Packing Of Alkyl Chains Research Articles

Using the pH sensitivity of switchable surfactants to understand the role of the alkyl tail conformation and hydrogen bonding at a molecular level in elucidating emulsion stability

HypothesisThe monoalkyl diamine surfactant, N-dodecylpropane-1,3-diamine (DPDA), is expected to exhibit a pH-dependent charge switchability. In response to pH changes, the interfacial self-assembly of DPDA becomes an intermediary constituent that can potentially modify the interfacial interactions and structural assembly of both the oil and water phases. Hence, we hypothesize that as we change the pH, DPDA will respond to it by changing its charge and alkyl tail conformation as well as the conformation of adjacent phases at the molecular level, consequently affecting emulsion formation and stability. A neutral pH, resulting in a mono-cationic dialkyl amine, affects the conformation, driving an ordered self-assembly and stable emulsion. ExperimentsThe pH-sensitivity and interfacial activity of DPDA were evaluated through pH titration and interfacial tension measurements. Subsequently, a molecular-level study of DPDA, as a pH-sensitive switchable surfactant, was performed at the dodecane-water interface using SFG spectroscopy. The interpretation of the vibrational spectra was further reinforced by determining the gauche defects in the interfacial alkyl chain organization and the extent of hydrogen (H) bonding between the interfacial water molecules. FindingsBy adjusting the pH of water, the charge of the adsorbed DPDA molecules, their self-assembly, the organization of interfacial molecules, and ultimately the stability of the emulsion were tuned. At pH 7.0, the SFG spectra of DPDA showed that the interfacial alkyl chains were relatively well-ordered, while water molecules also had stronger H-bonding interactions. As a result, the oil–water emulsion showed improved stability. When water was at a high pH, the water molecules had fewer H-bonding interactions and relatively disordered alkyl chains at the interface, providing desirable conditions for demulsification. These observations were compatible with the observation in bulk emulsion preparation, confirming that alkyl chain packing and water H-bonding interactions at the interface contribute to overall emulsion stability.

Thiophene structured additives toward enhanced structural order and reduced non-radiative loss for 19.9 % efficiency organic solar cells

Organic semiconductors usually exhibit low structural-order owing to their weak intermolecular interactions, which leads to inferior charge transport and strong carrier recombination in photovoltaics. In this work, three thiophene structured solid additives namely thieno[3,2-b]thiophene (TT), 3,6-dibromothieno[3,2-b]thiophene (TTBB) and 3-bromo-6-iodio-thieno[3,2-b]thiophene (TTBI) are utilized to enhance the molecular interactions in a range of electron donors and acceptors. X-ray technique and molecular dynamics simulations reveal that by adjusting their electrostatic potential and dipole moment, their interacting site and interaction energy with donor (PM6 and D18) or acceptor (L8-BO) can be finely tuned. We find the most electropositive TTBB shows the strongest interaction with PM6, leading to enhanced crystallization; whilst the asymmetric TTBI brings the strongest molecular packing of L8-BO, consequent to more compact π-π stacking and ordered alkyl chain packing. As the results, the bulk heterojunction PM6:L8-BO photovoltaics upon the assistance of TTBI or TTBB obtain improved charge transport and reduced non-radiative energy loss, translating to power conversion efficiency (PCE) values of 18.7 % and 19.1 %. When further taking the synergetic effect of TTBB and TTBI on PM6(D18) and L8-BO respectively, the layer-by-layer deposited PM6(TTBB)/L8-BO(TTBI) and D18(TTBB)/L8-BO(TTBI) allowed superior PCEs of 19.4 % and 19.9 %, which are among the highest values of single-junction organic solar cells.

π-Extended Nonfullerene Acceptor for Compressed Molecular Packing in Organic Solar Cells To Achieve over 20% Efficiency.

Organic photovoltaics (OPVs) suffer from a trade-off between efficient charge transport and suppressed nonradiative recombination due to the aggregation-induced luminance quenching of organic semiconductors. To resolve this grand challenge, a π-extended nonfullerene acceptor (NFA) B6Cl with large voids among the honeycomb network is designed and introduced into photovoltaic systems. We find that the presence of a small amount of (i.e., 0.5 or 1 wt %) B6Cl can compress the molecular packing of the host acceptor L8-BO, leading to shortened π-π stacking distance from 3.59 to 3.50 Å (that will improve charge transport) together with ordered alkyl chain packing (that will inhibit nonradiative energy loss due to the suppressed C-C and C-H bonds vibrations), as validated by high-energy X-ray scattering measurements. This morphology transformation ultimately results in simultaneously improved JSC, FF, and VOC of OPVs. As a result, the maximum PCEs of PM6:L8-BO and D18:L8-BO are increased from 19.1 and 19.3% to 19.8 and 20.2%, respectively, which are among the highest values for single-junction OPVs. The university of B6Cl to increase the performance of OPVs is further evidenced in a range of polymer:NFA OPVs.

