Chain Length Of Molecules Research Articles

Molecular understanding of the self-assembly of an N-isopropylacrylamide delivery system for the loading and temperature-dependent release of curcumin

Global changes and drug abuse are forcing humanity to face various disease problems, and alternative therapies with safe natural substances have important research value. This paper combines various techniques in quantum chemical calculations and molecular simulations to provide molecular-level insight into the dynamics of the self-assembly of N-isopropylacrylamide (NIPAM) for loading curcumin (CUR). The results indicate that increasing the chain length of NIPAM molecules reduces their efficiency in encapsulating and locking CUR, and electrostatic interactions and van der Waals interactions are the main driving forces behind the evolution of system configurations in these processes. The isopropyl groups of NIPAM and the two phenolic ring planes of CUR are the main contact areas for the interaction between the two types of molecules. The thermosensitive effect of NIPAM can alter the distribution of isopropyl groups in NIPAM molecules around CUR. As a result, when the temperature rises from ambient temperature (300 K) to human characteristic temperature (310 K), the NIPAM-CUR interactions and radial distribution functions suggest that body temperature is more suitable for drug release. Our findings offer a vital theoretical foundation and practical guidance for researchers to develop temperature-sensitive drug delivery systems tailored for CUR, addressing its clinical application bottleneck.

On the role of surface stress in environment-assisted fracture

Abstract Environment effects in plasticity and fracture of metals, well studied for several decades, still pose many unanswered questions. A micro-mechanics explanation of how dislocation activity is influenced by the material surface state, that can answer these questions, has been elusive. We build on a recently discovered effect in metal cutting – organic monolayer embrittlement (OME) – wherein metal surfaces are rendered brittle by long-chain organic adsorbates, to explore how material state variables influence surface plasticity and fracture. In particular, cutting experiments with Al containing Self Assembled Monolayers (SAMs), show that the OME is controlled by surface stress (f) induced by the adsorbates. This is contrary to many instances of environment-assisted fracture which are usually attributed to surface energy changes, and wherein f is largely ignored. Other contributions include (a) a cantilever technique to measure surface stress, (b) demonstration of strong effect of SAM molecule chain length on f, (c) characterization of how dislocation activity at crack-tips is affected by adsorbate-induced f, and (d) large improvements in machining processes enabled by controlled environment-assisted fracture. We make the case that surface stress, due to adsorbates, likely influences all environmentally assisted cracking (EAC) phenomena, warranting a revisit of extant models of EAC.

Enhancing the sodium-ion storage performance of two-dimensional layered Ti3CN with a molecular riveting strategy

Adjustable 2D layered MXenes hold considerable promising as anode materials for sodium-ion batteries. However, the serious self-stacking and volume variation during sodium-ions insertion/extraction processes inevitably result in inferior rate capability and terrible cycle stability. Herein, we report a novel and effective “molecular riveting” strategy to simultaneously adjust the interlayer spacing and stabilize layered structure of Ti3CN (TCN), which is realized by riveting L-Aspartic acid/L-Glutamic acid/L-2-Aminoadipic acid (LAA/LGA/L2AA, abbreviated as LXA) molecules into interlayers of TCN (named as LAA-TCN/LGA-TCN/L2AA-TCN and abbreviated as LXA-TCN) to form strong amido (HN-C = O) bonds. The riveted LXA molecules between the interlayer of TCN contribute double effects of pillar and strain, achieving the maximum utilization of the 2D layered TCN. As consequences, the interlayer spacing of TCN can be broadened from 1.04 nm to 1.31 nm via altering the carbon chain length of LXA molecules, and the Na+ migration barrier can be reduced from 0.71 eV to 0.08 eV. Meanwhile, the L2AA-TCN with maximum interlayer spacing exhibits a significantly improved reversible capacity of 121.7 mAh/g (45.0 mAh/g for TCN) at 1.0 A/g. The constructed L2AA-TCN//NVP sodium-ion battery (SIB) displays excellent cycle stability with the capacity-retention of 96.6 % after 200 cycles at 10 C. This work opens a new way to broaden interlayer spacing and hinder enormous volume variation of 2D layered MXenes.

