Low Molecular Weight Surfactants Research Articles

Novel fracturing fluid made of low molecular weight polymer and surfactant achieves proppant full suspension and filling entire area of hydraulic fractures

In large-scale hydraulic fracturing of unconventional reservoirs, high viscosity friction reducers (HVFR) which employ high concentration polymers of high molecular weight can improve proppant suspension, but still lack long-distance and long-time proppant transport capability. Herein, for the first time, we report a fracturing fluid made of self- assembled low molecular weight polymer and a surfactant (LMPS). When using only 0.1 wt% of the polymer, LMPS has a viscosity of 29.6 mPa·s (170 s−1, 25 ℃) and can achieve full suspension of 40/70 mesh sand at 80 ℃. LMPS can form robust short molecular chain networks through numerous self-assembling association sites, rather than relying on entanglement. Notably, it achieves a minimum loss tangent as low as 0.1 in the viscoelastic response, demonstrating its strong elastic characteristics. According to the creep-recovery test, the strain recovery rate (87.9 %) of LMPS at 0.2 wt% polymer concentration far exceeds that of the HVFR with a concentration as high as 10.1 %. This indicates that LMPS has a stronger deformation-resisting ability, thereby preventing proppant settling. Taking advantage of LMPS’ superior proppant suspension capability, proppant can move with the slurry to the whole fracture for placement, while the HVFR provides only 48 % height support of the fractures in the form of dunes. A field trial shows that at a polymer concentration of 0.2 wt%, LMPS can stably transport 20/40 mesh quartz sand under a slurry rate of 2.8 m3/min and a proppant concentration of 635 kg/m3 during the fracturing process.

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.

Effect of macromolecular sodium polyacrylate on the molecular structure and properties of polyvinyl butyral synthesized deep eutectic solvent

AbstractSodium polyacrylate (PAAS), a macromolecule surfactant, was employed in the synthesis of polyvinyl butyral (PVB) using a deep eutectic solvent (DES) as the catalyst. Contrasting with traditional low molecular weight surfactants, scanning electron microscopy (SEM) analysis has confirmed that PAAS enhanced the uniformity of PVB granules while minimizing PAAS residuals, facilitating the production of films with superior transparency and resistance to yellowing. Investigations into the effects of varying molecular weights, dosages of PAAS, and aging times on the properties of PVB revealed that an increase in PAAS molecular weight correspondingly raised the acetal degree (AD) of PVB without affecting the molecular weight of PVB itself. Furthermore, yhe dosage of PAAS significantly impacted the properties of PVB, whereas aging time exhibits minimal influence on the AD of PVB. 1H‐NMR analysis indicated that the structural stability of PVB is due to the dominance of meso acetal isomers, which improved its mechanical properties when synthesized with PAAS3 (molecular weight 60,000 g/mol), containing 91.5% hexamethylene cycloacetal. Notably, compared to PVB synthesized using sodium dodecyl sulphate (SDS), PVB synthesized with PAAS3 exhibits superior mechanical properties, with significantly improved tensile strength and elongation. This phenomenon is further elucidated by SEM images. A comparison between the optimized self‐made PVB and commercial PVB shows that the self‐made PVB performs better, highlighting the critical role of macromolecular PAAS in enhancing the structure and mechanical properties of PVB.

Polymeric surfactants with high acid values for emulsion type pressure-sensitive adhesives

Low molecular weight polymers with hydrophobic-carboxyl groups have been usually used as anionic surfactants in emulsion polymerization for coatings. However, such polymeric surfactants usually have low acid values below 200, because it is difficult to make high acid-value polymeric surfactants using a normal batch reactor. In this work, we polymerized high acid value polymeric surfactant having high acid values successfully up to 380 using CSTR (continuous stirring tank reactor). The synthesized polymeric surfactant was a random copolymer of P(BA-AA) and we applied them as anionic surfactants in making emulsion-type acrylic PSAs (Pressure-Sensitive Adhesives) to investigate the effects of high acid values on the adhesive properties. This CSTR can effectively control the composition and molecular weight of polymeric surfactants through varying monomer ratios, retention time, and initiator concentrations. The surface tension analysis and emulsion stability test indicated that the synthesized polymeric surfactants exhibited a similar levels of critical micelle concentration (CMC) and emulsion stability with other conventional anionic surfactants. Also, the adhesion property analysis showed that the PSA used high acid value polymeric surfactant resulting in superior adhesive properties and heat resistance than the PSAs used low acid value polymeric surfactant or conventional low molecular weight surfactant. It was very notable that polymeric surfactants having unusually high acid values above 300 because of their high contents of carboxylic acid groups could result in superior adhesive properties and heat resistance.

