Self‐Assembled Shape‐Memory Fibers of Triblock Liquid‐Crystal Polymers

New thermoplastic liquid‐crystalline elastomers have been synthesized using the telechelic principle of microphase separation in triblock copolymers. The large central block is made of a main‐chain nematic polymer renowned for its large spontaneous elongation along the nematic director. The effective crosslinking is established by small terminal blocks formed of terphenyl moieties, which phase separate into semicrystalline micelles acting as multifunctional junction points of the network. The resulting transient network retains the director alignment and shows a significant shape‐memory effect, characteristic and exceeding that of covalently bonded nematic elastomers. Its plasticity at temperatures above the nematic–isotropic transition allows drawing thin well‐aligned fibers from the melt. The fibers have been characterized and their thermal actuator behavior—reversible contraction of heating and elongation on cooling—has been investigated.     

光响应液晶嵌段共聚物研究进展

光响应液晶嵌段共聚物综合了光响应性液晶和嵌段聚合物两类材料的优异特性,是一种多功能性的新型材料。其中以偶氮苯为代表的光响应基团作为液晶基元的嵌段共聚物是其目前研究的主体。本文对光响应液晶材料和嵌段聚合物分别做了简要介绍,阐述了它们各自的优势和特点。对于光响应液晶嵌段共聚物的光响应机理、相分离过程和有序化调控手段进行了重点探讨。在此基础上,介绍了其在光子学、有机纳米模板和聚合物胶束等方面的研究进展。     

Nanoscale Organization of a Platinum(II) Acetylide Cholesteric Liquid Crystal Molecular Glass for Photonics Applications

The fabrication, molecular structure, and spectroscopy of a stable cholesteric liquid crystal platinum acetylide glass obtained from trans‐Pt(PEt₃)₂(C?C?C₆H₅?C?N)(C?C?C₆H₅?COO?Cholesterol), are described and designated as PE1‐CN‐Chol. Polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray scattering experiments show room temperature glassy/crystalline texture with crystal formation upon heating to 165 °C. Further heating results in conversion to cholesteric phase. Cooling to room temperature leads to the formation of a cholesteric liquid crystal glass. Scanning tunneling microscopy of a PE1‐CN‐Chol monolayer reveals self‐assembly at the solid?liquid interface with an array of two molecules arranged in pairs, oriented head‐to‐head through the CN groups, giving rise to a lamella arrangement. The lamella structure obtained from molecular dynamics calculations shows a clear phase separation between the conjugated platinum acetylide and the hydrophobic cholesterol moiety with the lamellae separation distance being 4.0 nm. Ultrafast transient absorption and flash photolysis spectra of the glass show intersystem crossing to the triplet state occurring within 100 ps following excitation. The triplet decay time of the film compared to aerated and deoxygenated solutions is consistent with oxygen quenching at the film surface but not within the film. The high chromophore concentration, high glass thermal stability, and long triplet lifetime in air show that these materials have potential as nonlinear absorbing materials.     

Self‐Healing Materials via Reversible Crosslinking of Poly(ethylene oxide)‐Block‐Poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) Block Copolymer Films

The application of well‐defined poly(furfuryl glycidyl ether) (PFGE) homopolymers and poly(ethylene oxide)‐b‐poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) block copolymers synthesized by living anionic polymerization as self‐healing materials is demonstrated. This is achieved by thermo‐reversible network formation via (retro) Diels‐Alder chemistry between the furan groups in the side‐chain of the PFGE segments and a bifunctional maleimide crosslinker within drop‐cast polymer films. The process is studied in detail by differential scanning calorimetry (DSC), depth‐sensing indentation, and profilometry. It is shown that such materials are capable of healing complex scratch patterns, also multiple times. Furthermore, microphase separation within PEO‐b‐PFGE block copolymer films is indicated by small angle X‐ray scattering (lamellar morphology with a domain spacing of approximately 19 nm), differential scanning calorimetry, and contact angle measurements.     

Effect of Molecular Weight on the Structure and Morphology of Oriented Thin Films of Regioregular Poly(3‐hexylthiophene) Grown by Directional Epitaxial Solidification