The Influence of Extractant Composition on the Asphaltenes Extracted from Asphalt

The compositions of extractants containing xylene (G) and n-heptane (P) recovered and reused in the asphaltene extraction process were determined by densimetry and the extracted asphaltenes were analyzed to study the influence of extractant composition on their elemental, spectral and structural properties. With increasing the number of extraction, the G/P ratio in extractant increases, which dissolves more asphaltenes of higher aromaticity and causes a decrease of asphaltene yield, the polarity and aromaticity in molecular structure of the extracted asphaltenes. Asphaltenes extracted at a higher G/P ratio were found to have less fractions of N and O elements as well as higher fractions of H and S elements, a lower C/H atom ratio and molecular unsaturation. Moreover, they have a smaller fraction of aromatic rings and aromatic carbon ratio, a higher substitution rate on aromatic rings, a higher fraction of alkyl chain and free ends in their average molecular structure. Compared with the base asphalt, asphaltenes’ infrared absorptions generally move towards smaller wave numbers owing to more aromaticity in their molecules and subsequent stronger conjugative and inductive effects. The asphaltenes extracted at a higher G/P ratio have a denser packing of alkyl chains and a looser packing of aromatic rings, according to their spectra of X-ray diffraction.

Crystal structure of 8-hex-yloxy-2-[(Z)-2-(naph-thal-en-2-yl)ethen-yl]quinoline.

In the title mol-ecule, C27H27NO, the naphthalene and quinoline groups are both planar and subtend a dihedral angle of 15.47 (7)°. They are nearly coplanar with the cis-vinyl bridge and the hex-yloxy chain, which adopts an all-trans conformation, resulting in transannular bifurcated intra-molecular C-H⋯N,O contact. The crystal structure features γ-packing of the aromatic moieties, while the parallel packing of alkyl chains resembles that of alkanes.

Zinc Anodes Modified by One-Molecular-Thick Self-Assembled Monolayers for Simultaneous Suppression of Side-Reactions and Dendrite-Formation in Aqueous Zinc-Ion Batteries.

Repeated charge/discharge in aqueous zinc-ion batteries (ZIBs) commonly results in surface corrosion/passivation and dendrite formation on zinc anodes, which is a major challenge for the commercialization of zinc-based batteries. In this work, metallic Zn modified by self-assembled monolayers is described as a viable anode for ZIBs. ω-mercaptoundecanoic acid that is spontaneously adsorbed on Zn (MUDA/Zn) contributes to the simultaneous suppression of side reactions and dendrite formation in ZIBs. Though one-molecular-thick, densely packed alkyl chains prohibit H2 O and H+ from making direct contact with the underlying Zn, and surface carboxylate moieties (-COO- ) effectively repel anionic species (OH- ) in a solution, which renders a Zn anode inert against zincate formation within a wide range of pH. In contrast, the electrostatic attraction between surface-carboxylates and cations increases the concentration of Zn2+ on the surface of MUDA/Zn to facilitate Zn plating/stripping with less overpotentials. The high concentration of Zn2+ also results in an increased number of nucleation sites, which enhances the lateral growth of Zn with no formation of dendrites. As a result, MUDA/Zn shows excellent stability during prolonged Zn plating/stripping within a wide range of pH. The advantageous properties of MUDA/Zn are also retained in full-cells coupled with δ-MnO2 cathodes.

Selective CO2 adsorption and bathochromic shift in a phosphocholine-based lipid and conjugated polymer assembly.