Effective pickering emulsifiers based on submicron carboxymethyl cellulose/chitosan polymer particles

In this study, cross-linked carboxymethyl cellulose/chitosan submicron particles were employed to facilitate the stabilization of Pickering emulsion. The polymer particles were prepared using the polyelectrolyte self-assembly method in conjunction with isocyanide based multicomponent reactions and the characteristics were obtained using: nuclear magnetic resonance, Fourier-transform infrared spectroscopy and dynamic light scattering. Atomic force microscopy revealed the heterogeneous structure of the resulting submicron particles with domains of 20–30 nm in size. The average diameter was found to be in the range of 229–378 nm and they were found to be suitable for the fabrication of oil/water Pickering emulsion when proceeded via the homogenization method followed by sonication. The results obtained revealed that carboxymethyl cellulose/chitosan particles significantly stabilized the droplets at the oil/water interface. Even at low particle concentrations of 0.3 g/L (which is close to that of low molecular weight surfactants) stable Pickering emulsions have been obtained. Additionally, the resulting emulsions showed a high level of stability with regard to changes in pH, temperature and ionic strength. The natural alkaloid piperine was used as a model compound to load the resulting particles, which possessed encapsulation efficiency of 90.6±0.4%. Furthermore, the in vitro release profile of piperine from the Pickering emulsion revealed a much-controlled release in both acidic and neutral media as compared to the unformulated piperine. Additional findings in this work revealed important information on the application of carboxymethyl cellulose/chitosan submicron particles as Pickering stabilizers for creation of new delivery systems.

Construction of fracturing fluid with excellent proppant transport capacity using low molecular weight hydrophobic association polymer and surfactant

Slick water fracturing fluid is widely used for fracturing unconventional reservoirs such as shale and tight gas, and it has aided in developing unconventional oil and gas reservoirs. However, the problem of slick water in terms of its weak proppant transport capacity has not been effectively solved. Conventional methods of increasing the proppant transport capacity of a fracturing fluid by increasing viscosity and pumping rate have resulted in serious reservoir damage and increased costs, showing more and more limitations. To address this issue, a low molecular weight polymer/surfactant (LMPS) fracturing fluid system was developed. LMPS increased the fluid elasticity through the interaction between the hydrophobic groups on the polymer and the surfactant while maintaining low viscosity, thus obtaining excellent proppant transport capacity. The low molecular weight polymer is a type of hydrophobic association water-soluble polymer (HAWSP) prepared by photoinitiation. Its viscosity-average molecular weight was determined to be 1.24 × 106 g/mol, much more than that of a typical drag reducer of traditional slick water (about 1 × 107 g/mol). The low molecular weight of HAWSP is conducive to preparation, dissolution, pumping, and reducing the damage of polymer to the reservoir. When 300 mg/L of sodium dodecyl benzene sulfonate (SDBS) surfactant was added to a 0.2 wt% HAWSP solution, it formed a robust self-assembled network that significantly enhanced the elasticity and raised the storage modulus G' from 0.11 to 5.95 Pa. The 20/40 mesh ceramsite proppant remained suspended in the LMPS solution (36 mPa·s) for 30 min, whereas ceramsite completely settled within 30 s in an ordinary linear polymer solution with similar viscosity. Simultaneously, despite having a lower molecular weight, the drag reduction rate test shows that the drag reduction performance of the LMPS fracturing fluid was similar to the tested conventional commercial linear polymer. The self-assembled network of HAWSP/surfactant can increase the viscoelasticity of the fracturing fluid, which is expected to overcome the weakness of insufficient proppant transport capacity of slick water, thus improving development efficiency of unconventional gas reservoirs.