Positively Charged Silver and Gold Nanoparticles with Controllable Size Distribution for SERS Detection of Negatively Charged Molecules.

Surface-enhanced Raman spectroscopy (SERS) has been demonstrated as an ultrasensitive tool for various molecules. However, for the negatively charged molecules, the widely used SERS substrate [negatively charged Ag and Au nanoparticles (Ag or Au NPs (-)] showed either low sensitivity or poor stability. The best solution is to synthesize positively charged silver or gold nanoparticles [Ag or Au NPs (+)] with high stability and excellent SERS performance, which are currently unavailable. To this end, we revitalized the strategy of "charge reversal and seed growth". By selection of ascorbic acid as the reductant and surfactant, the surface charge of Ag or Au NP (-) seeds is adjusted to a balanced state, where the surface charge is negative enough to satisfy the stabilization of the NPs (-) but does not hinder the subsequent charge reversal. By optimization of the chain length and electric charge of polyamine molecules, the highly stable and size-controllable uniform Ag NPs (+) and Au NPs (+) were seed-growth synthesized with high reproducibility. More importantly, the SERS performance of both Ag NPs (+) and Au NPs (+) achieved the trace detection of negatively charged molecules at the level of 1 μg/L, demonstrating an improved SERS sensitivity of up to 3 orders of magnitude compared to the previously reported sensitivity. Promisingly, the introduction of polyamine-capped Ag NPs (+) and Au NPs (+) as SERS substrates with high stability (1 year shelf life) will significantly broaden the application of SERS.

The influence of the molecular chain length of PVA on the toughening mechanism of calcium silicate hydrates.

In recent years, polymers have been demonstrated to effectively toughen cementitious materials. However, the mechanism of interaction between the polymers and C-S-H at the nanoscale remains unclear, and the quantitative impact of the polymer chain length on toughening effectiveness is lacking in research. This study employs molecular dynamics techniques to examine the impact of the polyvinyl alcohol (PVA) chain length on the tensile performance and toughening mechanism of C-S-H. The toughening effect in both the X and Z directions exhibits an initial enhancement followed by a decline with increasing chain length. The optimal degrees of polymerization are determined to be 8 and 12 in the X and Z directions, respectively, resulting in an improvement of fracture energy by 146.7% and 29.5%, respectively. During the stretching process along the X and Z axes, the chain length of PVA molecules significantly influences the variation in the number of Ca⋯O bonds in the system, leading to different stress responses. Additionally, PVA molecules form C-O-Si bonds with the silicate layers of C-S-H, bridging the adjacent layers in a left-right or up-down manner. The toughening effect of PVA on C-S-H depends on the behavior of PVA molecules with different chain lengths, and there exists an optimal range of chain length for PVA, enabling it to enhance structural uniformity and adjust its own conformation to absorb strain energy. When the length of PVA molecular chains is too short, it can easily cause stress concentration in the system and its connection with silicates is not significant. Conversely, when the length of PVA molecular chains is too long, the large molecular structure restricts its extension in the defects of C-S-H, and as the stretching progresses, PVA molecules break and form numerous small segments, thereby losing the advantage of the chain length. This study provides a theoretical basis for the ability of polymers to toughen cementitious materials.

