Distribution of surface-active substances in the sea surface microlayers off the Malaysian peninsula.

The sea surface microlayer (SML), particularly in monsoon-influenced regions, remains largely unexplored. This study aims to determine the concentrations, enrichment, and factors controlling the enrichment processes of surface-active substances (SASs), which include surfactants, dissolved monosaccharides (MCHOs), polysaccharides (PCHOs), total dissolved carbohydrates (TDCHOs), and transparent exopolymer particles (TEPs) around the coastal area of Malaysian Peninsula. The SML samples and underlying water (ULW) from a depth of 1 m were collected during the southwest (August and September 2023) and northeast (November 2023) monsoons. Surfactants, TEPs, and dissolved carbohydrates were measured spectrometrically using methylene blue, the Alcian blue assay, and 2,4,6-Tri(2-pyridyl)-s-triazine (TPTZ), respectively. The results showed that stations influenced by anthropogenic activities were generally enriched with surfactants (Enrichment factor, EF = 1.40 ± 0.91) and carbohydrate species (TDCHOs = 1.38 ± 0.28, MCHOs = 1.54 ± 0.57, PCHOs = 1.85 ± 1.43). However, TEP enrichment was not observed in our study (EF = 0.68 ± 0.24). The SASs in the SML were correlated with their underlying concentrations, implying that transport from underlying water could be a major source of substances in the SML. High carbohydrate concentrations and enrichment were found during the northeast monsoon, implying that rain and runoff water affect concentrations in the SML. Besides, the enrichment of SASs persists at moderate wind speeds and is depleted at high wind speeds.

Intrinsic dynamics of emulsions: Experiments in microgravity on the International Space Station.

HYPOTHESIS: In order to understand the basic mechanisms affecting emulsion stability, the intrinsic dynamics of the drop population must be investigated. We hypothesize that transient ballistic motion can serve as a marker of interactions between drops. In 1G conditions, buoyancy-induced drop motion obscures these interactions. The microgravity condition onboard the International Space Station enable this investigation. EXPERIMENTS: We performed Diffusing Wave Spectroscopy (DWS) experiments in the ESA Soft Matter Dynamics (SMD) facility. We used Monte Carlo simulations of photon trajectory to support data analysis. The analysis framework was validated by ground-based characterizations of the initial drop size distribution (DSD) and the properties of the oil/water interface in the presence of surfactant. FINDINGS: We characterized the drop size distribution and found to be bi-disperse. Drop dynamics shows transient ballistic features at early times, reaching a stationary regime of primarily diffusion-dominated motion. This suggests different ageing mechanisms: immediately after emulsification, the main mechanism is coalescence or aggregation between small drops. However at later times, ageing proceeds via coalescence or aggregation of small with large drops in some emulsions. Our results elucidate new processes relevant to emulsion stability with potential impact on industrial processes on Earth, as well as enabling technologies for space exploration.

Investigation of keratolytic impact of synthetic bolalipids on skin penetration of a model hydrophilic permeant.

Synthetic single-chain bolalipids (SSCBs) are novel excipients in drug delivery, with potential as stabilizers or solubilizers. However, their impact on skin barrier function has not been comprehensively studied. Therefore, two SSCBs (PC-C24-PC and PC-C32-PC) were studied in aqueous systems for their impact on penetration of a model permeant into porcine skin. Concentrations of 0.05 - 5 % w/w were tested; PC-C24-PC formulations were low-viscosity liquids while PC-C32-PC formed viscous dispersions to gels at room temperature. Formulations were compared for their ability to enhance sodium fluorescein penetration (SF, 0.1 % w/w) into skin via tape stripping. Using NIR-densitometry, the effect of SSCB formulations on corneocyte cohesion was evaluated. Data were compared with phospholipid mixture Lipoid S-75, sodium dodecyl sulfate (SDS), and polyethylene glycol 12-hydroxystearate (PEG-HS), and distilled water as negative control. Contrary to the hypothesis, both SSCBs failed to increase SF penetration into the stratum corneum, but rather showed a significant decrease in penetration depth compared to water. Both SSCBs exhibited a keratolytic effect at 5 % w/w, leading to substantial removal of proteins from the skin surface. Consequently, SSCBs may not enhance penetration of hydrophilic drugs into skin, but could be used as keratolytic agents.

