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We studied the co-assembly of an oppositely changed binary mixture of selenium-doped carbon quantum dots (Se-CQDs) and N,N-dimethyl octylamide-propyl tertiary amine (DOAPA) through turbidity, ζ potential measurement, and cryogenic transmission electron microscopy (cryo-TEM) with the aim of fabricating supramolecular assemblies with multiple dimensions and novel morphologies. The Se-CQD/DOAPA binary mixture exhibited abundant phase behavior, in which an isotropic phase (I1) was first observed, followed by turbidity (T), precipitation (P), and a second isotropic phase (I2), as the DOAPA concentration increased. Then we focused on investigating the morphologies of samples. In cryo-TEM observations, spherical aggregates were observed in all phase sequences, whereas the aggregates have different ζ potentials and sizes. In the I2 phase, interesting nanocapsule-like aggregates and spindle-like aggregates can be identified in addition to spherical aggregates. In combination with the rheological behaviors of the I2 phase solution and the detailed structure of the aggregates from enlarged cryo-TEM images, it is possible that the Se-CQDs and DOAPA co-assemble with novel network-like building blocks. The turbid solutions were found to be responsive to pH in phase P, and spherical aggregates were obtained at pH 6.5 but turned into vesicles when the pH reached 5.0. On the basis of these findings, CQDs and surfactants can be good structural building blocks for supramolecular structures, and the diverse morphologies of aggregates offer the prospect of multiple applications in the future.

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Microbial infections have become a great threat to human health and one of the main risks arises from direct contact with the surfaces contaminated by pathogenic microbes. Herein, a kind of hexagonal column interpenetrated spheres (HCISs) are fabricated by non-covalent assembly of plant gallic acid with quaternary ammonium surfactants. Different from one-time burst release of conventional antimicrobial agents, the HCIS acts like a "antimicrobial molecular bank" and releases the antimicrobial ingredients in a multistage way, leading to long-lasting antimicrobial performance. Taking advantage of strong hydrophobicity and adhesion, HCISs are applicable to various substrates and endowed with anti-water washing property, thus showing high in vitro antimicrobial efficiency (>99 %) even after being used for 10 cycles. Meanwhile, HCISs exhibit broad-spectrum antimicrobial activity against bacteria and fungi, and have good biocompatibility with mammalian cells. Such a low-cost and portable long-lasting antimicrobial agent meets the growing anti-infection demand in public spaces.

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Mercury ion (Hg2+) is one of the most toxic heavy metal ions and lowering the detection limit of Hg2+ is always a challenge in analytical chemistry and environmental analysis. In this work, sulfhydryl functionalized carbon quantum dots (HS-CQDs) were synthesized through a one-pot hydrothermal method. The obtained HS-CQDs were able to detect mercury ions Hg2+ rapidly and sensitively through fluorescence quenching, which may be ascribed to the formation of nonfluorescent ground-state complexes and electron transfer reaction between HS-CQDs and Hg2+. A modification of the HS-CQD surface by -SH was confirmed using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The HS-CQDs sensing system obtained a good linear relationship over a Hg2+ concentration ranging from 0.45 µM to 2.1 µM with a detection limit of 12 nM. Delightfully, the sensor has been successfully used to detect Hg2+ in real samples with satisfactory results. This means that the sensor has the potential to be used for testing actual samples.

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The detection of mitochondrial Cu2+ and cysteine is very important for investigating cellular functions or dysfunctions. In this study, we designed a novel cyclometalated iridium(iii) luminescence chemosensor Ir bearing a bidentate chelating pyrazolyl-pyridine ligand as a copper-specific receptor. The biocompatible and photostable Ir complex exhibited not only mitochondria-targeting properties but also an "on-off-on" type phosphorescence change for the reversible dual detection of Cu2+ and cysteine. Ir had a highly sensitive (detection limit = 20 nM) and selective sensor performance for Cu2+ in aqueous solution due to the formation of a non-phosphorescent Ir-Cu(ii) ensemble through 1 : 1 binding. According to the displacement approach, Ir was released from the Ir-Cu(ii) ensemble accompanied with "turn-on" phosphorescence in the presence of 0-10 µM cysteine, with a low detection limit of 54 nM. This "on-off-on" process could be accomplished within 30 s and repeated at least five times without significant loss of signal strength. Moreover, benefiting from its good permeability, low cytotoxicity, high efficiency, and anti-interference properties, Ir was found to be suitable for imaging and detecting mitochondrial Cu2+ and cysteine in living cells and zebrafish.

