathione, glycine, and nicotinamide. Using the solvent drop grinding method, we prepared three different molar ratios of hesperidin to co-formers (1:1, 1:3, and 1:5) and conducted in-vitro solubility and dissolution studies. The results demonstrated that the prepared co-crystals exhibited significantly enhanced solubility and dissolution rates compared to untreated hesperidin. Of particular note, the HSP co-crystals formula (HSP: L-arg 1:5) displayed approximately 4.5 times higher dissolution than pure hesperidin. Further analysis using FTIR, powder x-ray diffraction patterns, and DSC thermograms validated the formation of co-crystals between HSP and L-arginine. Additionally, co-crystallization with L-arginine improved the in vitro anti-inflammatory and antioxidant activities of hesperidin compared to the untreated drug. This study highlights the potential of using water-soluble small molecules (co-formers) through co-crystallization to enhance the solubility, dissolution, and biological activities of poorly water-soluble drugs. Furthermore, in vivo studies are crucial to validate these promising results.

Primordial aqueous alteration recorded in water-soluble organic molecules from the carbonaceous asteroid (162173) Ryugu

We report primordial aqueous alteration signatures in water-soluble organic molecules from the carbonaceous asteroid (162173) Ryugu by the Hayabusa2 spacecraft of JAXA. Newly identified low-molecular-weight hydroxy acids (HO-R-COOH) and dicarboxylic acids (HOOC-R-COOH), such as glycolic acid, lactic acid, glyceric acid, oxalic acid, and succinic acid, are predominant in samples from the two touchdown locations at Ryugu. The quantitative and qualitative profiles for the hydrophilic molecules between the two sampling locations shows similar trends within the order of ppb (parts per billion) to ppm (parts per million). A wide variety of structural isomers, including α- and β-hydroxy acids, are observed among the hydrophilic molecules. We also identify pyruvic acid and dihydroxy and tricarboxylic acids, which are biochemically important intermediates relevant to molecular evolution, such as the primordial TCA (tricarboxylic acid) cycle. Here, we find evidence that the asteroid Ryugu samples underwent substantial aqueous alteration, as revealed by the presence of malonic acid during keto–enol tautomerism in the dicarboxylic acid profile. The comprehensive data suggest the presence of a series for water-soluble organic molecules in the regolith of Ryugu and evidence of signatures in coevolutionary aqueous alteration between water and organics in this carbonaceous asteroid.

The membrane transporter SLC25A48 enables transport of choline into human mitochondria

Choline has important physiological functions as a precursor for essential cell components, signaling molecules, phospholipids, and the neurotransmitter acetylcholine. Choline is a water-soluble charged molecule requiring transport proteins to cross biological membranes. Although transporters continue to be identified, membrane transport of choline is incompletely understood and knowledge about choline transport into intracellular organelles such as mitochondria remains limited. Here we show that SLC25A48 imports choline into human mitochondria. Human loss-of-function mutations in SLC25A48 show impaired choline transport into mitochondria and are associated with elevated urine and plasma choline levels. Thus, our studies may have implications for understanding and treating conditions related to choline metabolism.

Molecular Modelling Comparisons, Optical and Band Gap Characterisation of 4-Sulfocalix[4]arene Thin Film

The advantageous property of water-soluble calixarenes is their ability to form stable complexes with inorganic guest molecules. Due to these attributes, their application in areas including molecular recognition, sensing, and supramolecular chemistry is extraordinarily alluring. The 4-sulfocalix[4]arene (SC[4]) is a water-soluble molecule and a derivative of the calixarene family that has both aromatic rings and sulfonate groups. The thin films were prepared using a spin-coating technique and characterised by Ultraviolet-Visible Spectroscopy (UV-Vis). By employing the Corey-Pauling-Koltun (CPK) model in conjunction with density functional theory (DFT), the height and diameter of SC[4] were precisely determined by devotedly representing its molecular shape and size. Then, the calixarene thin film’s optical properties and light absorption by the thin film were determined using the absorbance graph and Beer-Lambert law equation. The band gap energy of the thin film was determined to be equal to 4.44 eV through the Tauc-plot method. These results substantiate the integration of CPK models validated using DFT for measuring the size of SC[4] molecules and characterising the thin film’s optical characteristics. In a nutshell, the implementation of the CPK models was validated with DFT to determine the height and diameter of the SC[4] and the optical characterisation of its thin film was thoroughly determined in this study. The results obtained from this study are not only essential for understanding the properties of SC [4] but also inspire further research for multiple applications such as molecular recognition, adsorption and supramolecular chemistry.