Insulin fibrillation under physicochemical parameters of bioprocessing and intervention by peptides and surface-active agents.

Even after the centenary celebration of insulin discovery, there prevail challenges concerning insulin aggregation, not only after repeated administration but also during industrial production, storage, transport, and delivery, significantly impacting protein quality, efficacy, and effectiveness. The aggregation reduces insulin bioavailability, increasing the risk of heightened immunogenicity, posing a threat to patient health, and creating a dent in the golden success story of insulin therapy. Insulin experiences various physicochemical and mechanical stresses due to modulations in pH, temperature, ionic strength, agitation, shear, and surface chemistry, during the upstream and downstream bioprocessing, resulting in insulin unfolding and subsequent fibrillation. This has fueled research in the pharmaceutical industry and academia to unveil the mechanistic insights of insulin aggregation in an attempt to devise rational strategies to regulate this unwanted phenomenon. The present review briefly describes the impacts of environmental factors of bioprocessing on the stability of insulin and correlates with various intermolecular interactions, particularly hydrophobic and electrostatic forces. The aggregation-prone regions of insulin are identified and interrelated with biophysical changes during stress conditions. The quest for novel additives, surface-active agents, and bioderived peptides in decelerating insulin aggregation, which results in overall structural stability, is described. We hope this review will help tackle the real-world challenges of insulin aggregation encountered during bioprocessing, ensuring safer, stable, and globally accessible insulin for efficient management of diabetes.

PFAS distribution in cascade derived foam at wastewater treatment plants: The role of non-linear drainage, collapse induced enrichment, and implications for removal.

Per- and polyfluorinated alkyl substances (PFAS) enrichment in foam was investigated for the first time at a wastewater treatment plant cascade. A novel sampling device was utilized to allow spatial and temporal heterogeneity in PFAS concentrations and liquid content to be characterized. Concentrations of 8 PFAS compounds were normalized to liquid content and fit to a power law model revealing strong correlation (R2 = 0.91) between drainage induced enrichment and PFAS molar volume. Short chain PFAS such as perfluorobutanoate (PFBA) exhibited minor to no enrichment factors in foam (0.24-5.9) compared to effluent concentrations across the range of foam liquid contents (0.28-6.24 %), while long chain compounds such as perfluorooctane sulfonate (PFOS) became highly enriched with factors of 295-143,000. A conceptual model is proposed to explain higher than expected enrichment of more surface-active PFAS relative to liquid content, which combines continuous partitioning of PFAS to air bubbles during foam formation with additional partitioning during non-linear drainage and foam collapse, both controlled by their affinity for the air-water interface. Scoping calculations suggest the majority of PFOS and other long chain PFAS may be removed if foam is continuously collected with potential to reduce waste volume under economic barriers for current destructive technologies.

Electroactive biofilters outperform inert biofilters for treating surfactant-polluted wastewater by means of selecting a low-growth yield microbial community.