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Background: Postoperative cognitive dysfunction (POCD) is a great problem for anesthetized subjects and is associated with poor short- and long-term outcomes. We explored promising predictors for POCD in elderly patients after hip fracture surgery.Methods: Elderly subjects (aged ≥65 years) undergoing surgery for hip fracture were consecutively recruited. Neuropsychological assessments were performed 1 day preoperatively (baseline) and 7 days postoperatively, and POCD was defined using the 'Z scores' method. Clinical data and laboratory tests were compared between patients with and without POCD development. Binary univariate and multivariate logistic regression analyses were conducted for risk factor assessment. Receiver operating characteristic (ROC) curve analysis was performed to investigate the predictive value of malondialdehyde (MDA) on postoperative day 1 (POD1) for POCD.Results: A total of 198 patients were finally enrolled in the analysis and 51 patients exhibited POCD within 7 postoperative days, with an incidence rate of 25.8%. MDA expression on POD1 (OR: 1.12, 95%CI: 1.03-1.23, P=0.017) was the only independent risk factor for POCD according to the final multivariate logistic regression analysis. ROC curve analysis indicated that MDA on POD1 was a predictor for POCD, with an area under the curve (AUC) of 0.683 and 95%CI of 0.590-0.775 (P<0.001).Conclusions: In conclusion, we demonstrated that MDA on POD1 was an independent risk factor for POCD in elderly subjects undergoing hip fracture surgery.

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Coacervation is liquid-liquid phase separation ubiquitous in industrial applications and cellular biology. Inspired by cellular manipulation of coacervate droplets such as P granules, we report here a regulatory strategy to manipulate synthetic coacervation in a spatiotemporally controllable manner. Two oppositely charged small molecules are shown to phase separate into coacervate droplets in water as a result of electrostatic attraction, hydrophobic effect, and entropy. We identify a down regulator, ß-cyclodextrin, to disrupt the hydrophobic effect, thus dissolving the droplets, and an up regulator, amylase, to decompose ß-cyclodextrin, thus restoring the droplets. The regulation kinetics is followed in real time on a single-droplet level, revealing diffusion-limited dissolution and reaction-limited condensation, respectively, taking ∼4 s and 2-3 min. Versatility of this strategy to manipulate the coacervation is demonstrated in two aspects: spatially distributed coacervation in virtue of amylase-grafted hydrogel frameworks and coacervate transportation across membranes and hydrogel networks via a disassemble-to-pass strategy. The current regulatory pairs and strategies are anticipated to be general for a wide variety of synthetic self-assembly systems.

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BACKGROUND: Postoperative cognitive dysfunction (POCD) is a very common postoperative complication occurring mainly after high-risk surgery, especially in the elderly individuals. This study aimed to investigate potential risk factors for POCD in elderly patients after total joint arthroplasty (TJA). MATERIALS AND METHODS: A total of 257 eligible elderly patients (≥65 years) who were scheduled for elective TJA for osteoarthritis with general anesthesia were enrolled. An experienced psychiatrist was invited to evaluate the cognitive function at baseline (1 day before the surgery) and at day 7 after the surgery. Univariate and multiple logistic regression analyses were performed to screen risk factors associated with POCD. Receiver-operating characteristic curve analysis was performed to assess the predictive value of serum 25-hydroxyvitamin D [25(OH)D] expression for POCD. RESULTS: Of all the 257 enrolled patients, 55 (21.4%) developed POCD within 7 days after the surgery. Serum 25(OH)D level was the only independent risk factor associated with POCD (odds ratio: 1.77, 95% confidence interval: 1.13-2.78, P = 0.016) by multiple logistic regression analysis. The area under the curve of 25(OH)D for POCD was 0.687, with the cut-off value of 11.2 ng/mL, sensitivity of 41.82% and specificity of 78.71% respectively (95% confidence interval: 0.617-0.757, P < 0.001). CONCLUSIONS: Our results revealed that preoperative serum 25(OH)D level was an independent risk factor for POCD in elderly subjects after TJA.