We assemble a film of a phosphocholine-based lipid and a crystalline conjugated polymer using hydrophobic interactions between the alkyl tails of the lipid and alkyl side chains of the polymer, and demonstrated its selective gas adsorption properties and the polymer's improved light absorption properties. We show that a strong attractive interaction between the polar lipid heads and CO2 was responsible for 6 times more CO2 being adsorbed onto the assembly than N2, and that with repeated CO2 adsorption and vacuuming procedures, the assembly structures of the lipid-polymer assembly were irreversibly changed, as demonstrated by in situ grazing-incidence X-ray diffraction during the gas adsorption and desorption. Despite the disruption of the lipid structure caused by adsorbed polar gas molecules on polar head groups, gas adsorption could promote orderly alkyl chain packing by inducing compressive strain, resulting in enhanced electron delocalization of conjugated backbones and bathochromic light absorption. The findings suggest that merging the structures of the crystalline functional polymer and lipid bilayer is a viable option for solar energy-converting systems that use conjugated polymers as a light harvester and the polar heads as CO2-capturing sites.

Effect of Lithium-Ion on the Structural Organization of Monocationic and Dicationic Ionic Liquids.

In recent times, ionic liquid-based (ILs) electrolytic system has emerged as suitable alternative to the conventional organic solvent-based electrolytic system. However, since, anion of ILs is known to form aggregates in the presence of lithium-ions (Li+), and this can influence the transport properties of Li+ ion in a significant manner, it is, therefore, important to understand how lithium-ions influence the structure and dynamics of ILs. With this objective, in the present study, intermolecular interaction, structural organization, and dynamics of monocationic ILs (MILs) and dicationic IL (DIL) have been studied in the absence and presence of lithium salt. Specifically, for this purpose, two MILs, 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide ([C3C1im][NTf2]), 1-hexyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide ([C6C1im][NTf2]), and a DIL, 1,6-bis(3-methylimidazolium-1-yl)hexane bis(trifluoromethylsulfonyl)amide ([C6(mim)2][NTf2]2) have been chosen in such a way that either the alkyl chain of MILs becomes equal or half of the spacer chain length of DIL. To understand the effect of the addition of lithium-ion on the structural organization of MILs and DIL, steady-state absorption and fluorescence spectroscopies, time-resolved fluorescence anisotropy and nuclear magnetic resonance (NMR) techniques have been used. Structural organization in the apolar and polar domains of ILs has been probed by following the rotational diffusion of suitably chosen solute in the concerned media through time-resolved fluorescence anisotropy (TRFA) measurements. TRFA studies have revealed that with the addition of Li+ ion, coordination between the Li+ ions and anions of MILs and DILs takes place in the ionic region leading to a change in the structural organization of the apolar regions of the respective medium. In fact, upon adding lithium-ions, a reduction in the packing of alkyl chains has also been observed for the MILs. However, not much change in the structural organization of the apolar region of the DIL has been observed when Li+ ion is added to it. In the presence of Li+ ions, a similar trend in the change of structural organization of polar regions for both MILs and DIL has been observed. Further, measurements of the self-diffusion coefficient through NMR have also supported the observation that Li+ ion also perturbs the nanostructural organization of the MIL in a significant manner than that it does for the DIL. The behavior of DIL in the presence of Li+ ion, as revealed by the present study, has been rationalized by considering the folded arrangement of DIL in the fluid-structure. Essentially, all of these investigations have suggested that the addition of lithium-ion significantly alters the microscopic behavior of MILs in comparison to that of DIL. The outcome of this study is expected to be helpful in realizing the potentials of these media as electrolytes in battery applications.

Rheology of α-Gel Formed by Amino Acid-Based Surfactant with Long-Chain Alcohol: Effects of Inorganic Salt Concentration.

Mixtures of surfactants, long-chain alcohols, and water sometimes yield lamellar gels with hexagonally packed alkyl chains. This assembly is called “α-gel” or “α-form hydrated crystal.” In this study, we characterized the rheological properties of α-gel prepared using disodium N-dodecanoylglutamate (C12Glu-2Na), 1-hexadecanol (C16OH), and water at different NaCl concentrations. The α-gel structure was assessed using small- and wide-angle X-ray scattering (SWAXS). The SWAXS measurements revealed that an increased NaCl concentration (0–200 mmol dm–3) resulted in a decreased d-spacing caused by the screening of electrostatic repulsion between lamellar bilayers. This led to an increased amount of excess water (i.e., the water present between the α-gel domains), and hence, the viscosity of the α-gel decreased in the range of the NaCl concentration. A further increase in the NaCl concentration (200–1000 mmol dm–3) resulted in decreased electrostatic repulsion between the α-gel domains and/or an increased number of α-gel domains (multilamellar vesicles). These effects increased the domain-to-domain interactions, leading to increased viscosity. Therefore, we concluded that the viscosity of the α-gel was controlled by the amount of excess water and the domain-to-domain interactions. Once the network structure collapsed under the strain, it was difficult to recover the original network structure. The low recoverability resulted from increased cohesion between the domains at high NaCl concentrations.