Electrobioremediation is one of the most innovative disciplines for treating organic pollutants and it is based on the ability of electroactive bacteria to exchange electrons with electroconductive materials. Electroactive biofilters have been demonstrated to be efficient for treating urban wastewater with a low footprint; however, their application can be expanded for treating industrial wastewater containing significant concentrations (2.4 %vol) of commercial surfactants (containing lauryl sulfate, lauryl ether sulfate, cocamydopropyl betaine, and dodecylbenzene sulfonate, among others). Our electroactive biofilter outperformed a conventional inert biofilter made of gravel for all tested conditions, reaching removal rates as high as 4.5 kg COD/m3bed·day and withstood Organic Loading Rates as high as 9 Kg COD/m3·d without significantly affecting removal efficiency. The biomass accumulation reduced available bed volume in the electroactive biofilter just by 39 %, while the gravel biofilter decreased by 80 %. Regarding microbial communities, anaerobic and electroactive bacteria represented a substantial proportion of the total population in the electroactive biofilter. Pseudomonas was the dominant genus, while Cupriavidus, Shewanella, Citrobacter, Desulfovibrio, and Arcobacter were potential electroactive strains found in relevant proportions. The microbial community's composition might be the key to understanding how high removal rates can coexist with limited biomass production, making electroactive biofilters a promising strategy to overcome classical biofilter limitations.

Highly 002-Oriented Dendrite-Free Anode Achieved by Enhanced Interfacial Electrostatic Adsorption for Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries (AZIBs) are gaining recognition as promising next-generation energy storage solution, due to their intrinsic safety and low cost. Nevertheless, the advancement of AZIBs is greatly limited by the abnormal growth of zinc dendrites during cycling. Electrolyte additives are effective at suppressing zinc dendrites, but there is currently no effective additive screening criterion. Herein, we propose employing the interfacial electrostatic adsorption strength of zinc ions for the initial screening of additives. Subsequently, dendrite-free plating is achieved by employing the anionic surfactant sodium dodecyl benzenesulfonate (SDBS) to enhance electrostatic adsorption. The cycled zinc anode exhibited a dense plating morphology and a high (002) orientation (I002/I101 = 22). The Zn||MnO2 full cell with SDBS exhibited a capacity retention of 85% after 1000 cycles at 1 A g-1. Furthermore, an instantaneous nucleation model and continuous nucleation model (CNM) are constructed to reveal the microscale plating/stripping dynamics under the scenarios of weak adsorption and strong adsorption. The CNM accurately explains the self-optimizing reconstruction of electrodes resulting from enhanced electrostatic adsorption. Our exploration was extended to other anionic surfactants (sodium dodecyl sulfate and disodium laureiminodipropionate), confirming the effectiveness of strong electrostatic adsorption in the screening of electrolyte additives.

Surface Tension Manipulation with Visible Light through Sensitized Disequilibration of Photoswitchable Amphiphiles.

Azoarene isomerization lies at the heart of numerous applications from catalysis or energy storage to photopharmacology. While efficient switching between their E and Z isomers predominantly relies on UV light, a recent study by Klajn and co-workers introduced visible light sensitization of E azoarenes and subsequent isomerization as a tool coined disequilibration by sensitization under confinement (DESC) to obtain high yields of the Z isomer. This host-guest approach is, however, still constrained to minimally substituted azoarenes with limited applicability in advanced molecular systems. Herein, we expand DESC for the assembly of surfactants at the air-water interface. Leveraging our expertise with photoswitchable amphiphiles, we induce substantial alterations of water's surface tension through reversible arylazopyrazole isomerization. After studying the binding of charged surfactants to the host, we find that the surface activity differences upon visible light irradiation for both isomers are comparable to those obtained by UV light excitation. The method is demonstrated on a large concentration range and can be activated using green or red light, depending on the sensitizer chosen. The straightforward implementation of photoswitch sensitization in a complex molecular network showcases how DESC enables the improvement of existing systems and the development of novel applications driven by visible light.

Speed of lung inflation at birth influences the initiation of lung injury in preterm lambs.

Gas flow is fundamental for driving tidal ventilation and thus the speed of lung motion, but current bias flow settings to support the preterm lung after birth are without an evidence base. We aimed to determine the role of gas bias flow rates to generate positive pressure ventilation in initiating early lung injury pathways in the preterm lamb. Using slower speeds to inflate the lung during tidal ventilation (gas flow rates 4-6 L/min) did not impact lung mechanics, mechanical power or gas exchange compared to those currently used in clinical practice (8-10 L/min). Speed of pressure and volume change during inflation were faster with higher flow rates. Lower flow rates resulted in less bronchoalveolar fluid protein, better lung morphology and fewer detached epithelial cells. Overall, relative to unventilated fetal controls, there was greater protein change using 8-10 L/min, which was associated with enrichment of acute inflammatory and innate responses. Slowing the speed of lung motion by supporting the preterm lung from birth with lower flow rates than currently used clinically resulted in less lung injury without compromising tidal ventilation or gas exchange.