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The surface structure of the trimeric surfactant tri(dodecyldimethylammonioacetoxy)diethyltriamine trichloride (DTAD) on mica and the interactions between two such DTAD-coated surfaces were determined using atomic force microscopy and a surface force balance. In an aqueous solution of 3 mM, 5 times the critical aggregation concentration (CAC), the surfaces are coated with wormlike micelles or hemimicelles and larger (∼80 nm) bilayer vesicles. Repulsive normal interactions between the surfaces indicate a net surface charge and a solution concentration of ions close to that expected from the CAC. Moreover, this surface coating is strongly lubricating up to some tens of atmospheres, attributed to the hydration-lubrication mechanism acting at the exposed, highly hydrated surfactant headgroups. Upon replacement of the DTAD solution with surfactant-free water, the surface structures have changed on the DTAD monolayers, which then jump into adhesive contact on approach, both in water and following addition of 0.1 M NaNO3. This trimeric surfactant monolayer, which is highly hydrophobic, is found to be positively charged, which is evident from the attraction between the DTAD monolayer and negatively charged bare mica across water. These monolayers are stable over days even under a salt solution. The stability is attributed to the several stabilization pathways available to DTAD on the mica surface.

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Despite efficacious antimicrobial activity, cationic oligomeric surfactants show strong skin irritation potential due to their larger cationic charge numbers and multiple hydrophobic chains. This work reports that the incorporation of α-, ß-, and γ-CDs with different cavity sizes can effectively improve the mildness of cationic ammonium trimeric surfactant DTAD with a star-shaped spacer while maintaining its high antibacterial activity. On the basis of the different cavity sizes of CDs and the asymmetry in the spacer of DTAD, the CD/DTAD mixtures form α-CD@DTAD, 2α-CD@DTAD, ß-CD@DTAD, and γ-CD@DTAD complexes. Compared to DTAD, these CD/DTAD complexes show much stronger self-assembly ability with much lower critical aggregation concentrations (CAC) and form more diverse aggregates with reduced zeta potential. Just above their CACs, the CD/DTAD complexes form vesicles or solid spherical aggregates of ∼50 nm and then transform into small micelles of ∼10 nm as the concentration increases. The strong self-assembly ability and the multiple sites of hydrogen bonds of the CD/DTAD complexes endow them with high antibacterial activity against E. coli, showing a very low minimum inhibitory concentration (2.22-2.48 µM) comparable to that of DTAD. In particular, the addition of CDs significantly reduces the abilities of DTAD in solubilizing zein (a skin model protein) and in binding with zein, and the mildness decreases in the order of 2α-CD@DTAD > ß-CD@DTAD > γ-CD@DTAD > α-CD@DTAD. This tendency depends on their different self-assembling structures, and the formation of vesicles is approved to be in favor of the improvement of the mildness.

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This work reports that cationic micelles formed by cationic trimeric, tetrameric, and hexameric surfactants bearing amide moieties in spacers can efficiently kill Gram-negative E. coli with a very low minimum inhibitory concentration (1.70-0.93 µM), and do not cause obvious toxicity to mammalian cells at the concentrations used. With the increase of the oligomerization degree, the antibacterial activity of the oligomeric surfactants increases, i.e., hexameric surfactant > tetrameric surfactant > trimeric surfactant. Isothermal titration microcalorimetry, scanning electron microscopy, and zeta potential results reveal that the cationic micelles interact with the cell membrane of E. coli through two processes. First, the integrity of outer membrane of E. coli is disrupted by the electrostatic interaction of the cationic ammonium groups of the surfactants with anionic groups of E. coli, resulting in loss of the barrier function of the outer membrane. The inner membrane then is disintegrated by the hydrophobic interaction of the surfactant hydrocarbon chains with the hydrophobic domains of the inner membrane, leading to the cytoplast leakage. The formation of micelles of these cationic oligomeric surfactants at very low concentration enables more efficient interaction with bacterial cell membrane, which endows the oligomeric surfactants with high antibacterial activity.