Crystal Packing‐Guided Construction of Hetero‐Oligomeric Peptidic Ensembles as Synthetic 3‐in‐1 Transporters

AbstractStrategies to generate heteromeric peptidic ensembles via a social self‐sorting process are limited. Herein, we report a crystal packing‐inspired social self‐sorting strategy broadly applicable to diverse types of H‐bonded peptidic frameworks. Specifically, a crystal structure of H‐bonded alkyl chain‐appended monopeptides reveals an inter‐chain separation distance of 4.8 Å dictated by the H‐bonded amide groups, which is larger than 4.1 Å separation distance desired by the tightly packed straight alkyl chains. This incompatibility results in loosely packed alkyl chains, prompting us to investigate and validate the feasibility of applying bulky tert‐butyl groups, modified with an anion‐binding group, to alternatively interpenetrate the straight alkyl chains, modified with a crown ether group. Structurally, this social self‐sorting approach generates highly stable hetero‐oligomeric ensembles, having alternated anion‐ and cation‐binding units vertically aligned to the same side. Functionally, these hetero‐oligomeric ensembles promote transmembrane transport of cations, anions and more interestingly zwitterionic species such as amino acids.

Crystal Packing‐Guided Construction of Hetero‐Oligomeric Peptidic Ensembles as Synthetic 3‐in‐1 Transporters

Strategies to generate heteromeric peptidic ensembles via a social self-sorting process are limited. Herein, we report a crystal packing-inspired social self-sorting strategy broadly applicable to diverse types of H-bonded peptidic frameworks. Specifically, a crystal structure of H-bonded alkyl chain-appended monopeptides reveals an inter-chain separation distance of 4.8 Å dictated by the H-bonded amide groups, which is larger than 4.1 Å separation distance desired by the tightly packed straight alkyl chains. This incompatibility results in loosely packed alkyl chains, prompting us to investigate and validate the feasibility of applying bulky tert-butyl groups, modified with an anion-binding group, to alternatively interpenetrate the straight alkyl chains, modified with a crown ether group. Structurally, this social self-sorting approach generates highly stable hetero-oligomeric ensembles, having alternated anion- and cation-binding units vertically aligned to the same side. Functionally, these hetero-oligomeric ensembles promote transmembrane transport of cations, anions and more interestingly zwitterionic species such as amino acids.

The flexibility of long chain substituents influences spin-crossover in isomorphous lipid bilayer crystals.

[Fe(bpp)2][BF4]2 (bpp = 2,6-di{pyrazol-1-yl}pyridine) derivatives with a bent geometry of hexadec-1-ynyl or hexadecyl pyrazole substituents are isomorphous, and high-spin at room temperature. However, only the latter compound undergoes an abrupt, stepwise spin-transition on cooling. This may reflect the different conformational flexibilities of their long chain substituents.

Phase Transition from the Interdigitated to Bilayer Membrane of a Cationic Surfactant Induced by Addition of Hydrophobic Molecules.

Although the transition between a bilayer and an interdigitated membrane of a surfactant and lipid has been widely known for long, its mechanism remains unclear. This study reveals the transition mechanism of a cationic surfactant, dioctadecyldimethylammonium chloride (DODAC), through experiments and theoretical calculations. Experimentally, the transition from the interdigitated to bilayer structure in the gel phase of DODAC is found to be induced by adding hydrophobic molecules such as n-alkane and its derivatives. Further addition induces a different transition to another bilayer phase. Our theory, considering the competition of the electrostatic interaction between cationic headgroups and the hydrophobic interaction emerging at the alkyl-chain ends exposed to water, reproduces these two phase transitions. In addition, changes in alkyl-chain packing in the membranes at these transitions are reproduced. The underlying mechanism is that the interdigitated membrane is formed at a small additive content due to electrostatic repulsion. As the energetic disadvantage with respect to the hydrophobic interaction becomes dominant as the content increases, the transition to the bilayer occurs at a specific content. The bilayer-bilayer transition at a higher content is induced by the change in the balance of these interactions. Based on a similar concept, we suggest the mechanism of the additive-induced bilayer-interdigitated transition of phospholipids, i.e., neutrally charged (zwitterionic) surfactants.