Ultrasonic destruction of surfactants.

This study investigates the effectiveness of ultrasonic (US) treatment in removing and mineralizing surfactants in wastewater. It examines the complex mechanisms and variables (acoustic conditions, solution temperature, initial dose, etc.) that affect sonolytic processes. The effect of water matrix components (such as salts and the presence of secondary pollutants) on process performance is thoroughly investigated. Various treatments are analyzed through a detailed comparison of synergistic hybridization processes. The study also provides a comprehensive review of current environmental applications and explores potential directions for surfactant degradation using ultrasound. Insightful information is presented to advance sustainable wastewater treatment techniques. The literature review clearly reveals the promising future of sonotreatment for degrading various surfactants under different conditions. The use of multifrequency mechanisms and the integration of other advanced oxidation processes (AOPs) with the US process have significantly enhanced the energy efficiency of the sonochemical system. Additionally, the results highlight the need to focus on developing new sonoreactor designs, identifying degradation intermediates, and hybridizing the sonochemical system under innovative operating conditions.

Determining the Role of Surfactant on the Cytosolic Delivery of DNA Cross-Linked Micelles.

Nucleic Acid Nanocapsules (NANs) are nucleic acid nanostructures that radially display oligonucleotides on the surface of cross-linked surfactant micelles. Their chemical makeup affords the stimuli-responsive release of therapeutically active DNA-surfactant conjugates into the cells. While NANs have so far demonstrated the effective cytosolic delivery of their nucleic acid cargo, as seen indirectly by their gene regulation capabilities, there remain gaps in the molecular understanding of how this process happens. Herein, we examine the enzymatic degradation of NANs and confirm the identity of the DNA-surfactant conjugates formed by using mass spectrometry (MS). With surface enhanced (resonance) Raman spectroscopy (SE(R)RS), we also provide evidence that the energy-independent translocation of such DNA-surfactant conjugates is contingent upon their release from the NAN structure, which, when intact, otherwise buries the hydrophobic surfactant tail in its interior. Such information suggests a critical role of the surfactant in the lipid disruption capability of the DNA surfactant conjugates generated from degradation of the NANs. Using NANs made with different tail lengths (C12 and C10), we show that this mechanism likely holds true despite significant differences in the physical properties (i.e., critical micelle concentration (CMC), surfactants per micelle, Nagg) of the resultant particles (C12 and C10 NANs). While the total cellular uptake efficiencies of C12 and C10 NANs are similar, there were differences observed in their cellular distribution and localized trafficking, even after ensuring that the total concentration of DNA was the same for both particles. Ultimately, C10 NANs appeared less diffuse within cells and colocalized less with lysosomes over time, achieving more significant knockdown of the target gene investigated, suggesting more effective endosomal escape. These differences indicate that the surfactant assembly and disassembly properties, including the number of surfactants per particle and the CMC can have important implications for the cellular delivery efficacy of DNA micelles and surfactant conjugates.

Exfoliation of Molecular Solids by the Synergy of Ultrasound and Use of Surfactants: A Novel Method Applied to Boric Acid.

Boric acid, H3BO3, is a molecular solid made up of layers held together by weak van der Waals forces. It can be considered a pseudo "2D" material, like graphite, compared to graphene. The key distinction is that within each individual layer, the molecular units are connected not only by strong covalent bonds but also by hydrogen bonds. Therefore, classic liquid exfoliation is not suitable for this material, and a specific method needs to be developed. Preliminary results of exfoliation of boric acid particles by combination of ultrasound and the use of surfactants are presented. Ultrasound provides the system with the energy needed for the process, and the surfactant can act to keep the crystalline flakes apart. A system consisting of a saturated solution and large excess solid residue of boric acid was treated in this way for a few hours at 40 °C in the presence of various sodium stearate, proving to be very promising, and an incipient exfoliation was achieved.