Effect of Surfactant Type on Foaming Properties of Milk

The presence of low molecular weight surfactants is suspected as one of the causes of poorly foaming milk, as they can interfere with milk proteins in the formation and stabilization of foam. Here, we explore the effect of various surfactants on the foaming properties of reconstituted skim milk powders. Each surfactant is different in electrical charge and molecular weight, including cleaning O- and E-coded chemicals, Tween 80, sucrose stearate, sodium oleate, sodium dodecyl sulfate, cetyltrimethylammonium bromide, benzalkonium chloride, and lecithin. The results showed that surfactants had different effects on foamability, foam stability, and structure, due to their varied effects on milk properties (e.g., pH, zeta potential, and surface tension). E-coded chemicals and sucrose stearate markedly decreased milk foamability, while the impact of Tween 80 and lecithin was considered detrimental to foam stability, as they mostly induced the production of large air bubbles in the foam.

Quantitative analysis and interfacial properties of mixed pea protein isolate-phospholipid adsorption layer

Proteins and low-molecular-weight (LMW) surfactants are widely used for the physical stabilization of many emulsion-based food products. This study investigated the oil-water interfacial behavior between pea protein isolate (PPI) and phospholipid (PL). The emulsions prepared with different concentrations of PPI and PL were stabilized by their synergetic or competitive adsorption at the oil-water interface. In addition, the quantitative proteomics results could illustrate the displacements of proteins by PL. The result showed that the vicilin (7S) could be preferentially displaced by PL. Meanwhile, the results of quartz crystal microbalance with dissipation (QCM-D) indicated the high affinity of legumin (11S) with PL, suggesting that the legumin possessed higher interfacial affinity to prevent interfacial displacement. This research could help us to understand the interaction and competitive adsorption between plant proteins and LMW surfactants profoundly, which could promote the development of plant protein-based emulsion beverage with improved stability.

Demulsification of water-in-oil emulsions stabilized with glycerol monostearate crystals

HypothesisColloidal particles can be used to generate water-in-oil (W/O) emulsions resistant against coalescence. Demulsification is possible with addition of low molecular weight surfactants to the emulsion continuous oil phase. Whether surfactants demulsify particle-stabilized W/O emulsions depends on their ability to modify the wettability of interfacially-bound particles. ExperimentalCrystals of glycerol monostearate (GMS) were prepared followed by water addition to generate GMS-stabilized W/O emulsions. The surfactants sorbitan monooleate (SMO), sorbitan monolaurate (SML), citric acid esters of monoglycerides (CITREM), sorbitan trioleate (STO), propylene glycol monolaurate (PgML), and polyglycerol polyricinoleate (PGPR) were added to the emulsion oil phase. Emulsion microstructure was characterized by light microscopy and cryo-scanning electron microscopy. Surfactant activity and crystal wetting were characterized by interfacial tension and three-phase contact angle measurements. Salt release from within the emulsions was used to assess demulsifier efficacy. FindingsEmulsions stabilized by platelet-like GMS crystals were generated. Of the six surfactants, SMO, SML, and CITREM were effective demulsifiers whereas STO, PgML, and PGPR were ineffective. The former three sufficiently modified the wettability of GMS crystals on the droplet surface, as they adsorbed to both the oil–water interface and GMS crystal surface. Emulsion destabilization was associated with faster NaCl release from the emulsion internal phase.

Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic Media

Fluorescent derivatives attract the attention of researchers for their use as sensors, photocatalysts and for the creation of functional materials. In order to create amphiphilic fluorescent derivatives of calixarenes, a fluorescein derivative containing oligoethylene glycol and propargyl groups was obtained. The resulting fluorescein derivative was introduced into three different (thia)calix[4]arene azide derivatives. For all synthesized compounds, the luminescence quantum yields have been established in different solvents. Using UV-visible spectroscopy, dynamic light scattering, as well as transmission and confocal microscopy, aggregation of macrocycles was studied. It was evaluated that calixarene derivatives with alkyl substituents form spherical aggregates, while symmetrical tetrafluorescein-containing thiacalix[4]arene forms extended worm-like aggregates. The macrocycle containing tetradecyl fragments was found to be the most efficient in photoredox ipso-oxidation of phenylboronic acid. In addition, it was shown that in a number of different electron donors (NEt3, DABCO and iPr2EtN), the photoredox ipso-oxidation proceeds best with triethylamine. It has been shown that a low molecular weight surfactant Triton-X100 can also improve the photocatalytic abilities of an oligoethylene glycol fluorescein derivative, thus showing the importance of a combination of micellar and photoredox catalysis.