Two-phase imbibition of water-oil displacement in silica nanochannels

Classical imbibition theory cannot describe imbibition flow dynamics in nanoporous media in tight reservoirs and other industrial applications. In this work, the two-phase imbibition flow of water-oil displacement in silica nanochannels is studied by using molecular dynamics simulations. Interestingly, it is found that the two-phase imbibition length is shown to increase linearly with increasing time, which is inconsistent with the variation of single-phase imbibition length. The imbibition rate increases with the increase of external driving force, and the large channel height can accelerate the two-phase imbibition flow. As the increase of chain length of alkane molecules, the imbibition rate reduces gradually. The more oil-wet the silica surface is, the slower the imbibition rate is. Furthermore, we derive a theoretical model to describe the two-phase imbibition flow of water-oil displacement in nanochannels by considering the static force equilibrium of external driving forces, capillary forces, and viscous forces of the water and oil phases. The theoretical model can well describe the two-phase imbibition flow under various conditions using the pre-calculated oil-water interfacial tension, the viscosity of fluids, and the three-phase contact angle. This study will enrich the theoretical understanding of oil-water two-phase flow at nanoscale.

The structure effect on the physicochemical properties of Gemini surfactants used as viscosity reducer for heavy oil

The structure of surfactants is a key factor affecting their physicochemical properties. Our earlier work synthesized Gemini surfactants CEA-n with different structures. In this paper, the effects of polyether chain length, spacer groups number and the hydrophobic alkyl chain length of surfactants CEA-n on the interfacial properties, wettability, rheological properties and emulsion stability were fully studied in detail, and the effects of surfactant structure on their temperature tolerance and salt resistance properties were explored. The results showed that the variation of polyether chain length of surfactant molecules had the greatest impact on the interfacial tension (IFT), and the surfactants with longer alkyl chains had better interfacial film strength. The wettability of various surfactant systems was investigated by the sessile drop method, and the contact angle decreased remarkably from 92.6° to 17.9° in a short time (300 s) after adding surfactant CEA-6. Judging from the fluid type, each heavy oil emulsion system exhibited pseudoplastic fluid characteristics, and dilute shear phenomenon was observed in the range of 0–50 s−1 with an increasing shear ratio. The particle size, dispersibility and coalescence of the heavy oil O/W emulsion droplets of each system were observed through the microscopic images of the emulsions, and the factors affecting the stability of the emulsions were systematically studied by bottle test. It was found that the increase of oil-water ratio, surfactant concentration and mixing speed would improve the stability of O/W emulsions, while high temperature would accelerate the demulsification process. All these results established the structure-property relationship of surfactant molecules.

Studies of monomer–dimer equilibria of methylene blue as a probe to investigate the solute–solvent and hydrophobic interactions in aqueous solutions of polyethylene glycols at 298 K

Electronic absorption spectrums of methylene blue (MB) in the concentration range wherein monomer–dimer equilibria exist have been systematically investigated in aqueous solutions of polyethylene glycols (PEG's) having molar mass 400, 1000 and 4000 g∙mol–1, at 298 K. The data on the absorption spectrums (550–700 nm) of MB are resolved to obtain monomer and dimer spectrums as well the geometrical details of the species (such as oscillatory strength, dipole moment etc.) are calculated. The molar absorption extinction coefficients for monomer and dimer cations of MB, the dimer dissociation constant values are calculated as a function of PEG concentrations. It has been noted that, absorption maximum occurs at 664 ± 1 and 605 ± 1 nm, respectively, for monomer and dimers which do not get affected much by presence of polymeric molecules and the data show perfect obedience of Beer–Lambert's law. The changes in dimer geometry from sandwich type to end–on–end type have been studied by applying exciton theory of Kasha et al. The dimer dissociation constant values at finite as well for infinitely dilute concentration of PEG's exhibit orderly amendment with respect to molar mass of PEG's and alteration in chain length of molecules. We report the free energy changes of transfer of dimeric cations of different concentrations from water to aqueous solutions of PEG's of fixed concentration, that is, to probe the interactions of water and PEG molecules with a hope of getting information about salting–in/salting–out effects, as well of binding of dye molecules with PEG's. We have suggested complexation of end hydroxylic groups of PEG's with dimer cations. The results are further interpreted as salting–in of PEG complex with MB–dimers only in the limit of infinite dilution (solute–solvent interactions) while salting–out of these complexed species is observed as a function of MB–dimer concentration.