Marangoni flows triggered by cationic-anionic surfactant complexation.

HYPOTHESIS: The gradients in surfactant distribution at a fluid-fluid interface can induce fluid flow known as the Marangoni flow. Fluid interfaces found in biological and environmental systems are seldom clean, where mixtures of various surfactants are present. The presence of multi-component surfactant mixtures introduces the possibility of interactions among constituents, which may impact Marangoni flows and alter flow dynamics. EXPERIMENTS: We employed flow visualization, surface tension and reaction kinetic measurements, and numerical simulations to quantitatively investigate the Marangoni flows induced by the reacting surfactant mixtures. Different binary surfactant mixtures were utilized for comparative analysis. FINDINGS: The impact of surfactant interactions on Marangoni flows is confirmed through the observation of diverse complex flow patterns that result from the combination of oppositely charged surfactants in varying composition ratios and concentrations. Unique flow patterns originate from the composition-dependent interfacial phenomena upon mixing surfactants. Our findings provide vital insights that could be used to guide the development of effective oil remediation or the spreading of waterborne pathogens in contaminated regions.

Nanostructured gadolinium(III) micelles: Synthesis, characterization, cytotoxic activities, and MRI applications in vivo.

Gadolinium-based contrast agents (GBCAs) are used in around 40 % of MRI procedures. Despite initial perceptions of minimal risk, their long-term use has emphasized the need to reduce toxicity and develop more efficient GBCAs with extended blood retention. Advancements in nanomaterials have led to improved GBCAs, enhancing MRI diagnostics. This study synthesizes and characterizes nanostructured gadolinium(III) micelles as superior MRI contrast agents. The complexes, [Gd(L)2], where L is a ligand of the N-alkyl-N-methylglucamine surfactant series (L8, L10 or L12, L10), form nanostructured micelles in aqueous solution. Gd(L8)2 and Gd(L10)2 relaxivities remained stable across concentrations. Compared to Gd-DTPA, Gd(III) micelles showed enhanced T1-weighted MRI contrast. Gd(L12)2 micelles exhibited cytotoxicity against B16F10 melanoma cells (IC50 42.5 ± 2.2 µM) and L292L929 fibroblasts (IC50 52.0 ± 2.5 µM), with a selectivity index of 1.2. In vivo application in mice brain T2-weighted images suggests nanostructured Gd(III) micelles are promising MRI contrast agents for targeting healthy organs or tumors.

Impact of surfactant raw material variability on extrudate clarity appearance (transparency) in HME continuous manufacturing.

The appearance of an extrudate formulation was monitored during hot-melt extrusion (HME) continuous manufacturing over 3 days. The formulation matrix consisted of a polymeric component, copovidone, and a low molecular weight surfactant, polysorbate 80. Based on studies prior to the continuous manufacturing, the desired appearance of the target extrudate is translucent. Although process parameters such as feed rate and screw speed were fixed during the continuous manufacturing, the extrudate appearance changed over time from turbid to translucent. For root-cause investigation, the extrudates were analyzed offline by differential scanning calorimetry (DSC) and advanced polymer chromatography (APC™). Although the polysorbate 80 content of both turbid and translucent extrudates was within target, the glass transition temperature of the turbid extrudate was 2 °C above expected value. The observed turbidity was traced to lot-to-lot variability of the polysorbate 80 used in the continuous manufacturing, where APC™ analysis revealed that the relative content of the low molecular weight component varied from 23% to 27% in correlation with the evolution from turbid to translucent extrudates. This work stresses the importance of taking feeding material variability into account during continuous manufacturing.