Thoroughly review the recent progresses in improving O/W interfacial properties of proteins through various strategies.

Along with the future food market developing world widely, the personalized nutrition and rational function food design are found to be urgently attracted. Oil in a water (O/W) emulsion system has an excellent ability to maintain nutraceuticals and thus plays a promising role in producing future functional foods. Understanding the interfacial related mechanisms involved are essential for improving the quality of food products. Protein can effectively reduce interfacial tension and stable immiscible phases. The interfacial properties of proteins directly affect the emulsion qualities, which have gradually become a prospective topic. This review will first briefly discuss the interfacial-related fundamental factors of proteins. Next, the paper thoroughly overviewed current physical and chemical strategies tailored to improving the interfacial and emulsion properties of proteins. To be summarized, a higher flexibility could allow protein to be more easily unfolded and adsorbed onto the interface but could also possibly form a softer interfacial film. Several physical strategies, such as thermal, ultrasound and especially high-pressure homogenization are well applied to improve the interfacial properties. The interfacial behavior is also altered by various green chemical strategies, such as pH adjustment, covalent modification, and low molecular weight (LMW) surfactant addition. These strategies upgraded emulsion properties by increasing adsorption load, accelerating diffusion and adsorption rate, associated with lowering interfacial tension, and promoting interfacial protein interactions. Future researches targeted at elucidating interfacial-bulk protein interactions, unraveling interfacial behavior through in silico tools, exploring connection between interfacial-industrial processing properties, and clarifying the interfacial-sensory-digestive relationships of O/W emulsions is needed to develop emulsion applications.

The potential and mechanism of nonionic polyether surfactants dissolved in CO2 to improve the miscibility of CO2–hydrocarbon systems

Certain unique reservoir conditions and technical difficulties have greatly limited the use of CO2 miscible injection in unconventional reservoirs. Lowering the miscibility pressure to realize the miscibility of CO2 and crude oil is critical for achieving the most efficient recovery process. In this study, we investigated whether nonionic polyether surfactants could improve the miscibility of CO2 and hydrocarbons. And an improved experimental method for a quantitative evaluation of additive efficiencies in lowering the miscibility pressure was introduced for the first time. The dissolution behaviors of nonionic polyether surfactants in CO2 and phase behaviors of CO2–hydrocarbon systems with and without surfactant additives were conducted. The effects of surfactant structure and concentration and temperature on the solubility of nonionic polyether surfactants in CO2 along with the efficiency of miscibility pressure reduction for CO2–hydrocarbon systems were analyzed. The results showed that the polyoxypropylene alkyl ethers exhibited excellent potential for improving the miscibility of the CO2 and hydrocarbons, especially when low molecular weight surfactant molecules with high polyoxypropylene group content were used. The first-contact miscibility pressure (FCMP) of the mixed oil and CO2 could be reduced by as much as 22.51% with 3 wt% C4(PO)3 addition. Furthermore, a mechanistic understanding showed that the solubilization of the CO2 caused by polyether reverse micelles resulted in a reduction of miscibility pressures for CO2–hydrocarbon systems. The study results and the novel evaluation method provided guidance for designing and selecting appropriate additive structures to reduce miscibility pressures of CO2–oil systems and meet the CO2 miscible injection technology requirements.

Comb-like polyelectrolytes – New surfactants with controlled solubilization capacity

Cationic surface-active monomers with 11-acryloyloxyundecyl tail in quaternary ammonium group and the corresponding comb-like polyelectrolytes are investigated. The sources of quaternary ammonium were aliphatic amines (trimethylamine and triethylamine) or aromatic and aliphatic cyclic amines (N-methylpiperidine, N-methylmorpholine, pyridine, quinoline). The monomer to polymer transformation increases the solubilization capacity of surfactant in one order of magnitude. The comb-like polyelectrolytes are capable to effective solubilization of hydrophobic probe over the wide concentration range including extremely low concentrations of the polymer. There aren’t any precipitations of comb-like polyelectrolytes with temperature decrease unlike of many ionic low-molecular weight surfactants. Solubilization capacity of the hydrophobic probe by comb-like polyelectrolyte is slightly influenced by the molecular weight of the polymer and is determined by the nature of the ionic group of comb-like polyelectrolyte and counterion.

