Hydrophobic Building Blocks Research Articles

Dynamic Dance of Chirality and Morphology: Interplay of Solvent-Sensitive Self-Assembly in Topological Evolution and Chirality Amplification.

The building block Pyra-Chol has been designed and synthesized, which exhibits different achiral morphologies in good solvents, forming nanospheres in THF and nanoflowers in 1,4-dioxane. In the presence of water as a poor cosolvent, Pyra-Chol demonstrates an agnostic behavior, generating left-handed superhelices in the water:THF (80:20) solvent system. However, when the good solvent is switched to 1,4-dioxane, a change in chirality is observed in the water:1,4-dioxane (30:70) solvent system, resulting in the formation of fused nanospheres. Interestingly, when the poor cosolvent is changed from water to MCH in THF, the chiral pattern remains unchanged, but the morphology changes completely. Supported by the collective spectroscopic and microscopic analysis, the present study efficaciously demonstrates the remarkable control of hydrophobic building block over the chiral sense and also highlights the fascinating influence of good as well as poor cosolvent in supporting the distinct molecular packing.

DNA Hierarchical Superstructures from Micellar Units: Stiff Hydrogels and Anisotropic Nanofibers.

Supramolecular materials have been assembled using a wide range of interactions, including the hydrophobic effect, DNA base-pairing, and hydrogen bonding. Specifically, DNA amphiphiles with a hydrophobic building block self-assemble into diverse morphologies depending on the length and composition of both blocks. Herein, we take advantage of the orthogonality of different supramolecular interactions - the hydrophobic effect, Watson-Crick-Franklin base pairing and RNA kissing loops - to create hierarchical self-assemblies with controlled morphologies on both the nanometer and the micrometer scales. Assembly through base-pairing leads to the formation of hybrid, multi-phasic hydrogels with high stiffness and self-healing properties. Assembly via hydrophobic core interactions gives anisotropic, discrete assemblies, where DNA fibers with one sequence are terminated with DNA spheres bearing different sequences. This work opens new avenues for the bottom-up construction of DNA-based materials, with promising applications in drug delivery, tissue engineering, and the creation of complex DNA structures from a minimum array of components.

Apoptosis-induced treatment for ovarian cancer from self-assembled nanocomposites of Fe3O4 nanoparticles and porous organic cages

HypothesisOvarian cancer is one of the most common tumors in gynecology and imposes a heavy burden on patients and their families. Fe3O4 nanoparticles are one of the few nanomaterials approved by the FDA for clinical use, which has been widely used in the diagnosis and treatment of tumor. ExperimentsThe aqueous colloids made from hydrophobic building blocks were fabricated through an oil-in-water emulsion confined assembly strategy. In vitro, the proliferation, migration, invasion of SKOV3 cell after the treatment of iron oxide based assemblies were detected using Test-EdU assay and wound-healing assay. The ovarian cancer of the Nude Mice model was used to investigate the anti-cancer effect of Fe3O4 assemblies and Fe3O4-CC3 co-assemblies in vivo. FindingsThe applied nanocomposites inhibited ovarian cancer cells by CytC/caspase-3 pathway. The results in vivo revealed that treatment of nanocomposites significantly restrained the growth of subcutaneous transplantation tumor in Ovarian Cancer of the Nude Mice model. Our study demonstrated that colloidal nanocomposites assembled from Fe3O4 nanoparticles and porous organic cages inhibits cancer progression and induces apoptosis via caspase pathway. The effect of Fe3O4-CC3 co-assemblies is more profound due to their better contact with the biological matter.

