Charged Core Research Articles

Removal of core hole distortion from ionization edges in electron energy loss spectroscopy

The near-edge fine structure in electron energy loss spectra is used to probe the electronic bonding environment of materials at high spatial resolution. Often, however, deviations from the ground state electronic properties are observed, due to the core hole created within the ionized atom. A method is proposed to remove core hole distortion from experimental electron energy loss spectra by calculating the electrodynamic work done in separating the moving, incident electron from the oppositely charged core hole. Dynamic screening of the core hole is modeled using the material dielectric properties. The resulting energy gain spectrum is deconvolved from the experimental measurement to give a ``fully screened'' spectrum that is free of core hole distortion. The method is tested on core loss edges in elemental Si, SiC, and ${\mathrm{SiO}}_{x}$. Despite assuming classical electrodynamics, the fundamental principle of an energy gain correction can be shown to be consistent with quantum mechanics, although shortcomings in some of the assumptions made on the nature of the core hole are also identified.

Ionic amphiphile stabilized reverse micellar systems and their implications for nanoencapsulation

HypothesisEncapsulation of core nanoparticles using reverse micelles is a widely used approach owing to its effective organization. Hence, it is of value to analyze the physicochemical mechanisms associated with the reverse micelle-based encapsulation for the choice of appropriate surfactant for the encapsulation process. The presence of ionic micelles, catalyst ions and surface charge of the core nanoparticles are expected to influence the stability of reverse micelles. Hence, it is of value to find the optimized conditions for stable reverse micelles formation through understanding the multiple double layer formation inside of ionic reverse micelles. ExperimentsReverse micelle systems stabilized by non-ionic, anionic and cationic surfactants are formulated with the presence of ammonia ions and negatively charged core nanoparticles. The structure of reverse micelles is studied by measuring its average hydrodynamic diameter and optical transmittance measurements. Shell encapsulation experiments are performed in stable and unstable reverse micellar structures. FindingsIonic surfactants help to form stable reverse micellar structures. Multiple double layers formation is explained in ionic reverse micelles for the first time. Magnetite@silica is chosen as a model system to demonstrate the observed effects. The results obtained could remove the complexity in understanding the ionic reverse micellar systems for the functionalization of nanoparticles.

Viscous Core Liposomes Increase siRNA Encapsulation and Provides Gene Inhibition When Slightly Positively Charged.

Since its discovery, evidence that siRNA was able to act as an RNA interference effector, led to its acceptation as a novel medicine. The siRNA approach is very effective, due to its catalytic mechanism, but still the limitations of its cellular delivery should be addressed. One promising form of non-viral gene delivery system is liposomes. The variable and versatile nature of the lipids keeps the possibility to upgrade the liposomal structure, which makes them suitable for encapsulation and delivery of drugs. However, to avoid the limitation of fast release for the hydrophilic drug, we previously designed viscous core liposomes. We aimed in this work to evaluate if these viscous core liposomes (NvcLs) could be of interest for siRNA encapsulation. Then, we sought to add a limited amount of positive charges to provide cell interaction and transfection. Cationic lipid dimyristoylaminopropylaminopropyl or the polymer poly(ethylenimine) were incorporated in NvcL to produce positively charged viscous core liposomes (PvcL) by a customized microfluidic device. We found that NvcLs increased the encapsulation efficiency and loading content with regards to the neutral liposome. Both PvcLPEI and PvcLDMAPAP exhibited transfection and GFP knock-down (≈40%) in both 2D and 3D cell cultures. Finally, the addition of slight positive charges did not induce cell toxicity.

Charge-reversal nanocomolexes-based CRISPR/Cas9 delivery system for loss-of-function oncogene editing in hepatocellular carcinoma

Hepatocellular carcinoma (HCC) is one of the most lethal cancers worldwide. There are still challenges for HCC treatments, especially high resistance of the cancer cells to chemotherapy and/or target therapy. In this study, a responsive charge-reversal vehicle consists of negatively charged heparin core and positively charged ethanolamine (EA)-modified poly(glycidyl methacrylate) (PGEA) shell (named Hep@PGEA) with self-accelerating release for condensed nucleic acids was proposed to deliver the pCas9 plasmid encoding clustered regularly interspaced short palindromic repeats (CRISPR)-associated protein 9 (Cas9) and the sgRNA targeting oncogene survivin to treat HCC. The Hep@PGEA/pCas9 system showed high anti-tumor efficiency via inducing apoptosis and inhibiting proliferation, migration and invasion capability of HCC cells. The Hep@PGEA/pCas9 system was further utilized to treat orthotopic HCC in mice via tail vein injection. The system exhibited an evident accumulation in the liver of mice and achieved obvious anti-tumor effects. The Hep@PGEA/pCas9 system also showed marked improvement of HCC therapy with sorafenib and provided promising combination HCC treatment potentials. Moreover, enrichment of the Hep@PGEA-based delivery system in liver highlights its possibilities for treatments of other liver diseases.