Dynamic impact and tensile strength characteristics of novel shear thickening fluid (STF)-treated fabric and modeling tensile strength using artificial intelligence

A series of shear thickening fluids (STFs) were prepared based on dispersed fumed silica in virgin polyethylene glycol (V/PEG) and modified PEGs by malonic acid (M/PEG) and tartaric acid (T/PEG). Rheological examination revealed that modification of PEG to a higher chain length of medium molecules remarkably improves STF peak viscosity and decreases the critical shear rate. High-velocity impact resistance of V/STF, M/STF, and T/STF-treated fabric was investigated at different layers and impact velocities and found significant improvement over neat fabric targets. Investigation of the results of two-layer samples showed the energy dissipation of V/STF, M/STF, and T/STF-treated fabrics at an impact velocity of 240 m/s is improved by 30.04%, 40.60%, and 46.06%, compared to the neat fabric, respectively. Furthermore, the tensile strength test revealed that these STFs fill the spaces between the fibers and make the fabric stronger and more resistant to breaking. In addition, a Linear/Nonlinear artificial intelligence regression analysis was performed. The results showed a strong correlation between composite mechanical response and speed. The proposed model can be further used to predict material behavior at other tensile speeds.

The alterations in granule, shell, blocklets, and molecular structure of pea starch induced by ultrasound

Understanding the alterations to starch multi-scale structure induced by ultrasound treatment can help in determining the effective application of ultrasound in functional-starch preparation. This study aimed to comprehensively characterize and understand the morphological, shell, lamellae, and molecular structures of pea starch granules treated by ultrasound under different temperatures. Scanning electron microscopy and X-ray diffraction analyses showed that UT (ultrasound treatment) did not change C-type of crystalline, but caused a pitted surface and endowed a looser structure and higher enzyme susceptibility as the temperature increased above 35 °C for pea starch granules. Fourier transform infrared spectroscopy and small-angle X-ray scattering analyses revealed that UT reduced the short-range ordering and increased the thickness of semi-crystalline and amorphous lamellae by inducing starch chain depolymerization, which was manifested by molecule weight and chain length distribution analysis. The sample ultrasound-treated at 45 °C had the higher proportion of B2 chains compared with the other ultrasound-treated samples because the higher ultrasonic temperature altered the disruption sites of starch chains.

Combined interaction of PCE chains lengths, C3A and water content in cementitious systems

In this study, the interaction of polycarboxylate ether-based water reducing admixture (PCE) molecule chain length variation with cements having different C3A contents and water content was investigated. For this purpose, a total of seven PCEs were synthesized following three different approaches, i.e., the main chain length changed at a constant side chain length, the side chain lengths varied at a constant main chain length, and both main and side chain lengths changed at a similar molecular weight. Paste and mortar mixtures were prepared with the PCEs and CEM I-42.5R type cements containing three different C3A contents (3.60%, 6.82%, 9.05%). The effects of above mentioned variables on the rheological properties and compressive strength of the paste/mortar mixtures were determined. The interaction of PCEs with cements having different C3A contents was investigated in detail by performing total organic carbon (TOC) and dynamic light scattering (DLS) analyses. The increase in the main and side chain lengths of PCE molecule up to a certain point positively affected the fresh properties of cementitious systems. Beyond a certain point (i.e. when main chain length is higher than 21 k), the increase in main chain length reduced the hydrodynamic diameter of PCE molecules (up to 32%), and decreased the dispersion performance of the admixture. The increment in side chain length (i.e. when side chain length is higher than 2100 g/mole), on the other hand, adversely affected the rheological properties, especially with high C3A cements.