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Structural health monitoring (SHM) is challenged by massive data storage pressure and structural fault location. In response to these issues, a bio-inspired memory model that is embedded with a causality reasoning function is proposed for fault location. First, the SHM data for processing are divided into three temporal memory areas to control data volume reasonably. Second, the inherent potential of the causal relationships in structural state monitoring is mined. Causality and dependence indices are also proposed to establish the mechanism of quantitative description of the reason and result events. Third, a mechanism of causality reasoning is developed for the reason and result events to locate faults in a SHM system. Finally, a deformation experiment conducted on a steel spring plate demonstrates that the proposed model can be applied to real-time acquisition, compact data storage, and system fault location in a SHM system. Moreover, the model is compared with some typical methods based on an experimental benchmark dataset.

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The self-assembly of a 1% hydrophobically modified and 30% hydrolyzed polyacrylamide (C12PAM) with cationic star-shaped oligomeric surfactants has been investigated by isothermal titration microcalorimetry, turbidimetry, ζ potential, scanning electron microscopy, and (1)H NMR techniques. The oligomeric surfactants are composed of quaternary dodecyldimethylammonium ions with three or six hydrophobic chains connected by a polyamine spacer at the headgroup level, abbreviated as DTAD and PAHB, respectively. DTAD/C12PAM and PAHB/C12PAM mixed systems undergo the same aggregate transitions with increases in surfactant concentration from soluble networklike aggregates to precipitated denser and more cross-linked structures and then to soluble spherical aggregates. The networklike aggregates are generated at very low surfactant concentration. However, at the corresponding surfactant concentration without C12PAM, DTAD cannot form aggregates and PAHB forms only networklike aggregates with a very loose structure. The strong electrostatic and hydrophobic interaction of DTAD and PAHB with C12PAM and the hydrophobic interaction between the alkyl chains of DTAD and PAHB themselves evidently promote the formation of networklike aggregates. As the surfactant concentration increases, cationic surfactants become excessive. The molecular configuration is changed by the stronger hydrophobic association among the DTAD and PAHB molecules and the enhanced electrostatic repulsion between the mixed aggregates. Thus, the networklike aggregates transfer to spherical aggregates.

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Interactions of trianionic curcumin (Cur(3-)) with a series of cationic surfactants, monomeric surfactant dodecyl trimethylammonium bromide (DTAB), dimeric surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) (12-6-12) and trimeric surfactant tri(dodecyldimethylammonioacetoxy)diethyltriamine trichloride (DTAD), have been investigated in aqueous solution of pH 13.0. Surface tension and spectral measurements indicate that the cationic surfactants display a similar surfactant concentration dependent interaction process with Cur(3-), involving three interaction stages. At first the three cationic surfactants electrostatically bind on Cur(3-) to form the surfactant-Cur(3-) complex. Then the bound and unbound cationic surfactants with Cur(3-) aggregate into surfactant-Cur(3-) mixed micelles through hydrophobic interactions above the critical micelle concentration of the surfactants (CMCC) in the presence of Cur(3-). Finally excess unbound surfactants self-assemble into micelles like those without Cur(3-). For all the three surfactants, the addition of Cur(3-) only decreases the critical micelle concentration of 12-6-12 but does not affect the critical micelle concentration of DTAB and DTAD. As the oligomeric degree of surfactants increases, the intermolecular interaction of the cationic surfactants with Cur(3-) increases and the surfactant amount needed for Cur(3-) encapsulation decreases. Compared with 12-6-12, either the weaker interaction of DTAB with Cur(3-) or stronger interaction of DTAD with Cur(3-) limits the stability or solubility of Cur(3-) in surfactant micelles. Therefore, gemini surfactant 12-6-12 is the best choice to effectively suppress Cur(3-) degradation at very low concentrations. Isothermal titration microcalorimetry, surface tension and (1)H NMR results reveal that 12-6-12 and Cur(3-) form a (12-6-12)2-Cur(3-) complex and start to form micelles at extremely decreased concentrations, where either 12-6-12 or Cur(3-) works as a bridge linkage and the resultant structure exhibits the characteristics of oligomeric surfactants.