Comparison of Tetraselmis suecica Cell Disruption Techniques: Kinetic Study and Extraction of Hydrosoluble Compounds

The optimization of cell disruption is a critical step in microalgal biorefineries. We used the same batch of Tetraselmis suecica culture to compare two mechanical cell disruption techniques, focusing on the extraction yield of water-soluble molecules. The conditions for high-pressure homogenization (HPH) studied were two passes at a moderate pressure of 300 bars. For ultrasound (US) treatment, we used an amplitude of 20% (equivalent to 100 W) for 25 min. These conditions were chosen on the basis of a preliminary screen of extraction conditions. HPH extracted proteins and pigments more efficiently than US, whereas US was superior for uronic acid extraction. Interestingly, the two methods had similar extraction yields for carbohydrates under the studied conditions. We also analyzed the kinetics of molecule release by considering the centrifugation time lag for HPH and applying a first-order kinetic model for US. HPH outperformed US in terms of the immediate extraction and release of molecules.

Transforming the Stability, Encapsulation, and Sustained Release Properties of Calcium Alginate Beads through Gel-Confined Coacervation.

Calcium alginate (Ca2+/alginate) gel beads find use in diverse applications, ranging from drug delivery and tissue engineering to bioprocessing, food formulation, and agriculture. Unless modified, however, these gels have limited stability in alkaline media (including phosphate buffers), and their high solute permeability limits their ability to efficiently encapsulate and slowly release water-soluble small molecules. Here, we show how these limitations can be addressed by mixing the alginate solutions used in the bead preparation with the nontoxic anionic polymer polyphosphate (PP). Upon complexing Ca2+ ions, PP undergoes complex coacervation (i.e., liquid/liquid phase separation into a Ca2+/PP-rich coacervate phase and a dilute supernatant phase). At lower PP concentrations, the Ca2+/PP coacervate appears to simply remain dispersed within the beads. Though its presence makes the beads more stable in alkaline media (phosphate-buffered saline and seawater), it has little impact on the bead stiffness, morphology, and (at least in the absence of substantial payload/coacervate association) encapsulation and release properties. When the PP concentrations exceed a critical value, however, Ca2+/PP coacervation within the gelling Ca2+/alginate beads collapses the resulting beads into more compact, interpenetrating polymer networks. Besides their enhanced stability to alkaline environments, these hybrid beads exhibit irregular morphologies with wrinkled and dimpled surface structures and macroscopic (closed) internal pores, and their collapse into these polymer-rich networks also makes them significantly stiffer than their PP-free counterparts. Crucially, these beads also exhibit a much lower solute permeability, which enables highly efficient encapsulation and multiday release of water-soluble small molecules (with the beads encapsulating >90% of the added model payload and sustaining its release over 3-5 d). Collectively, these findings provide a mild and simple (single-step) pathway to generating ionically cross-linked alginate beads with significantly enhanced stability, encapsulation efficiency, and sustained release.

Bis-butoxyphenyl dipyridine cation with high affinity for PF6−: Enhancement of solid fluorescence and inhibits Escherichia coli and Staphylococcus aureus activity through anion-π+ interactions