Ionically Charged Topological Defects in Nematic Fluids

Charge profiles in liquid electrolytes are of crucial importance for applications, such as supercapacitors, fuel cells, batteries, or the self-assembly of particles in colloidal or biological settings. However, creating localised (screened) charge profiles in the bulk of such electrolytes, generally requires the presence of surfaces -- for example, provided by colloidal particles or outer surfaces of the material -- which poses a fundamental constraint on the material design. Here, we show that topological defects in nematic electrolytes can perform as regions for local charge separation, forming charged defect cores and in some geometries even electric multilayers, as opposed to the electric double layers found in isotropic electrolytes. Using a Landau-de Gennes-Poisson-Boltzmann theoretical framework, we show that ions highly effectively couple with the topological defect cores via ion solvability, and with the local director-field distortions of the defects via flexoelectricity. The defect charging is shown for different defect types -- lines, points, and walls -- using geometries of ionically screened flat isotropic-nematic interfaces, radial hedgehog point defects and half-integer wedge disclinations in the bulk and as stabilised by (charged) colloidal particles. More generally, our findings are relevant for possible applications where topological defects act as diffuse ionic capacitors or as ionic charge carriers.

Dendrimer-decorated nanogels: Efficient nanocarriers for biodistribution in vivo and chemotherapy of ovarian carcinoma

Nanomedicine has revolutionized disease theranostics by the accurate diagnosis and efficient therapy. Here, the PAMAM dendrimer decorated PVCL-GMA nanogels (NGs) were developed for favorable biodistribution in vivo and enhanced antitumor efficacy of ovarian carcinoma. By an ingenious design, the NGs with a unique structure that GMA-rich domains were localized on the surface were synthesized via precipitation polymerization. After G2 dendrimer decoration, the overall charge is changed from neutral to positive, and the NGs-G2 display the whole charge nature of positively charged corona and neutral core. Importantly, the unique architecture and charge conversion of NGs-G2 have a profound impact on the biodistribution and drug delivery in vivo. As a consequence of this alteration, the NGs-G2 as nanocarriers emerge the highly sought biodistribution of reduced liver accumulation, enhanced tumor uptake, and promoted drug release, resulting in the significantly augmented antitumor efficacy with low side effects. Remarkably, this finding is contrary to some reported work that the nanocarriers with positive charge have preferential liver uptake. Moreover, the NGs-G2 also displayed thermal/pH dual-responsive behaviors, excellent biocompatibility, improved cellular uptake, and stimuli-responsive drug release. Encouragingly, this work demonstrates a novel insight into the strategy for optimizing design, improving biodistribution and enhancing theranostic efficacy of nanocarriers.

Relativistic electric potential near a resting straight carbon nanotube of a finite-length with stationary current

Based on the Lienard – Wiechert potentials for a uniformly and rectilinearly moving electron, a relativistic electric field is studied near a densely filled with potassium atoms single-walled carbon nanotube (K@CNT) with a stationary electric current inside it. The relativistic electric field in the laboratory coordinate system arises (due to the Lorentz transformations) only for a nanotube of a finite length. This field is a result of summation of the Coulomb fields of stationary positively charged ionic cores of potassium and an equal number of ballistically moving valence electrons of potassium that create a current. It is shown that the magnitude of the negative relativistic electric potential of K@CNT in the direction perpendicular to the nanotube does not depend on the direction of the current density. The relationship is obtained between the K@CNT radius and the number of open channels of ballistic electron transfer over potassium atoms. The Landauer formula is used, which relates the number of open quasi-one-dimensional channels and the direct current electrical conduction. For the first time, analytical formulas are obtained for the dependence of the relativistic potential near K@CNT on the electric voltage between the ends of the nanotube and on its radius in the limit of zero absolute temperature. The case is considered when the distance from the point of registration of the relativistic potential above the center of the nanotube is much less than its length. For nanotube with diameter of 2 nm and length of 100 mm, under an external electric field strength of 5 mV/mm, the magnitude of the potential of the relativistic electric field is of about 2 mV. Modern measurement techniques make it possible to register the predicted relativistic potential.