Starch structural reasons for the effects of SSIIIa deficiency on the textural and digestive properties of cooked rice

Due to the urgent requirements for development of healthy diets, foods with slow digestibility combined with superior eating quality attract increasingly more attention. A high amylose indica rice mutant with starch synthase IIIa (SSIIIa) deficiency was reported to have higher resistant starch content, while how the starch structure affects the textural and digestive properties of the cooked rice have not been clarified. The ss3a starch had a significantly higher amylose content (AC), longer amylose intermediate chains but shorter amylose long chains, and also displayed a higher proportion of amylopectin A, B1, and B2 chains but a lower amount of B3 chains and shorter chain length of amylopectin molecules. The gelatinization temperatures and paste viscosity were decreased because of the increased AC and more amylopectin short chains, which further contributed to the harder texture of cooked rice. In addition, more amylose intermediate to long chains and longer amylose intermediate chains of the mutant resulted in the slow digestion rate of the fast-digestible fraction, and less amylopectin intermediate to long chains caused the complete digestion of cooked rice. These findings explained the nutritional benefits of the ss3a rice and its importance to the production of slow-digestive food products with acceptable texture.

Studies of frictional sliding contact by molecular dynamics assisted continuum mechanics

Lubricants are usually utilized to decrease wear, reduce friction, and release heat. Although the lubrication approximation originated from thin-film studies, it has limitations because of continuum mechanics assumptions. To overcome these limitations, for the first time, this article employs a hierarchical multiscale approach to study the frictional sliding contact considering elastohydrodynamic lubrication. This multiscale model consists of a molecular model of lubricant and a continuum model of sliding contact components. Specifically, the molecular dynamics method is used at the nanoscale to model the lubricant and analyze the friction coefficient in contacted surfaces. Through MD simulation, the effects of hydrocarbon chain lengths, temperature, and sliding velocity on a constant friction coefficient are studied in this article. The calculated friction coefficients from the molecular model are passed to the continuum model, in which the finite element method is employed to conduct stress and strain analysis of the sliding contact components. Although variations in the frictional sliding response are invariably coupled with the friction coefficients, the molecular-to-continuum hierarchical approach enables us to isolate the relative contributions from the chemical formulation of the lubricant and the temperature. This approach has further potential implications for the evaluation of tribological damage. The results demonstrate that an increase in temperature or the chain length of lubricant hydrocarbon molecules can significantly decrease the friction coefficient and, as a result, reduce contact shear stress, plastic deformation, and pile-up height.

In-situ polymerization of different molecular weight polyethylene glycol and maleic acid onto carbon fiber for reinforcing polyamide 66

ABSTRACT The interfacial adhesion character highly depends on the molecular interactions on the interface, including bond combination and molecular entanglement, and mobility for sharing load. In situ polymerization of different molecular weight polyethylene glycol (PEG) and maleic acid (MA) is used to form a hyperbranched polyester (HBPE) layer on an electrochemically oxidized carbon fiber (OCF) surface. It is found that more terminal hydroxyl groups are formed under the reaction at 280°C than that at other temperature. The branch extent and molecule chain length on the HBPE sizing reach balance by choice of 2000 molecular weight PEG monomer. HBPE as a film has uniform coverage on the OCF surface. The interlaminar shear strength of polyamide 66 composite reinforced with the sized OCF by in situ polymerization of 2000 molecular weight PEG and MA at 280°C is the optimal, which is enhanced to 90.5 MPa by 169% compared to unoxidized fiber and by 70% compared to OCF. The significant interfacial property improvement is attributed to the abundant terminal hydroxyl groups and appropriate chain length of the formed HBPE sizing, which enhanced optimally the interaction of fiber/sizing and sizing/matrix by balancing the contribution of molecular entanglement, deformation and covalent interconnection to interface.