The contamination of anions and the overuse of antibiotics pose significant hazards to human health. Excess anions can cause serious damage to organisms and the natural environment, while the misuse of antibiotics has led to the emergence of multi-drug resistant bacteria. Therefore, it is important to develop multifunctional fluorescent sensing devices that integrate the rapid and sensitive detection of specific anions and that exhibit excellent antimicrobial activity against multi-resistant bacteria. This study describes the synthesis of three water-soluble cationic fluorescent molecules, DPPT-R (R = 5C, 6C, 7C). Their structures were characterized using 1H NMR spectroscopy, HRMS, and single crystal X-ray diffraction. Spectroscopic properties of the probes were recorded using UV–visible absorption and fluorescence spectroscopy. The recognition mode and mechanism of the fluorescent probes towards PF6− were investigated. Under aqueous solution conditions involves the PF6− induced aggregation of the probe via strong electrostatic interactions, leading to fluorescence quenching. Adjusting the alkyl chain length of the probe can enhance the sensitivity for the detection of the target anions. The detection limits are 0.892 μM, 0.786 μM and 0.444 μM for R = 5C, 6C, 7C, respectively. In addition, DPPT-R and DPPT-R@PF6 exhibit good inhibitory activity and fluorescence imaging capability against methicillin-resistant Staphylococcus aureus and multidrug-resistant Escherichia coli. Among them, the side chain of DPPT-R@PF6 with an almost 90° bend may be more advantageous for membrane insertion, thus enhancing its antimicrobial activity. In particular, after DPPT-R and PF6− form the DPPT-R@PF6 complex, the complex enhances its solid-state fluorescence, intensity of bacterial fluorescence imaging, and antibacterial activity through anion-π+ interactions. Therefore, this study can provide a new strategy and theoretical basis for the design and application of multifunctional fluorescent sensing materials and antibacterial molecules based on electrostatic interactions and anion-π+ interactions.

Composite Hydrogel with Oleic Acid-Grafted Mesoporous Silica Nanoparticles for Enhanced Topical Delivery of Doxorubicin.

Mesoporous silica nanoparticles (MSNs) are inorganic nanocarriers presenting versatile properties and the possibility to deliver drug molecules via different routes of application. Their modification with lipids could diminish the burst release profile for water-soluble molecules. In the case of oleic acid (OA) as a lipid component, an improvement in skin penetration can be expected. Therefore, in the present study, aminopropyl-functionalized MSNs were modified with oleic acid through carbodiimide chemistry and were subsequently incorporated into a semisolid hydrogel for dermal delivery. Doxorubicin served as a model drug. The FT-IR and XRD analysis as well as the ninhydrin reaction showed the successful preparation of the proposed nanocarrier with a uniform particle size (352-449 nm) and negative zeta potential. Transmission electron microscopy was applied to evaluate any possible changes in morphology. High encapsulation efficiency (97.6 ± 1.8%) was achieved together with a sustained release profile over 48 h. The composite hydrogels containing the OA-modified nanoparticles were characterized by excellent physiochemical properties (pH of 6.9; occlusion factor of 53.9; spreadability of factor 2.87 and viscosity of 1486 Pa·s) for dermal application. The in vitro permeation study showed 2.35 fold improvement compared with the hydrogel containing free drug. In vitro cell studies showed that loading in OA-modified nanoparticles significantly improved doxorubicin's cytotoxic effects toward epidermoid carcinoma cells (A431). All of the results suggest that the prepared composite hydrogel has potential for dermal delivery of doxorubicin in the treatment of skin cancer.

Water-Ice Microstructures and Hydration States of Acridinium Iodide Studied by Phosphorescence Spectroscopy.

Ice has been suggested to have played a significant role in the origin of life partly owing to its ability to concentrate organic molecules and promote reaction efficiency. However, the techniques for studying organic molecules in ice are absorption-based, which limits the sensitivity of measurements. Here we introduce an emission-based method to study organic molecules in water ice: the phosphorescence displays high sensitivity depending on the hydration state of an organic salt probe, acridinium iodide (ADI). The designed ADI aqueous system exhibits phosphorescence that can be severely perturbed when the temperature is higher than 110 K at a concentration of the order of 10-5 M, indicating changes in hydration for ADI. Using the ADI phosphorescent probe, it is found that the microstructures of water ice, i.e., crystalline vs. glassy, can be strongly dictated by a trace amount (as low as 10-5 M) of water-soluble organic molecules. Consistent with cryoSEM images and temperature-dependent Raman spectral data, the ADI is dehydrated in more crystalline ice and hydrated in more glassy ice. The current investigation serves as a starting point for using more sensitive spectroscopic techniques for studying water-organics interactions at a much lower concentration and wider temperature range.