A Strained Ion Pair Permits Carbon Dioxide Fixation at Atmospheric Pressure by C-H H-Bonding Organocatalysis.

The cycloadditions of carbon dioxide into epoxides to afford cyclic carbonates by H-bond donor (HBD) and onium halide (X) cocatalysis have emerged as a key strategy for CO2 fixation. However, if the HBD is also a halide receptor, the two will quench each other, decreasing the catalytic activity. Here, we propose a strained ion pair tris(alkylamino)cyclopropenium halide (TAC·X), in which TAC repels X. TAC possesses a positively charged cyclopropenium core that makes the vicinal C-H or N-H a nonclassical HBD. The interionic strain within TAC·X makes TAC a more electrophilic HBD, allowing it to activate the oxygen of the epoxide and making X more nucleophilic and better able to attack the methylene carbon of the epoxide. NMR titration spectra and computational studies were employed to probe the mechanism of the cycloaddition of CO2 to epoxides reactions under the catalysis of TAC·X. The 1H and 13C{1H}NMR titration spectra of the catalyst with the epoxide substrate unambiguously confirmed H-bonding between TAC and the epoxide. DFT computational studies identified the transition states in the ring-opening of the epoxide (TS1) and in the ring-closure of the cyclic carbonate (TS2).

From Antiaromatic Norcorrolatonickel(II) to Aromatic and Nonaromatic Zwitterions: Innocent Ligands with Unbalanced Charge of the Core.

A three-component reaction of antiaromatic meso-mesityl-3-nitronorcorrolatonickel(II) 1-NO2 with dialkyl acetylenedicarboxylate and PBu3 yields aromatic zwitterionic corrole nickel(II) complexes 3-R with one of the meso-substituents comprising a positively charged tributyl phosphonium group and negatively charged coordination core. Reaction of 1-NO2 with PBu3 alone resulted in a nonaromatic chiral adduct 5 of a zwitterionic phlorine character with a −PBu3+ group at a pyrrole β-position.

Dual-Responsive Polyprodrug Nanoparticles with Cascade-Enhanced Magnetic Resonance Signals for Deep-Penetration Drug Release in Tumor Therapy.

Smart transformable nanocarriers are promising to treat deep-seated diseases but require adaptable diagnostic/imaging potency to reflect the morphology change and therapeutic feedback, yet their design and synthesis remains challenging. Herein, stimuli-responsive polyprodrug nanoparticles (SPNs) are formulated from the co-assembly of negatively charged corona and positively charged polyprodrug cores, exhibiting high loading content of camptothecin (CPT, ∼28.6 wt %) tethered via disulfide linkages in the core. SPNs are sequentially sensitive to tumor acidic condition and elevated reductive milieu in the cytosol for deep-penetration drug delivery. Upon accumulation at acidic tumor sites, SPNs dissociate to release smaller positively charged polyprodrug nanoparticles, which efficiently enter deep-seated tumor cells to trigger high-dosage parent CPT release in the reductive cytosolic milieu. Meanwhile, the polyprodrug cores of SPNs labeled with DTPA(Gd), a magnetic resonance imaging contrast agent, can trace the cascade degradation and biodistribution of SPNs as well as the resulting intracellular CPT release. The longitudinal relaxivity of SPNs increases stepwise in the above two processes. The size-switchable polyprodrug nanoparticles exhibit remarkable tumor penetration and noteworthy tumor inhibition in vitro and in vivo, which are promising for endogenously activated precision diagnostics and therapy.

The structure of the antimicrobial human cathelicidin LL-37 shows oligomerization and channel formation in the presence of membrane mimics

The human cathelicidin LL-37 serves a critical role in the innate immune system defending bacterial infections. LL-37 can interact with molecules of the cell wall and perforate cytoplasmic membranes resulting in bacterial cell death. To test the interactions of LL-37 and bacterial cell wall components we crystallized LL-37 in the presence of detergents and obtained the structure of a narrow tetrameric channel with a strongly charged core. The formation of a tetramer was further studied by cross-linking in the presence of detergents and lipids. Using planar lipid membranes a small but defined conductivity of this channel could be demonstrated. Molecular dynamic simulations underline the stability of this channel in membranes and demonstrate pathways for the passage of water molecules. Time lapse studies of E. coli cells treated with LL-37 show membrane discontinuities in the outer membrane followed by cell wall damage and cell death. Collectively, our results open a venue to the understanding of a novel AMP killing mechanism and allows the rational design of LL-37 derivatives with enhanced bactericidal activity.