Particle Engineering via Supramolecular Assembly of Macroscopic Hydrophobic Building Blocks

AbstractTailoring the hydrophobicity of supramolecular assembly building blocks enables the fabrication of well‐defined functional materials. However, the selection of building blocks used in the assembly of metal–phenolic networks (MPNs), an emerging supramolecular assembly platform for particle engineering, has been essentially limited to hydrophilic molecules. Herein, we synthesized and applied biscatechol‐functionalized hydrophobic polymers (poly(methyl acrylate) (PMA) and poly(butyl acrylate) (PBA)) as building blocks to engineer MPN particle systems (particles and capsules). Our method allowed control over the shell thickness (e.g., between 10 and 21 nm), stiffness (e.g., from 10 to 126 mN m−1), and permeability (e.g., 28–72 % capsules were permeable to 500 kDa fluorescein isothiocyanate‐dextran) of the MPN capsules by selection of the hydrophobic polymer building blocks (PMA or PBA) and by controlling the polymer concentration in the MPN assembly solution (0.25–2.0 mM) without additional/engineered assembly processes. Molecular dynamics simulations provided insights into the structural states of the hydrophobic building blocks during assembly and mechanism of film formation. Furthermore, the hydrophobic MPNs facilitated the preparation of fluorescent‐labeled and bioactive capsules through postfunctionalization and also particle–cell association engineering by controlling the hydrophobicity of the building blocks. Engineering MPN particle systems via building block hydrophobicity is expected to expand their use.

Particle Engineering via Supramolecular Assembly of Macroscopic Hydrophobic Building Blocks.

Tailoring the hydrophobicity of supramolecular assembly building blocks enables the fabrication of well-defined functional materials. However, the selection of building blocks used in the assembly of metal-phenolic networks (MPNs), an emerging supramolecular assembly platform for particle engineering, has been essentially limited to hydrophilic molecules. Herein, we synthesized and applied biscatechol-functionalized hydrophobic polymers (poly(methyl acrylate) (PMA) and poly(butyl acrylate) (PBA)) as building blocks to engineer MPN particle systems (particles and capsules). Our method allowed control over the shell thickness (e.g., between 10 and 21 nm), stiffness (e.g., from 10 to 126 mN m-1 ), and permeability (e.g., 28-72 % capsules were permeable to 500 kDa fluorescein isothiocyanate-dextran) of the MPN capsules by selection of the hydrophobic polymer building blocks (PMA or PBA) and by controlling the polymer concentration in the MPN assembly solution (0.25-2.0 mM) without additional/engineered assembly processes. Molecular dynamics simulations provided insights into the structural states of the hydrophobic building blocks during assembly and mechanism of film formation. Furthermore, the hydrophobic MPNs facilitated the preparation of fluorescent-labeled and bioactive capsules through postfunctionalization and also particle-cell association engineering by controlling the hydrophobicity of the building blocks. Engineering MPN particle systems via building block hydrophobicity is expected to expand their use.

Hydrophobic building blocks enable unprecedented durability for chemically recyclable and biodegradable polymer

The widespread usage and improper disposal of conventionally non-degradable petrochemical-based polymers have led to anabatic energy depletion, significant resource shortages, and severe environmental concerns, motivating the development of polymers that combine chemical recyclability, biodegradability, and mechanical properties suitable for applications. However, there remains an irreconcilable contradiction between property retention in service and post-use degradation or recycling in this category of polymers. Herein, through the introduction of hydrophobic building blocks, a biodegradable polymer that shows excellent mechanical properties (elongation at break of 891.5 ± 23.2%, and maximum strength of 56.9 ± 0.9 MPa) and good thermal stability (decomposition temperature of approximately 290 °C) was obtained. Moreover, the polymer possessed not only easy-access-to-monomer recyclability (yield of 95.4% and purity of 99.9%) but also unprecedented durability (elongation-at-break retention of 54.4 ± 7% and maximum-strength retention of 79.6 ± 14% on the 30th day) under highly moist air (25 °C, relative humidity (RH) of 90%). In addition, the origins and mechanism of the performance improvement were investigated, and a proof of concept for chemical closed-loop recycling between monomers and polymers was demonstrated.

Robust hydrophobic veova10-based colloidal photonic crystals towards fluorescence enhancement of quantum dots.