Treatment of greywater and presence of microplastics in on-site systems.

Eight on-site greywater treatment facilities of four different types (A, B, C and D) were investigated. Three were commercially available package plants (A-C) and one was a conventional sand filter (D). The treatment unit of Type A consisted of a geotextile-fitted trickling filter and a sand filter bottom layer, the Type B consisted of packs of fibrous mineral wool filter materials, and the Type C consisted of a fine-meshed plastic filter. The treatment systems were assessed in terms of their removal efficiency for organic matter (e.g. BOD, COD, TOC), nutrients (nitrogen and phosphorus), surfactants, indicator bacteria (E. coli and enterococci) as well as microplastics. Systems A and D effectively reduced organic matter by >96% BOD, >94% COD and >90% TOC. Their effluent BOD was <29 mg/l. The BOD reduction in the treatment facilities of types B and C was in the range of 70-95%. Removal of anionic surfactants was >90% with effluent concentration <1 mg/l in all facilities. In general, the treatment systems were ineffective in removing E. coli and enterococci; the most efficient was the sand filter (type D), achieving 1.4-3.8 log10 for E. coli and 2.3-3.3 log10 for enterococci. Due to the high E. coli in the effluents, all the on-site systems were classified as Poor (score: 0-44) according to the water quality index (WQI) assessment. In two of the studied facilities, nine microplastic polymers were targeted (i.e. PVC, PS, PET, PE, PC, NG, PMMA, PP and PA6) and analyzed using the thermal extraction desorption gas chromatography-mass spectrometry (TED-GCMS) technique. PVC, PS, PET and PA6 were commonly detected in the influent and effluent. The effluent quality from type A and D systems was found to comply with the European Commission's guideline for the reuse of reclaimed water except for the indicator bacteria concentration.

Gemini surfactants as next-generation drug carriers in cancer management.

INTRODUCTION: Gemini surfactants (GS) are an elite class of amphiphilic molecules that have shown up as a potential candidate in the field of drug delivery because of their exceptional physicochemical properties. They comprise two hydrophilic headgroups connected by an adaptable spacer and hydrophobic tails that has shown promising results in delivering different therapeutic agents to cancer cells at preclinical level. However further studies are in demand to unlock the full potential of GS in this field. AREAS COVERED: This review summarizes the new advancements in GS as drug carriers in cancer therapy, their capacity to overcome conventional shortcomings and the demand for innovative approaches in disease treatment. A detailed list of GS-based formulations along with a brief description on oligomeric surfactants have also been provided in this review. This article summarizes data from studies identified through literature database searches including PubMed and Google Scholar (2010-2023). EXPERT OPINION: There are major challenges that need to be addressed in this field which restrict their progression toward clinical phase. Further research can focus on developing a theranostic system that can provide simultaneous real-time monitoring along with treatment care. Nevertheless, ensuring the safety parameters of these nanocarriers followed by their regulatory approval is a time-consuming and expensive process. A collaborative approach between regulatory bodies, research institutions, and pharmaceutical companies can speed up the process in the upcoming years.

Developing a Passive Dosing Method for Acute Aquatic Toxicity Tests of Cationic Surfactant Benzalkoniums (BACs).

Benzalkonium chlorides (BACs) have been of environmental concern due to their widespread use and potential harm. However, challenges arise in defining and controlling the exposure concentration (Cw) in aquatic toxicity tests involving BACs with a long alkyl chain (i.e., #C > 14). To address this, a novel passive dosing method was introduced in the 48 h-acute ecotoxicity test on Daphnia magna and compared to the conventional solvent-spiking method in terms of Cw stability and toxicity results. Among 13 sorbent materials tested for their sorption capacity, poly(ether sulfone) (PES) membrane was an optimal passive dosing reservoir, with equilibrium desorption of BACs to water achieved within 24 h. The Cw of BACs remained constant in both applied dosing methods during the test period. However, the Cw in solvent-spiking tests was lower than the nominal concentration for long-chain BACs, particularly at low exposure concentrations. Notably, the solvent-spiking tests indicated that the toxicity of BACs increased with alkyl chain length from C6 to 14, followed by a decline in toxicity from C14 to 18. In contrast, the passive dosing method displayed similar or slightly increasing toxicity levels of BACs from C14 to C18, indicating higher toxicity of C16 and C18-BACs than that inferred by the solvent spiking test. These findings emphasize the potential of applying this innovative passive dosing approach in aquatic toxicity tests to generate reliable and accurate toxicity data and support a comprehensive risk assessment of cationic surfactants.