Impact of charged polarizable core on mobility of a soft particle embedded in a hydrogel medium

Electrophoresis of a soft particle with a charged polarizable core is analyzed theoretically. The soft particle is embedded in an uncharged hydrogel medium. The hydrodynamics in both the gel medium and the soft layer encapsulating the hard core are governed by the Darcy-Brinkman model. We have considered the numerical model based on the conservation principle of mass, momentum, and ion flux, leading to a coupled set of partial differential equations. A simplified approach under the weak field and low charge density consideration is also proposed. The subtle nonlinear effects arising due to the polarization and relaxation of the double layer and the convective transport of counterions induced by the immobile charge of soft layer are elucidated. These nonlinear effects have negligible impact when the bulk ionic concentration becomes high. The simplified model under the weak field consideration is independent of the core dielectric permittivity. However, the numerical model shows a strong dependence on core permittivity when the applied electric field is moderate. We have also addressed the ion partitioning effect when the dielectric permittivity of the soft layer is different from the gel medium. This creates a counterion saturation in the soft layer, and hence an augmentation in the electrophoresis.

Self-Assembled Dual-Targeted Epirubicin-Hybrid Polydopamine Nanoparticles for Combined Chemo-Photothermal Therapy of Triple-Negative Breast Cancer.

PurposeFolic acid and cyclic arginylglycylaspartic acid peptides were introduced to the surface of negatively charged lipid-coated hybrid polydopamine-cysteine cores for the delivery of epirubicin (EPI) (E/PCF-NPs). The combined chemo-photothermal therapy using E/PCF-NPs for triple-negative breast cancer was evaluated.Materials and MethodsThe temperature elevation and thermal toxicity of nanoparticles were studied. The morphology and properties of E/PCF-NPs were characterized by transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Physicochemical properties, including particle size, zeta potential, drug loading, entrapment efficiency (EE%), stability and in vitro release, were determined. The cell viability, reactive oxygen species (ROS) levels, ratios of oxidized nicotinamide adenine dinucleotide to its reduced form (NAD+/NADH), apoptosis assays, and cellular uptake of E/PCF-NPs were determined on 4T1 cells. Pharmacokinetic studies and tissue distributions were performed and detected by an ultra-high performance liquid chromatography/mass spectrometry system. The antitumor effects of E/PCF-NPs under near-infrared (NIR) laser irradiation were also evaluated.ResultsThe sphere-like morphology of E/PCF-NPs showed a high EE%, uniform size of 106.7 nm, remarkable stability, and highly improved cytotoxicity under NIR laser, when compared to that of photothermal treatment alone. In vitro release of EPI from E/PCF-NPs was pH sensitive, and a greater response was achieved under NIR laser irradiation. Compared to chemotherapy or photothermal treatment alone, the combined treatment in vitro significantly inhibited the survival rate of 4T1 cells to 17.7%, induced ROS generation, and reduced NAD+/NADH significantly. Treatment with E/PCF-NPs under irradiation induced 4T1 cell apoptosis in approximately 93.6% cells. In vitro cellular uptake of E/PCF-NPs was time-dependent. The long-circulating and higher tumor accumulation of E/PCF-NPs resulted in complete ablation of breast tumor tissue through the enhanced photothermal effect by NIR laser irradiation-mediated cell apoptosis.ConclusionE/PCF-NPs show enhanced anti-cancer effects due to synergistic effects of chemotherapy with photothermal therapy and may be potential therapeutic agents for cancer treatment.