Hydrophobic photonic crystals (PCs) has been increasingly appreciated as a promising functional material due to their distinct surface characteristic of structural color and hydrophobicity. However, it remains a challenge to fabricate hydrophobic PCs via a one-step process. Inspired by the development of high-performance waterborne coatings, we propose an easy-to-perform and high-efficiency strategy to construct hydrophobic building blocks (diameter of 221, 247, 276 and 305 nm), where the umbelli-form hydrophobic long chain (veova10 Cn > 9) was loaded onto polystyrene (PS) colloidal particles in situ. Taking advantage of the hydrophobic driving force between the colloidal particles, large-scale colloidal photonic crystals (CPCs) film with crack-free morphology was obtained efficiently. The derived CPCs exhibit robust mechanical stability, prominent hydrophobicity and excellent optical properties. In addition, the colloidal latex holds great potential toward PCs coatings on a variety of substrates (glass, plastic and steel) with excellent adhesiveness. Furthermore, we contrive to construct angle-independent structural color films and supraballs, and explore their application in quantum dots (QDs) fluorescence enhancement, which achieved an enhancement effect by more than eight times. From the standpoint of practical applications, we achieved the flexible high-brightness wearable light-emitting diode (LED) displays. This work will lay a foundation for the development of high-efficiency PCs building blocks, and indicate the direction for the meaningful application of CPCs.

Dextran-Benzoporphyrin Derivative (BPD) Coated Superparamagnetic Iron Oxide Nanoparticle (SPION) Micelles for T2-Weighted Magnetic Resonance Imaging and Photodynamic Therapy.

Photodynamic therapy (PDT) has attracted extensive attention in recent years as a noninvasive and locally targeted cancer treatment approach. Nanoparticles have been used to improve the solubility and pharmacokinetics of the photosensitizers required for PDT; however, nanoparticles also suffer from many shortcomings including uncontrolled drug release and low tumor accumulation. Herein, we describe a novel biodegradable nanoplatform for the delivery of the clinically used PDT photosensitizer benzoporphyrin derivative monoacid ring A (BPD-MA) to tumors. Specifically, the hydrophobic photosensitizer BPD was covalently conjugated to the amine groups of a dextran-b-oligo (amidoamine) (dOA) dendron copolymer, forming amphiphilic dextran-BPD conjugates that can self-assemble into nanometer-sized micelles in water. To impart additional imaging capabilities to these micelles, superparamagnetic iron oxide nanoparticles (SPIONs) were encapsulated within the hydrophobic core to serve as a magnetic resonance imaging (MRI) contrast agent. The use of a photosensitizer as a hydrophobic building block enabled facile and reproducible synthesis and high drug loading capacity (∼30%, w/w). Furthermore, covalent conjugation of BPD to dextran prevents the premature release of drug during systemic circulation. In vivo studies show that the intravenous administration of dextran-BPD coated SPION nanoparticles results in significant MR contrast enhancement within tumors 24 h postinjection and PDT led to a significant reduction in the tumor growth rate.

Counteracting in Vitro Toxicity of the Ionophoric Mycotoxin Beauvericin-Synthetic Receptors to the Rescue.

Beauvericin (BEA) and enniatins are toxic ionophoric cyclodepsipeptides that mainly occur in grains. As such, their presence in food commodities poses a concern for public health. To date, despite recent European Food Safety Authority emphasis on the need for more data to evaluate long-term toxicity effects, no suitable affinity reagents are available to detect the presence of BEA and derivatives in food samples. We here report on the synthesis of a small library of artificial receptors with varying cavity sizes and different hydrophobic building blocks. Immobilization of one of the receptors on solid support resulted in a strong retention of beauvericin, thus revealing promising properties as solid-phase extraction material for sample pretreatment. Furthermore, treatment of HepG2 cells with the most promising receptor markedly reduced beauvericin-induced cytotoxicity, hinting toward the possibility of using synthetic receptors as antidotes against ionophoric toxins.

Building Functional Nanodevices with Vesicle-Templated Porous Polymer Nanocapsules.