Parity Effects in the Physicochemical Properties of Self-Assembled Monolayers

Large-area metal/molecule/metal junctions based on self-assembled monolayers (SAMs) of organothiolates are of interest for investigations of charge transport across ultrathin organic films and the fabrication of molecular electronic devices. Several recent reports demonstrate an odd-even dependency in the rate of charge transport through SAMs of the insulating n-alkanethiolates (CH3C n S)1,2 or the redox-active ferrocenylalkanethiolates (FcC n S)3. This parity effect has been attributed to differences in the orientation of the terminal functional group and alkyl chain packing in SAMs consisting of an odd versus even number of methylene repeat units.We have sought experimental evidence for odd-even distinctions in the molecular organization of these SAMs using infrared reflection-adsorption spectroscopy (IRRAS), electrochemistry, and contact angle goniometry. The findings of the investigations will be presented in this talk and the molecular origin of the parity effect of SAM macroscopic properties will be discussed.

Influence of Alkyl Substitution Position on Wide-Bandgap Polymers in High-Efficiency Nonfullerene Polymer Solar Cells.

Two wide-bandgap (WBG) conjugated polymers (PBPD-p and PBPD-m) based on phenyl-substituted benzodithiophene (BDT) with the different substitution position of the alkyl side chain and benzodithiophene-4,8-dione (BDD) units are designed and synthesized to investigate the influence of alkyl substitution position on the photovoltaic performance of polymers in polymer solar cells (PSCs). The thermogravimetric analysis, absorption spectroscopy, molecular energy level, X-ray diffraction, charge transport and photovoltaic performance of the polymers are systematically studied. Compared with PBPD-p, PBPD-m exhibits a slight blue-shift but a deeper highest occupied molecular orbital (HOMO) energy level, a tighter alkyl chain packing and a higher hole mobility. The PBPD-m-based PSCs blended with acceptor IT-4F shows a higher power conversion efficiency (PCE) of 11.95% with a high open-circuit voltage (Voc ) of 0.88 V, a short-circuit current density (Jsc ) of 19.76 mA cm-2 and a fill factor (FF) of 68.7% when compared with the PCE of 6.97% with a Voc of 0.81 V, a Jsc of 15.97 mA cm-2 and an FF of 53.9% for PBPD-p. These results suggest that it is a feasible and effective strategy to optimize photovoltaic properties of WBG polymers by changing the substitution position of alkyl side chain in PSCs.

Interaction of the (2√3 × 3)rect. Adsorption-Site Basis and Alkyl-Chain Close Packing in Alkanethiol Self-Assembled Monolayers on Au(111): A Molecular Dynamics Study of Alkyl-Chain Conformation.

We show that the adsorption site basis of the (2√3 × 3)rect. phase of n-alkanethiol self-assembled monolayers plays a key role in determining the molecular conformation of the close-packed alkyl chains. Ten proposed reconstructed Au–S interfaces are used to explore the minimized energy alkyl-chain packing of n-decanethiol molecules using molecular dynamics with the all-atom description. In this comparative study, all models have the same alkyl-chain surface density of four molecules per unit cell; thus, differences are due to the headgroup spacing within the 4-molecule basis as opposed to the average surface density. We demonstrate for the first time the 4-molecule-basis twist structure driven by the packing of alkanethiol molecules in a large simulation box (100 molecules, 25 unit cells) using molecular dynamics. Our results validate the prediction put forward by Mar and Klein that to achieve the 4-molecule-basis twist symmetry observed by the experiment, the headgroups must deviate from the high-symmetry (√3 × √3)R30° sites. The key structural parameters: tilt, twist, and end-group height, as well as their spatial order, are compared with experimental results, which we show is a highly sensitive approach that can be used to vet proposed Au–S interfacial models.