Impact of oppositely charged shell and cores on interaction of core-shell colloids with differently charged proteins as a route for tuning of the colloids cytotoxicity

The present work represents interactions between the core-shell nanoparticles and different proteins, exemplified by lysozyme (LSZ), pepsin, bovine serum albumin (BSA), thioredoxin (TRX) and yellow fluorescent protein (YFP). The core-shell morphology derives from the non-covalent deposition of polyethyleneimine (PEI) onto nanoprecipitated luminescent complex (AuCl)2L (L is cyclic PNNP ligand). Analysis of the data obtained by DLS, CD spectroscopy, luminescence derived from both (AuCl)2L and YFP reveal the electrostatically driven interaction of negatively charged proteins with the shell of PEI-(AuCl)2L. The fluorescence of YFP enables to reveal the inclusion of the protein molecules into the shell. The lack of any luminescent response of PEI-(AuCl)2L on TRX conforms its electrostatically driven interactions with the shell which, in turn, excludes a binding of the exposed thiol moieties with (AuCl)2L. The negatively charged surface of pepsin provides the greatest recharging of the PEI-based shell versus the other proteins, which is followed by the enhanced luminescence of (AuCl)2L. The significant effect of PEI-(AuCl)2L on the CD spectra of LSZ followed by the decreased intensity of (AuCl)2L-based luminescence points to specific interaction mode of PEI-(AuCl)2L with LSZ. The flow cytometry and fluorescent microscopy measurements revealed efficient internalization of PEI-(AuCl)2L into the Wi-38 cell samples resulting in the efficient staining of all cell organelles. The concentration dependent cytotoxicity of PEI-(AuCl)2L is detectably enhanced by LSZ, which is correlated with its interaction mode with the nanoparticles.

Specific-oxygen-supply functionalized core-shell nanoparticles for smart mutual-promotion between photodynamic therapy and gambogic acid-induced chemotherapy

Photodynamic therapy (PDT) and chemotherapy of cancer both meet respective challenges. Tumor hypoxia, low penetration and high glutathione (GSH) level bear the brunt. Herein, a core-shell nanoparticle, with multi-function of hypoxia-responsiveness, specific oxygen supply and deep tumor penetration, was constructed for smart mutual-promotion between the both to overcome the respective restrictions. The nano platform (GC@MCS NPs) was composed of hypoxia-responsive hyaluronic acid-nitroimidazole (HA-NI) as shells, MnO2 NPs as oxygen modulators and reduction-responsive functionalized poly (l-glutamic acid) derivatives (γ-PFGA) as cores to deliver gambogic acid (GA) and Chlorine6 (Ce6). After endocytosis, the approximately 100 nm of GC@MCS NPs achieved hypoxia-responsive shell degradation and MnO2 release, followed by reduction-activated charge conversion to form positively charged cores. With the damage effect of superficial tumor cells by the partially released GA, GA&Ce6-loadedγ-PFGA penetrated deep inside through electronic interaction step by step. Upon irradiated with 638 nm of laser, widely permeated Ce6 was activated for enhanced PDT under the high oxygenation by MnO2 NPs. The generated reactive oxygen species (ROS) in return facilitated the GA-induced paraptosis by clearing high level of GSH. As a result, this mutual promotion strategy contributed to 92.41% of 4T1 tumor inhibition rate, exhibiting outstanding advantages. Our GC@MCS NPs provided a smart combination of chemo-photodynamic therapy and focused on addressing the tumor hypoxia and low penetration issues.

Particle-Size-Dependent Delivery of Antitumoral miRNA Using Targeted Mesoporous Silica Nanoparticles

Multifunctional core-shell mesoporous silica nanoparticles (MSN) were tailored in size ranging from 60 to 160 nm as delivery agents for antitumoral microRNA (miRNA). The positively charged particle core with a pore diameter of about 5 nm and a stellate pore morphology allowed for an internal, protective adsorption of the fragile miRNA cargo. A negatively charged particle surface enabled the association of a deliberately designed block copolymer with the MSN shell by charge-matching, simultaneously acting as a capping as well as endosomal release agent. Furthermore, the copolymer was functionalized with the peptide ligand GE11 targeting the epidermal growth factor receptor, EGFR. These multifunctional nanoparticles showed an enhanced uptake into EGFR-overexpressing T24 bladder cancer cells through receptor-mediated cellular internalization. A luciferase gene knock-down of up to 65% and additional antitumoral effects such as a decreased cell migration as well as changes in cell cycle were observed. We demonstrate that nanoparticles with a diameter of 160 nm show the fastest cellular internalization after a very short incubation time of 45 min and produce the highest level of gene knock-down.

Comparing Zwitterionic and PEG Exteriors of Polyelectrolyte Complex Micelles.