Role of Nanoscale Roughness and Polarity in Odd–Even Effect of Self‐Assembled Monolayers

AbstractThe dependency of substrate roughness on wetting properties of self‐assembled monolayers (SAMs) has been studied extensively, but most previous studies used limited selection of probing liquid and range of surface roughness. These studies disregarded the limit to observation of sub‐nanometer odd–even parity effect, hence are inconclusive. In this work we report the role of solvent polarity on the roughness‐dependency of wetting behavior of SAMs by studying static con‐tact angle of a variety of probing liquids, with different polarities, on SAMs formed on Ag‐based substrate with different surface morphology. By overlapping the roughness ranges with previous studies on Au, the limitation of surface roughness (RMS=1 nm) to observation of the odd–even effect using water as probing liquid was confirmed, but other probing liquid yielded different roughness‐dependent behaviors, with more polar solvent showing more roughness‐dependent behavior. Based on these observations, we concluded that there exists a phase‐transition like behavior in SAMs due to substrate roughness and molecule chain length, but whose determination is dependent on the probing liquid.

Role of Nanoscale Roughness and Polarity in Odd-Even Effect of Self-Assembled Monolayers.

The dependency of substrate roughness on wetting properties of self‐assembled monolayers (SAMs) has been studied extensively, but most previous studies used limited selection of probing liquid and range of surface roughness. These studies disregarded the limit to observation of sub‐nanometer odd–even parity effect, hence are inconclusive. In this work we report the role of solvent polarity on the roughness‐dependency of wetting behavior of SAMs by studying static con‐tact angle of a variety of probing liquids, with different polarities, on SAMs formed on Ag‐based substrate with different surface morphology. By overlapping the roughness ranges with previous studies on Au, the limitation of surface roughness (RMS=1 nm) to observation of the odd–even effect using water as probing liquid was confirmed, but other probing liquid yielded different roughness‐dependent behaviors, with more polar solvent showing more roughness‐dependent behavior. Based on these observations, we concluded that there exists a phase‐transition like behavior in SAMs due to substrate roughness and molecule chain length, but whose determination is dependent on the probing liquid.

Alkyl substituent-dependent systematic change in cold crystallization of azo molecules.

The thermal behavior of alkyl-derivatized 1-(2,4-dimethylphenylazo)-4-naphthol and 1-(2,4-dimethylphenylazo)-2-naphthol (2,4-DM-4-Cn and 2,4-DM-2-Cn, respectively) was investigated. The change in the position of the alkyl substituent led to a variation in the thermal behavior, including the cold crystallization, which is a heat-storing phenomenon. In addition, a comprehensive study of the alkyl chain length revealed that 2,4-DM-4-Cn had better crystallinity and exhibited cold crystallization with short alkyl chains. The π–π, C–H⋯N, and C–H⋯π interactions stabilized the crystal structure of 2,4-DM-4-Cn. On the other hand, the polymorphism of 2,4-DM-2-Cn inhibited the formation of a uniform crystalline phase during cooling, which led to poor crystallinity. The only difference between the compounds, the position of the substituent, resulted in a clear variation in the cold crystallization and heat storage properties.

Amphifunctional Mesoporous Silica Nanoparticles with “Molecular Gates” for Controlled Drug Uptake and Release

AbstractIt is demonstrated that the uptake and release of hydrophobic drugs/dyes by mesoporous silica nanoparticles (MSN) is critically dependent on the functional groups present on their outer surfaces. For this, amphifunctional MSNs are synthesized, possessing hydrophobic pores and hydrophilic functional groups on the outer surface. Further, the outer surface is modified with a different chain length of molecules, e.g., propargyl alcohol, triethylene glycol, and PEG (2000) via azide–alkyne click chemistry. The effect of these different surface functional groups on uptake of drug/dye is demonstrated with Nile red, proflavine (free base form), and rhodamine 6G. The uptake of these molecules is found to be inversely proportional to the bulkiness of surface functionality. To counter this effect, an alternate method of loading is proposed and demonstrated. Finally, the effect of these different functional groups on the release of loaded drug proflavine is studied, which supports the hypothesis that bulkier outer surface groups also hinder the release of drugs loaded in the porous MSN.