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Branched alkylbenzenesulfonate gemini surfactants: sodium 6,6'-(propane-1,3-diylbis(oxy))bis(3-(2-propylpentyl)benzenesulfonate) (C8BC3C8B), sodium 6,6'-(propane-1,3-diylbis(oxy))bis(3-(3,5,5-trimethylhexyl)benzenesulfonate) (C9BC3C9B), and sodium 6,6'-(propane-1,3-diylbis(oxy))bis(3-(2,4,4-trimethylpentan-2-yl)benzenesulfonate) (T-C8BC3C8B) have been synthesized. Their interfacial activity and aggregation behavior in aqueous solution were studied by surface/interface tension measurement, electrical conductivity, isothermal titration microcalorimetry, (1)H NMR spectroscopy, dynamic light scattering, steady-state fluorescence and cryogenic transmission electron microscopy. The critical aggregation concentration (CAC) and the minimum average surface area/molecule (A(min)) decrease with the decrease of the branching factor, i.e., in the order of T-C8BC3C8B, C8BC3C8B and C9BC3C9B. Moreover, alkyl side chain branches generate much more significant increases in CAC and A(min) for the gemini surfactants than single-chain surfactants. However, the branching factor does not change the air/water surface tension at CAC regularly. Instead, the air/water surface tension decreases with the increase of the carbon number of the hydrocarbon chains. In addition, it is noted that the branched gemini surfactants display high efficiency in reducing toluene/water interfacial tension. Interestingly, the increase in the branching factor leads to much more endothermic enthalpy of aggregation. All these three surfactants form spherical vesicles in aqueous solution and may present a parallel-displaced structure with a directional arrangement of the benzene ring in the vesicles.

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A star-shaped hexameric quaternary ammonium surfactant (PAHB), bearing six hydrophobic chains and six charged hydrophilic headgroups connected by an amide-type spacer group, was synthesized. The self-assembly behavior of the surfactant in aqueous solution was studied by surface tension, electrical conductivity, isothermal titration microcalorimetry, dynamic light scattering, cryogenic transmission electron microscopy, and NMR techniques. The results reveal that there are two critical aggregate concentrations during the process of aggregation, namely C(1) and C(2). The aggregate transitions are proved to be caused by the changes of the surfactant configuration through hydrophobic interaction among the hydrocarbon chains. Below C(1), PAHB may present a star-shaped molecular configuration due to intramolecular electrostatic repulsion among the charged headgroups, and large aggregates with network-like structure are observed. Between C(1) and C(2), the hydrophobic interaction among the hydrophobic chains may become stronger to make the hydrophobic chains of the PAHB molecules curve back and pack more closely, and then the network-like aggregates transfer to large spherical aggregates of ∼100 nm. Beyond C(2), the hydrophobic interaction may become strong enough to cause the PAHB molecular configuration to turn into a pyramid-like shape, resulting in the transition of the spherical large aggregates to spherical micelles of ∼10 nm. Interestingly, the PAHB displays high emulsification ability to linear fatty alkyls even at very low concentration.