Targeting CEBPA to restore cellular identity and tissue homeostasis in pulmonary fibrosis.

Fibrosis in the lung is thought to be driven by epithelial cell dysfunction and aberrant cell-cell interactions. Unveiling the molecular mechanisms of cellular plasticity and cell-cell interactions is imperative to elucidate lung regenerative capacity and aberrant repair in pulmonary fibrosis. By mining publicly available RNA-seq datasets, we identified loss of CCAAT enhancer-binding protein alpha (CEBPA) as a candidate contributor to idiopathic pulmonary fibrosis (IPF). We used conditional knockout mice, scRNA-seq, lung organoids, small-molecule inhibition and novel gene manipulation methods to investigate the role of CEBPA in lung fibrosis and repair. Long term (6 month+) of Cebpa loss in AT2 cells caused spontaneous fibrosis and increased susceptibility to bleomycin-induced fibrosis. Cebpa knockout in these mice significantly decreased AT2 cell numbers in the lung and reduced expression of surfactant homeostasis genes, while increasing inflammatory cell recruitment as well as upregulating S100a8/a9 in AT2 cells. In vivo treatment with an S100A8/A9 inhibitor alleviated experimental lung fibrosis. Restoring CEBPA expression in lung organoids ex vivo and during experimental lung fibrosis in vivo rescued CEBPA deficiency-mediated phenotypes. Our study establishes a direct mechanistic link between CEBPA repression, impaired AT2 cell identity, disrupted tissue homeostasis, and lung fibrosis.

Temperature dependence of the near infrared absorption spectrum of single-wall carbon nanotubes dispersed by sodium dodecyl sulfate in aqueous solution: experiments and molecular dynamics study.

CONTEXT: Single-wall carbon nanotubes (SWCNT) dispersed in water with the help of sodium dodecyl sulfate (SDS) surfactants exhibit a temperature dependent near infrared (NIR) exciton spectrum. Due to their biocompatibility and NIR spectrum falling within the transparent window for biological tissue, SWCNTs hold potential for sensing temperature inside cells. Here, we seek to elucidate the mechanism responsible for this temperature dependence, focusing on changes in the water coverage of the SWCNT as the surfactant structure changes with temperature. We compare optical absorption spectra in the UV-Vis-IR range and fully atomistic molecular dynamics (MD) simulations. The observed temperature dependence of the spectra for various SWCNTs may be attributed to changes in the dielectric environment and its impact on excitons. MD simulations reveal that the adsorbed SDS molecules effectively shield the SWCNT, with ~ 70% of water molecules removed from the first two adlayers; this coverage shows a modest temperature dependence. Although we are not able to directly demonstrate how this influences the NIR spectrum, this represents a potential pathway given the strong influence of the water environment on the excitons in SWCNTs. METHODS: Optical absorption measurements were carried out in the UV-Vis-NIR range using a Varian Cary 5000 spectrophotometer in a temperature-controlled environment. PeakFit™ v. 4.06 was used as peak-fitting program in the spectral range 900-1400 nm (890-1380 meV) as a function of the temperature. Fully atomistic molecular dynamics simulations were conducted using the NAMD2 package. The CHARMM force field comprising two-body bond stretching, three-body angle deformation, four-body dihedral angle deformation, and nonbonded interactions (electrostatic and Lennard-Jones 6-16 potentials) was employed.