Vesicle-templated nanocapsules offer a unique combination of properties enabled by robust shells with single-nanometer thickness containing programmed uniform pores capable of fast and selective mass transfer. These capsules emerged as a versatile platform for creating functional devices, such as nanoreactors, nanosensors, and containers for the delivery of drugs and imaging agents. Nanocapsules are synthesized by a directed assembly method using self-assembled bilayers of vesicles as temporary scaffolds. In this approach, hydrophobic building blocks are loaded into the hydrophobic interior of vesicles formed from lipids or surfactants. Pore-forming templates are codissolved with the monomers and cross-linkers in the interior of the bilayer. The polymerization forms a cross-linked shell with embedded pore-forming templates. Removal of the surfactant scaffold and pore-forming templates leads to free-standing nanocapsules with shells containing uniform imprinted nanopores. Development of reliable and scalable synthetic methods for the modular construction of capsules with tunable properties has opened the opportunity to pursue practical applications of nanocapsules. In this Account, we discuss how unique properties of vesicle-templated nanocapsules translate into the creation of functional nanodevices. Specifically, we focus the conversation on applications aiming at the delivery of drugs and imaging agents, creation of fast-acting and selective nanoreactors, and fabrication of nanoprobes for sensing and imaging. We present a brief overview of the synthesis of nanocapsules with an emphasis on recent developments leading to robust synthetic methods including the synthesis under physiological conditions and creation of biodegradable nanocapsules. We then highlight unique properties of nanocapsules essential for practical applications, such as precise control of pore size and chemical environment, selective permeability, and ultrafast transport through the pores. We discuss new motifs for catch and release of small molecules with porous nanocapsules based on controlling the microenvironment inside the nanocapsules, regulating the charge on the orifice of nanopores in the shells, and reversible synergistic action of host and guest forming a supramolecular complex in nanocapsules. We demonstrate successful creation of fast-acting and selective nanoreactors by encapsulation of diverse homogeneous and nanoparticle catalysts. Due to unhindered flow of substrates and products through the nanopores, encapsulation did not compromise catalytic efficiency and, in fact, improved the stability of entrapped catalysts. We present robust nanoprobes based on nanocapsules with entrapped sensing agents and show how the encapsulation resulted in selective measurements with fast response times in challenging conditions, such as small volumes and complex mixtures. Throughout this Account, we highlight the advantages of encapsulation and discuss the opportunities for future design of nanodevices.

Autopoietic Behavior of Dynamic Covalent Amphiphiles

The condensation of aldehydes and amines in water to give amphiphilic imines can lead to a particular autocatalytic behavior known as autopoiesis, in which the closed micellar structure made by the amphiphile at the mesoscale can accelerate the condensation of its constituents. Herein, through a combination of analytical tools, including diffusion ordered spectroscopy (DOSY) as well as light, neutron, and X-ray scattering techniques, the thermodynamic and kinetic parameters were probed at both the level of dynamic covalent imine bond formation and the level of the resulting micellar self-assemblies. It was found that the autopoietic behavior was the result of a combination of several parameters, including solubilization of hydrophobic building blocks, template effect at the core-shell interface, and growth/division cycles of the micellar objects.

On the influence of fatty acid chain unsaturation on supramolecular gelation of aminocarbohydrate-based supra-amphiphiles

Supramolecular gels are soft materials formed mainly by low molecular weight units held together by intermolecular interactions. Stabilizing these kinds of materials is quite a challenge due to the influence of multiple factors interfering with the integrity of the supramolecular structure. In our previous studies, we have shown that the aminocarbohydrate meglumine (MEG) interacts with organic acids by ion-pairing leading to the formation of MEG–carboxylate adducts. These adducts undergo supramolecular polymerization by heat treatment, but the macromolecular assembly was stable for a short period due to hydrogen bond (H-bond) breakup. Herein, we attempt to study the influence of hydrophobic building blocks on the formation of these compounds aiming to stabilize H-bonds to produce polymerizable supra-amphiphiles in water. Oleic acid and stearic acid are two analogous fatty acids differing only in the presence of unsaturation that were used in our studies. Results demonstrated that the presence of unsaturation hinders gelation in water by interfering with the self-assembly behavior of supra-amphiphiles. Thus, unsaturated supra-amphiphiles behave like traditional surfactants and gelify water at high concentrations (above 30% w/w). On the other hand, supramolecular gels with a polymer-like behavior could be produced with a saturated supra-amphiphile in water (above 4% w/w). The material was characterized by a lamellar arrangement that facilitates the alignment of H-bonds necessary to stabilize the self-assembled structure. These results have pivotal importance on the design of polymerizable supra-amphiphiles and demonstrate that the double bond of hydrophobic building blocks is an important design factor to be considered by scientists studying similar materials.