Phase Behaviour, Functionality, and Physicochemical Characteristics of Glycolipid Surfactants of Microbial Origin.

Growing demand for biosurfactants as environmentally friendly counterparts of chemically derived surfactants enhances the extensive search for surface-active compounds of biological (microbial) origin. The understanding of the physicochemical properties of biosurfactants such as surface tension reduction, dispersion, emulsifying, foaming or micelle formation is essential for the successful application of biosurfactants in many branches of industry. Glycolipids, which belong to the class of low molecular weight surfactants are currently gaining a lot of interest for industrial applications. For this reason, we focus mainly on this class of biosurfactants with particular emphasis on rhamnolipids and sophorolipids, the most studied of the glycolipids.

Stability of microemulsions containing red grape pomace extract obtained with a glycerol/sodium benzoate deep eutectic solvent

The valorization of red grape pomace is significant as grape is one of the most cultivated fruits worldwide and generated by-product quantities are enormous. For this purpose, numerous encapsulation techniques have been developed. However, the studies on microemulsions composed with deep eutectic solvent extracts are very limited. In this study, red grape pomace extract (RGPE) was first prepared by deep eutectic solvent extraction and characterized by HPLC analysis. Rutin, quercetin, catechin and caftaric acid were identified as the main non-pigment phenolic compounds. The RGPE was further encapsulated in microemulsions (MEs) following a low-energy approach using a mixture of low molecular weight surfactants, and the pseudo-ternary phase diagram was constructed. The physical and antioxidant stability of MEs containing 3–15 wt% RGPE was investigated for a period of 30 days. MEs were stable at an ambient temperature of 25 or 37 °C. The radical scavenging activity of encapsulated RGPE was improved up to 13% compared to the free extract. Our results indicate that microemulsions provide protection of valuable phenolic constituents especially under elevated temperature conditions and can therefore be used as systems for applications in nutraceuticals or cosmetics.

BIOSURFACTANTS FROM MARINE MICROORGANISMS: I. STRUCTURE AND FUNCTIONS

Marine microorganisms have unique metabolic and physiological characteristics and are an important source of new biomolecules such as biosurfactants. Low molecular weight surfactants are glycolipids, phospholipids, fatty acids, lipopeptides and lipoproteins, and high molecular weight surfactants are mixtures of heteropolysaccharides, lipopolysaccharides, lipoproteins and proteins. The main general of bacteria that synthesize biosurfactants are Pseudomonas, Bacillus, Acinetobacter, Antarctobacter, Rhodococcus, Halomonas, Alcanivorax, Pseudoalteromonas and Marinobacter. This review examines the structure and function of biosurfactants isolated from marine microorganisms.

Development of wet media milled purple sweet potato particle-stabilized pickering emulsions: The synergistic role of bioactives, starch and cellulose

Most food-grade Pickering particles nowadays are prepared using purified single-compound substances as starting materials. Fabrication of sustainable and multifunctional particles directly from raw biomass materials could avoid complexed isolation procedure, avoid use of harmful chemicals and maintain the bioactives in raw materials. Purple sweet potatoes, rich in bioactives, were used to produce purple sweet potato particles (PSPPs) via wet media milling, which effectively decreased the particle size of PSPPs from 3371 ± 109 nm to 312 ± 18 nm after 240 min of milling. And significant amounts of bioactives and their antioxidative activity were retained. Pickering emulsions (PSPP-Es) were successfully formed using PSPPs as Pickering stabilizers. These PSPP-Es exhibited good freeze-thaw and heating stability. Low pH (3–6) and strong ionic strength (150 mM–600 mM) conditions contributed to smaller droplet size (10–12 μm) and better storage stability of PSPP-Es. Besides, PSPP-Es possessed better lipid oxidative stability than Tween 80 (a low molecular weight surfactant) stabilized emulsion due to presence of intrinsic antioxidants. This work would facilitate the development of Pickering stabilizers with outstanding emulsifying ability, high food safety, and functional properties directly from whole grain materials, and widen the application of whole grain particle-stabilized Pickering emulsions in food, cosmetics and pharmaceutical industry.