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Monosulfuron-ester is a new, low rate, sulfonylurea herbicide that is being promoted for annual broadleaf and gramineal weed control; however, there is a lack of published information on its behavior in soils. The adsorption and desorption of monosulfuron-ester by seven type soils were measured using a batch equilibrium technique. The results showed that the Freundlich equation fitted its adsorption and desorption well, and the Freundlich constant values (K(f-ads)) ranged from 0.88 to 5.66. Adsorption isotherms were nonlinear with 1/n(f-ads) values < 1. Soil pH, organic matter (OM), and clay content were the main factors influencing its adsorption and desorption. Adsorption and desorption were negatively correlated with pH 4.0-8.0 while positively correlated with OM and clay content. The adsorption of monosulfuron-ester was mainly a physical process, because its free energy (deltaG) in seven soils was less than 40 kJ/mol. Monosulfuron-ester adsorption by three soils increased with increasing CaCl2 concentration using CaCl2 as a background electrolyte. Monosulfuron-ester desorption was hysteretic in all tested soils.

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Rapid and sensitive methods to detect proteins and protein denaturation have become increasingly needful in the field of proteomics, medical diagnostics, and biology. In this paper, we have reported the synthesis of a new cationic water-soluble conjugated polymer that contains fluorene and diene moieties in the backbone (PFDE) for protein identification by sensing an array of PFDE solutions in different ionic strengths using the linear discriminant analysis technique (LDA). The PFDE can form complexes with proteins by electrostatic and/or hydrophobic interactions and exhibits different fluorescence response. Three main factors contribute to the fluorescence response of PFDE, namely, the net charge density on the protein surface, the hydrophobic nature of the protein, and the metalloprotein characteristics. The denaturation of proteins can also be detected using PFDE as a fluorescent probe. The interactions between PFDE and proteins were also studied by dynamic light scattering (DLS) and isothermal titration microcalorimetry (ITC) techniques. In contrast to other methods based on conjugated polymers, the synthesis of a series of quencher or dye-labeled acceptors or protein substrates has been avoided in our method, which significantly reduces the cost and the synthetic complexity. Our method provides promising applications on protein identification and denaturation detection in a simple, fast, and label-free manner based on non-specific interaction-induced perturbation of PFDE fluorescence response.

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The effects of anionic surfactants on the aggregation-induced emission (AIE) feature of cationic M-silole molecules have been studied. The electrostatic binding of M-silole with the surfactants greatly promotes the aggregation of the mixtures. The M-silole/surfactant aggregates at 1:1 charge ratio exhibit the maximum fluorescence intensity. Excess surfactant molecules will distribute the M-silole molecules into different micelles and weaken the fluorescence. The fluorescence intensity of the mixed M-silole/surfactant aggregates can be effectively modulated by choosing different surfactants. The gemini surfactants display a much stronger ability of enhancing fluorescence intensity than do the single-chain surfactants. Especially, the gemini surfactant with benzene rings shows the best performance in enhancing fluorescence of M-silole due to both the strongest aggregation ability and the pi-pi interaction with M-silole.

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Two star-like trimeric cationic surfactants with amide groups in spacers, tri(dodecyldimethylammonioacetoxy)diethyltriamine trichloride (DTAD) and tri(dodecyldimethylammonioacetoxy)tris(2-aminoethyl)amine trichloride (DDAD), have been synthesized, and the aggregation behavior of the surfactants in aqueous solution has been investigated by surface tension, electrical conductivity, isothermal titration microcalorimetry, dynamic light scattering, cryogenic transmission electron microscopy, and NMR techniques. Typically, both the surfactants form vesicles just above critical aggregation concentration (CAC), and then the vesicles transfer to micelles gradually with an increase of the surfactant concentration. It is approved that the conformation of the surfactant molecules changes in this transition process. Just above the CAC, the hydrophobic chains of the surfactant molecules pack more loosely because of the rigid spacer and intramolecular electrostatic repulsion in the three-charged headgroup. With the increase of the surfactant concentration, hydrophobic interaction becomes strong enough to pack the hydrophobic tails tightly and turn the molecular conformation into a pyramid-like shape, thus leading to the vesicle to micelle transition.