Hydration Promoted by a Methylene Group: A Volumetric Study on Alkynes in Water.

Hydrocarbons including a methylene group are generally considered a hydrophobic building block, in the sense that the density of their hydration water is lower than that of bulk water. However, is the methylene group always hydrophobic? In this study, we experimentally determined the partial molar volume of a methylene group in water as 14.01 ± 0.46 cm3 mol-1 for 1-alkyne, 9.83 ± 0.35 cm3 mol-1 for 2-alkyne, and 11.39 ± 0.55 cm3 mol-1 for 3-alkyne. These values are all unusually small compared to the ∼16 cm3 mol-1 for model compounds from the literature. The subsequent volumetric analysis on the basis of the Kirkwood-Buff parameter indicates that the hydration water is enriched by the addition of a methylene group for 2-alkyne, while it is depleted for the reported model compounds that contain hydrophilic functional groups, 1-alkyne, and 3-alkyne. Our findings suggest that the triple bonded carbons in 2-alkyne that reduce hydration water act as a hydrophobic group in 2-alkyne. Thus, the methylene group should be called "hydrophilic" in this case because it actually recovers the hydration water when placed next to more hydrophobic groups. Therefore, we conclude that the hydrophobicity of a methylene group varies depending on its hydration environment due to other functional groups in the solute.

Synthesis of Trifluoromethyl Tetrafluoro‐λ6‐sulfanyl‐Substituted Alkenes, Ketones, and Acids: Polar Hydrophobic Building Blocks

The trifluoromethyl tetrafluoro‐λ6‐sulfanyl (CF3SF4) group is both extraordinarily lipophilic and profoundly electron withdrawing, properties associated with polar hydrophobicity. Utilization of the CF3SF4 group to prepare novel materials or biologically active agents will not be possible without new methods for the synthesis of aliphatic CF3SF4‐substituted building blocks. To advance those studies, trichloromethanesulfenyl chloride was conveniently converted to trans‐trifluoromethyl tetrafluoro‐λ6‐sulfanyl chloride (CF3SF4Cl) by oxidative chlorofluorination. Triethylborane‐promoted addition reactions of trans‐CF3SF4Cl to substituted olefins and alkynes yielded a variety of new materials. Those addition products were subsequently transformed to CF3SF4‐substituted carboxylic acids, CF3SF4‐substituted ketones, and a CF3SF4‐substituted aldehyde.

Facile dynamic one-step modular assembly based on boronic acid-diol for construction of a micellar drug delivery system.

Nano-assembled amphiphilic micelles with characteristics including facile control, a simplified construction procedure, convenient and efficient drug loading, and a controlled release at pathological sites are in high demand. This study reports a facile and dynamic one-step modular assembly strategy based on boronic acid-diol for constructing focus-responsive micellar drug delivery systems. In this manner, a dopamine modified hydrophilic building block, phenylboronic acid modified hydrophobic building block and drug molecules (Dox) spontaneously one-step assembled into drug encapsulated distinct core/shell micelles (Dox/PBAE-M) in mild physiological media. After a simple adjustment of weight ratios between these three building blocks, Dox/PBAE-M, with the highest Dox-loading capacity (22.4%) and optimal physical dimensions, was generated. Furthermore, the desirable pH-dependent disassembly of Dox/PBAE-M was independently verified by morphological changes alongside in vitro release of Dox in different simulated environments. The experimental results here demonstrated that Dox/PBAE-M kept structural integrity in normal physiological environments, while accomplishing a selective nano-disassembly and Dox release within acid endo/lysosomes. As a result, Dox/PBAE-M exhibited the highest cytotoxicity and apoptosis induction among all of the tested groups on the 4T1 breast cancer xenograft model. This newly proposed assembly strategy gave new insight into easy fabrication and disassembly of multi-functional micellar drug delivery systems.

Dynamic Sub-10-nm Nanostructured Ultrathin Films of Sugar-Polyolefin Conjugates Thermoresponsive at Physiological Temperatures.