A series of model polyelectrolyte complex micelles (PCMs) was prepared to investigate the consequences of neutral and zwitterionic chemistries and distinct charged cores on the size and stability of nanocarriers. Using aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization, we synthesized a well-defined diblock polyelectrolyte system, poly(2-methacryloyloxyethyl phosphorylcholine methacrylate)-block-poly((vinylbenzyl) trimethylammonium) (PMPC-PVBTMA), at various neutral and charged block lengths to compare directly against PCM structure–property relationships centered on poly(ethylene glycol)-block-poly((vinylbenzyl) trimethylammonium) (PEG-PVBTMA) and poly(ethylene glycol)-block-poly(l-lysine) (PEG-PLK). After complexation with a common polyanion, poly(sodium acrylate), the resulting PCMs were characterized by dynamic light scattering (DLS) and small angle X-ray scattering (SAXS). We observed uniform assemblies of spherical micelles with a diameter ~1.5–2× larger when PMPC-PVBTMA was used compared to PEG-PLK and PEG-PVBTMA via SAXS and DLS. In addition, PEG-PLK PCMs proved most resistant to dissolution by both monovalent and divalent salt, followed by PEG-PVBTMA then PMPC-PVBTMA. All micelle systems were serum stable in 100% fetal bovine serum over the course of 8 h by time-resolved DLS, demonstrating minimal interactions with serum proteins and potential as in vivo drug delivery vehicles. This thorough study of the synthesis, assembly, and characterization of zwitterionic polymers in PCMs advances the design space for charge-driven micelle assemblies.

Analytic Expression for Electrophoretic Mobility of Soft Particles with a Hydrophobic Inner Core at Different Electrostatic Conditions.

This paper presents a simplified model for the electrophoresis of a soft particle with a nonwettable rigid core with charged polyelectrolyte corona under a weak-field and low-charge density consideration. We have derived a closed form solution for the mobility, which reduces to the well-known expressions for mobility as derived by Ohshima for limiting cases such as a hydrophilic charged core coated with an uncharged polymer (Ohshima, H. J. Colloid Interface Sci. 2002, 252, 119-125) or an uncharged no-slip core coated with a polyelectrolyte layer (Ohshima, H. Electrophoresis 2006, 27, 526-533). The generalized mobility expression reduces to the existing expression for mobility of a rigid hydrophobic colloid as the soft layer shrinks to zero. The general form of the mobility expression involves elliptic integrals, which can be computed easily through a software like Mathematica. We have derived analytical solutions for mobility pertaining to several particular cases. The occurrence of mobility reversal when the core and polyelectrolyte layer has a charge of opposite polarity is demonstrated in this paper.

Long-Range N-N Bonding by Rydberg Electrons.

By using high-level ab initio methods, we examine the nature of bonding between Rydberg electrons hosted by two four-coordinate nitrogen centers embedded in a hydrocarbon scaffold. The electronic structure of these species resembles that of diradicals, yet the diffuse nature of the orbitals hosting the unpaired electrons results in unusual features. The unpaired Rydberg electrons exhibit long-range bonding interactions, leading to stabilization of the singlet state (relative to the triplet) and a reduced number of effectively unpaired electrons. However, thermochemical gains due to through-space bonding are offset by strong Coulomb repulsion between positively charged nitrogen cores. The kinetic stability of these Rydberg diradicals may be controlled by a judicious choice of the molecular scaffold, suggesting possible strategies for their experimental characterization.

Dual‐Scale Nanostructures via Evaporative Assembly

AbstractDual‐scale hierarchical structures with regular microscale patterns and varying degree of nanoscale crystalline order are synthesized on physically and chemically homogeneous substrates by evaporative self‐assembly with a suspension of DNA‐functionalized nanoparticles (NPs) with a charged core shell. For a certain NP concentration range, periodic concentric rings in a stripe‐like micropattern are produced over macroscale surface areas by an NP monolayer with hexagonal lattice structure at the nanoscale. The stripe width, spacing, and nanoparticle ordering can be controlled by varying the NP concentration. The results indicate that the interplay between “stick‐slip” motion of the droplet contact line and coulombic and steric NP interactions control the formation of the observed structures. A simple analytical model is proposed to account for the experimental observations and guide the future design of different nanostructure morphologies. This work demonstrates a simple cost‐effective mask‐free method for fabricating large‐area nanostructured 2D materials and metasurfaces for applications ranging from energy conversion/storage to optoelectronics and nanophotonics.