Stereostructural Effects in the Electrochemical Properties of Self-Assembled Monolayers

Large-area metal/molecule/metal junctions based on self-assembled monolayers (SAMs) of organothiolates are of interest for the investigation of charge transport across ultrathin organic films and the fabrication of molecular electronic devices such as diodes and switches. Several reports demonstrate an odd-even dependency in the rate of charge transport across SAMs of the redox-active ferrocenylalkanethiolates Fc(CH2) n S1, 2 and insulating n-alkanethiolates CH3(CH2) n S3-6. This parity effect is attributed to small changes in the orientation of the terminal functional group (ferrocene or methyl) and in the alkyl chain packing in SAMs consisting of an odd versus even number of methylene repeat units (n odd or n even). These odd-even differences ultimately impact device performance. For instance, junctions comprising gold-supported Fc(CH2) n S SAMs (Figure 1) of n even present lower leakage currents and rectify current, while those of n odd do not.1, 2 We have sought experimental evidence for odd-even distinctions in the molecular organization of these SAMs using electrochemistry,7 infrared reflection-absorption spectroscopy (IRRAS), contact angle goniometry, and surface stress measurements8. The findings of these investigations will be presented in this talk.

Defects in Self-Assembled Monolayers on Nanoparticles Prompt Phospholipid Extraction and Bilayer-Curvature-Dependent Deformations

Metal nanoparticles (NPs) functionalized with self-assembled monolayers (SAMs) of long alkanethiol ligands are subject to defects in the SAM structure due to the interplay between alkyl chain packing and the free volume available in space per ligand. We find via dissipative particle dynamics (DPD) simulations that hydrophobic contact between protruding acyl chains of phospholipids from lipid vesicles and exposed alkyl chains in SAM defects prompts NP insertion and that defects become sites for phospholipid extraction. Experiments show that AuNPs coated with cationic (11-mercaptoundecyl)trimethylammonium bromide, analogous to the models used for the simulations, attach to and acquire lipids from planar supported lipid bilayers, while AuNPs coated with anionic 11-mercaptoundecanoic acid do not. Phospholipid extraction and the structure of the ligands inserted in bilayers collectively contribute to bilayer thinning at the site of NP insertion and bilayer-curvature-dependent deformability, revealing how these typical engineered SAM-coated NPs interface with lipid-bilayer systems with potential biological consequences.

Plastically Deformable and Exfoliating Molecular Crystals of a 2-D Coordination Polymer and Its Ligand

4-n-Hexyloxybenzoic acid and the corresponding potassium salt were synthesized and crystallized, and their force-induced mechanical response was studied. 4-n-Hexyloxybenzoic acid is crystallized as large single crystals of the reported monoclinic polymorph, whereas, its potassium salt forms a 2D polymeric structure. When a localized mechanical force is applied, crystals of both materials undergo plastic deformation to the extent that they can be folded to resemble characters of the English alphabet. With few cycles of bending and unbending, the crystals can be exfoliated, and crystalline layers can be separated. In both structures, van der Waals interactions of the hexyl chains contribute toward the formation of slip plane parallel to the wider face of the crystals, which is necessary for their plastic deformability. Reported crystal structures of 4-n-alkoxybenzoic acids with alkyl chain length ranging from C1 to C10 and their inorganic salts were analyzed, and it was found that packing of alkyl chains su...

Aqueous dispersions of thienoisoindigo-based semiconductor nanorods assembled with 2-bromobenzaldehyde and a phospholipid

Nanoassemblies of an organic semiconductor based on thienoisoindigo were prepared by forming nanomorphologies in phase-separated films of a thienoisoindigo-based molecule (TIIG-Bz), bromobenzaldehydes (BBAs), and a phospholipid, 1,2-dioctanoyl-sn-glycero-3-phosphocholine (D8PC), and then shattering the films via penetration of water into polar domains. It was suggested that 2-BBA associated with TIIG-Bz via intermolecular halogen and chalcogen bonding between the electron-deficient δ-holes of bromine in 2-BBA and sulfur in TIIG-Bz, and their electron-rich counterparts, carbonyl oxygen, in TIIG-Bz and 2-BBA, filling empty space in the conjugated planes. This resulted in the π-π stacking of conjugated planes overwhelming the lateral packing of alkyl chains as the ratios of 2-BBA and the lipid to TIIG-Bz increased and decreased, respectively, as proven by bathochromic shifts in the absorption spectra and grazing incidence X-ray diffraction patterns. It was concluded that, by varying the 2-BBA and D8PC compositions, the water-dispersed nanomorphologies of the organic semiconductor can be controlled via the competition of hydrophobic interactions between alkyl chains for lateral association for zero-dimensional growth and intermolecular π-π interactions for one-dimensional growth.