The Impact of an Anchoring Layer on the Formation of Tethered Bilayer Lipid Membranes on Silver Substrates.

Tethered bilayer lipid membranes (tBLMs) have been known as stable and versatile experimental platforms for protein–membrane interaction studies. In this work, the assembly of functional tBLMs on silver substrates and the effect of the molecular chain-length of backfiller molecules on their properties were investigated. The following backfillers 3-mercapto-1-propanol (3M1P), 4-mercapto-1-butanol (4M1B), 6-mercapto-1-hexanol (6M1H), and 9-mercapto-1-nonanol (9M1N) mixed with the molecular anchor WC14 (20-tetradecyloxy-3,6,9,12,15,18,22 heptaoxahexatricontane-1-thiol) were used to form self-assembled monolayers (SAMs) on silver, which influenced a fusion of multilamellar vesicles and the formation of tBLMs. Spectroscopic analysis by SERS and RAIRS has shown that by using different-length backfiller molecules, it is possible to control WC14 anchor molecules orientation on the surface. An introduction of increasingly longer surface backfillers in the mixed SAM may be related to the increasing SAMs molecular order and more vertical orientation of WC14 at both the hydrophilic ethylenoxide segment and the hydrophobic lipid bilayer anchoring alkane chains. Since no clustering of WC14 alkane chains, which is deleterious for tBLM integrity, was observed on dry samples, the suitability of mixed-component SAMs for subsequent tBLM formation was further interrogated by electrochemical impedance spectroscopy (EIS). EIS showed the arrangement of well-insulating tBLMs if 3M1P was used as a backfiller. An increase in the length of the backfiller led to increased defectiveness of tBLMs. Despite variable defectiveness, all tBLMs responded to the pore-forming cholesterol-dependent cytolysin, vaginolysin in a manner consistent with the functional reconstitution of the toxin into phospholipid bilayer. This experiment demonstrates the biological relevance of tBLMs assembled on silver surfaces and indicates their utility as biosensing elements for the detection of pore-forming toxins in liquid samples.

Relative importance of branching enzyme isoforms in determining starch fine structure and physicochemical properties of indica rice.

Down-regulation of starch branching enzymes alters fine structure and starch properties, especially the B-type crystalline pattern and extremely high amylose content identified in the BEIIb-deficiency mutant in the indica rice. The relative importance of the starch branching enzymes in determining the molecular fine structure and starch functional properties were uncovered in this study. An indica rice, Guangluai 4 with high amylose content (AC) and high gelatinization temperature (GT) was used to generate the clustered regularly interspaced short palindromic repeats (CRISPR)/associated protein-9 (Cas9) knockout lines. Five mutant lines were identified including be1-1, be1-2, be2a-1, be2a-2 and be2b-1, and analysis of western blot showed the CRISPR/Cas9 system was successful in inducing mutations in the targeted genes. AC of be2b-1 (34.1%) was greater than that of wild type (WT) (27.4%) and other mutants. Mutations of either BEI or BEIIa did not alter the starch crystallite pattern (A-type). The BEIIb deficiency caused an opaque endosperm phenotype, changed the crystallite pattern from A- to B-type, and dramatically increased the degree of ordered structure, the relative proportion of amylose chains and intermediate to long amylopectin chains, average chain length of amylopectin molecules as well as GT. The BEIIa deficiency had no effect on the proportion of amylose chains, the length of amylopectin intermediate-long chains, conclusion temperature and enthalpy of gelatinization. Down-regulation of BEI increased the proportion of shortest amylopectin chains (fa) but decreased the proportion of long amylopectin chains (fb2 and fb3), leading to a lower GT. It is concluded that the relative importance in determining starch fine structures and functionality was in the order of BEIIb > BEI > BEIIa. Our results provide new information for utilizations of BE-deficient mutants in rice quality breeding.