Spin-casting of a cellobiose-atactic polypropene (CB-aPP) conjugate (1) from a 0.1% (w/w) n-butanol/hexane solution onto highly oriented pyrolytic graphite (HOPG) and carbon-coated Si(100) spontaneously produced microphase-separated sub-10-nm nanostructured ultrathin films in the form of alternating CB and aPP lamellar domains (d = 6.60 ± 0.68 nm) that are oriented perpendicular to the substrate surface. Thermal annealing at modest temperatures (e.g., 50-100 °C), and as low as the physiologically relevant temperature of 38 °C, serves to drive a structural transition that yields a parallel stacked bilayer assembly as the thermodynamically favored nanostructure. These results establish the advantage of low molecular weight, narrow polydispersity, and amorphous, low Tg, poly(α-olefinate)s (xPAOs) as a new class of hydrophobic building block for amphiphilic materials, and sugar-PAO conjugates in particular, for the development of stimuli-responsive, nanostructured materials for technological applications at physiological temperatures.

Self-assembly of supra-amphiphile of azobenzene-galactopyranoside based on dynamic covalent bond and its dual responses

In this paper, dynamic covalent bond has been employed to construct supra-amphiphile of carbohydrate for the first time. In neutral environment, the molecule was fabricated by reacting a hydrophobic building block bearing benzoic aldehyde with a hydrophilic building block bearing hydrazine to form a sugar-containing supra-amphiphile based on acylhydrazone bond. The obtained azobenzene-galactopyranoside (Azo-Gal) supra-amphiphile self-assembled to fibrillar structure in water, which showed dual responses to UV light and pH.

Molecular assembly of highly symmetric molecules under a hydrogen bond framework controlled by alkyl building blocks: a simple approach to fine-tune nanoscale structures.

To date, molecular assemblies under the contribution of hydrogen bond in combination with weak interactions and their consequent morphologies have been variously reported; however, how the systematic variation of the structure can fine-tune the morphologies has not yet been answered. The present work finds an answer through highly symmetric molecules, i.e. diamine-based benzoxazine dimers. This type of molecule develops unique molecular assemblies with their networks formed by hydrogen bonds at the terminal, while, at the same time, their hydrogen bonded frameworks are further controlled by the hydrophobic segment at the center of the molecule. When this happens, slight differences in hydrophobic alkyl chain lengths (, , and ) bring a significant change to the molecular assemblies, thus resulting in tunable morphologies, i.e. spheres, needles and dendrites. The superimposition between the crystal lattice obtained from X-ray single crystal analysis and the electron diffraction pattern obtained from transmission electron microscopy allows us to identify the molecular alignment from single molecules to self-assembly until the morphologies developed. The present work, for the first time, shows the case of symmetric molecules, where the hydrophobic building block controls the hydrogen bond patterns, leading to the variation of molecular assemblies with tunable morphologies.

Synthesis and evaluation of some derivatives of polysiloxanes

Silicone surfactants have been widely used in our daily life and many industrial fields on the basis of their unusual properties. Only in the past decades has the use of silicone as a hydrophobic building block for the preparation of surfactants become common. The recent trend to combine silicone, polyoxyalkylene and carbohydrate moieties in the same molecule has resulted in a plethora of new compounds with new properties.In this article, we report the preparation of a series of “glycopolysiloxanes” surfactants with different molecular weights. They were structurally characterized by IR, 1H NMR and MS.Specifically, the critical micelle concentration (cmc), effectiveness of surface tension reduction (πcmc), maximum surface excess (Γmax), minimum surface area (Amin) and standard free energies of micellization (ΔG°mic) and adsorption (ΔG°ads) have been determined from aqueous surface tension measurements using Du-Nouy Tensiometer (KRUSS K6 type 4851) with a platinum ring. All the surfactants have good surface properties and have low cmc.The bacteriostatic power of these polymers was tested and compared under the same conditions in aqueous solution against common strains of Gram positive bacteria and strains of Gram negative bacteria.

ChemInform Abstract: Efficient and Scalable Synthesis of 4‐Carboxy‐Pennsylvania Green Methyl Ester: A Hydrophobic Building Block for Fluorescent Molecular Probes.

AbstractThe improved reaction conditions allow the synthesis of multigram quantities of the title compound (VIII) in 28% overall yield.