Influence of low molecular weight surfactants on the stability of model infant formula emulsions based on hydrolyzed rice protein

The emulsifying properties of rice protein ingredients, and their behaviour in the presence of other non-protein emulsifiers, are essential to support food applications. The objective of this study was to investigate the influence of different low molecular weight surfactants (LMWS) on the stability of model infant formula emulsions (10 g protein L−1, 35 g soybean oil L−1, 50 g carbohydrate L−1) based on a rice protein hydrolyzate (RPH). Inclusion of CITREM and DATEM, at concentrations greater than 1 g L−1, gave emulsions with mean fat globule diameters (D[4,3]) less than 1 μm with good creaming stability, while lecithin was less effective across the concentration range tested (i.e., 1–3 g L−1). Coalescence of the control emulsion was observed upon both storage (10 d at 4 °C) and heat treatment (95 °C × 5 min). Increasing CITREM concentration increased storage and heat stability of the emulsions, while addition of CITREM at 2 g L−1 facilitated the formation of a very stable product. This study provides a first insight into the potential of hydrolyzed rice protein to be used as a value-added ingredient in the production of nutritional beverages such as infant formula emulsions, and the influence of LMWS on the stability of such products.

Insights into the composition, structure-function relationship, and molecular organization of surfactants from spent coffee grounds

Macromolecular/polymeric constituents of surfactants and their self-assembly in aqueous solutions play a key role in their technologically relevant application such as stabilization of foams and emulsions. However, such information on coffee-based surfactants is scarce. The present study is first-of-its-kind in elucidating the chemical and molecular fingerprints of surfactants derived from spent coffee grounds (SCG). Initial part of the study involved estimation of the total proteins and sugars, and monosaccharide composition of high (HMW) and low molecular weight (LMW) surfactants derived from dry and defatted SCG, which in turn is the residue obtained after hot water brewing of roasted Robusta and Arabica coffee granules. The HMW surfactants had higher protein and sugar contents that were directly related to their foamability and foam stability, respectively. Mannose and arabinose were the major sugars identified in HMW surfactants. LMW surfactants showed lower protein and sugar contents and absence of arabinose. Thus, only the HMW surfactants were subjected to MALDI-TOF mass spectrometry, LC-MS-MS based protein profiling, circular dichroism spectroscopy, and small-angle X-ray scattering. The presence of quercetin-sugar complexes, protease, transferase, and acylated proteins and a β-turn type protein secondary structure were detected in the SCG-surfactants. The transition from lamellar to rod-shaped micellar structures was observed when the surfactant concentration in aqueous solution was increased from a lower concentration to its critical micelle concentration (0.2%–0.8%, w/v).

Cooperative organizations of small molecular surfactants and amphiphilic block copolymers: Roles of surfactants in the formation of binary co‐assemblies

AbstractThe construction of highly ordered organizations through self‐assembly is one of the most popular phenomena both in natural and artificial environments. Amphiphilic molecules are the most commonly used building blocks for the self‐assembly, which are conventionally known as amphiphilic low molecular weight surfactants with polar heads and nonpolar tails, or amphiphilic block copolymers (BCPs) consisting of covalently bonded hydrophilic and hydrophobic block chains. Compared with single surfactant self‐assembly system, binary amphiphiles co‐assembly systems composing of both small mass surfactants and amphiphilic BCPs feature high flexibilities and versatilities in materials designing and structure regulation, ascribing to the vast possibilities of intermolecular interactions within the systems and facile component modulations during the assembly processes. The amphiphilic features of the two kinds of molecules endow them with similar self‐assembly behaviors, while the unique and distinct characters of each kind of amphiphiles lead to various complex but highly diversified co‐assembly systems. According to the roles of the surfactant played in the co‐assembly system, in this review, we summarize the binary co‐assembly systems from three distinct types: 1) the co‐micellization system in which the surfactants are added into the BCPs assemblies as a self‐assembly assistant; 2) the co‐emulsification system in which the surfactants work as an emulsion stabilizer to assist and confine the assembly of BCPs in 3D geometries; 3) the co‐templating system where the individual micelles of both surfactant and BCPs are hierarchically arranged and distributed to guide the formation of hierarchical nanomaterials. Following this, the major potential applications of the nanomaterials synthesized from the binary amphiphiles in biological field are described. Finally, we shortly discuss the current challenges and future perspectives of the binary amphiphiles self‐assembly systems.