Regioregular head‐to‐tail (HT)‐coupled poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) with a weight‐average molecular weight (M_w) in the 7.3–69.6 kDa range is crystallized by directional epitaxial solidification in 1,3,5‐trichlorobenzene (TCB) to yield highly oriented thin films. An oriented and periodic lamellar structure consisting of crystalline lamellae separated by amorphous interlamellar zones is evidenced by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Both the overall crystallinity as well as the orientation of the crystalline lamellae decrease significantly with increasing M_w. The total lamellar periodicity is close to the length of “fully extended” chains for M_w = 7.3 kDa (polystyrene‐equivalent molecular weight, eq. PS) and it saturates to a value of ca. (25–28) ± 2 nm for M_w ≥ 18.8 kDa (eq. PS). This behavior is attributed to a transition from an oligomeric‐like system, for which P3HT chains are essentially in a fully extended all‐trans conformation and do not fold, to a semicrystalline system that involves a periodic alternation of crystalline lamellae separated by extended amorphous interlamellar zones, which harbor chain folds, chain ends, and tie molecules. For P3HT with M_w of ca. 7.3 kDa (eq. PS), epitaxial crystallization on TCB allows for the growth of both “edge‐on” and “flat‐on” oriented crystalline lamellae on the TCB substrate. The orientation of the lamellae is attributed to 1D epitaxy. Because of the large size of the “flat‐on” crystalline lamellae, a characteristic single‐crystal electron diffraction pattern corresponding to the [001] zone was obtained by selected area electron diffraction (SAED), indicating that P3HT crystallizes in a monoclinic unit cell with a = 16.0 Å, b = 7.8 Å, c = 7.8 Å, and γ = 93.5°.     

Single‐Molecule Tracking of Fibrinogen Dynamics on Nanostructured Poly(ethylene) Films

Using fibrinogen (Fg) protein as a probe molecule, mapping using accumulated probe trajectories (MAPT) is performed on nanostructured melt‐drawn high‐density poly(ethylene) (HDPE) films composed of well‐oriented crystalline patches separated by amorphous regions. The spatially grouped molecular trajectories allow for identification of regions with distinct surface properties (i.e., crystalline vs. amorphous) while simultaneously determining the characteristic dynamic protein behavior within those regions. In the presence of solution with a sufficiently high Fg concentration, discrete patches of a dense, ordered protein layer form (presumably on crystalline HDPE regions), leading to a dramatic rise in the surface residence time (by more than two orders of magnitude) of molecules incorporated into the film. Within this ordered Fg layer, individual molecules exhibit slow anisotropic lateral diffusion; the mobility is restricted by the nanostructure boundaries of the underlying HDPE. On HDPE films at low Fg surface coverage, or on films that have been rendered hydrophilic with Ar plasma, short surface residence times and fast, isotropic diffusion are observed. These results demonstrate the ability of spatially resolved single‐molecule tracking to provide mechanistic information about biomolecule‐surface interactions in a highly heterogeneous environment.     

Liquid‐Crystalline Polymer with a Block Mesogenic Side Group: Photoinduced Manipulation of Nanophase‐Separated Structures

In this report, a novel type of photoresponsive liquid crystalline polymer with a block mesogenic side‐group is demonstrated. The block mesogene is an amphipathic molecule containing a hydrophobic mesogene (azotolane moiety) and hydrophilic oligooxyethylene moieties in the same unit. The block mesogene in the polymer plays a role in liquid crystalline, amphiphilic and photoresponsive properties. As expected, a film prepared from the polymer exhibits phase separation of a lamellar structure due to cooperative motion between liquid crystal assembly and nanophase separation. The morphology of the lamellae can be aligned upon irradiation of linearly polarized light. Moreover, a photochemical phase transition induced by unpolarized UV irradiation erases the surface morphology. The erased nanostructure can be recovered by annealing or irradiation of linearly polarized light, meaning that the surface morphology is rewritable via a photochemical process.     

Separating Crystallization Process of P3HT and O‐IDTBR to Construct Highly Crystalline Interpenetrating Network with Optimized Vertical Phase Separation

The morphology with the interpenetrating network and optimized vertical phase separation plays a key role in determining the charge transport and collection in polymer:nonfullerene small molecular acceptors (SMAs) solar cells. However, the crystallization of polymer and SMAs usually occurs simultaneously during film‐forming, thus interfering with the crystallization process of each other, leading to amorphous film with undesirable lateral and vertical phase separation. The poly(3‐hexylthiophene) (P3HT):O‐IDTBR blend is selected as a model system, and controlling film‐forming kinetics to solve these problems is proposed. Herein, a cosolvent 1,2,4‐triclorobenzene (TCB) with selective solubility and a high boiling point is added to the solution, leading to prior crystallization of P3HT and extended film‐forming duration. As a result, the crystallinity of both components is enhanced significantly. Meanwhile, the prior crystallization of P3HT induces solid–liquid phase separation, hence rationalizing the formation of the nano‐interpenetrating network. Moreover, the surface energy drives O‐IDTBR to enrich near the cathode and P3HT to migrate to the anode. Consequently, a highly crystalline nano‐interpenetrating network with proper vertical phase separation is obtained. The optimal morphology improves charge transport and suppresses bimolecular recombination, boosting the power conversion efficiency from 4.45% to 7.18%, which is the highest performance in P3HT‐based binary nonfullerene solar cells.     

Highly Organized Mesoporous TiO2 Films with Controlled Crystallinity: A Li‐Insertion Study

A study of electrochemical Li insertion combined with structural and textural analysis enabled the identification and quantification of individual crystalline and amorphous phases in mesoporous TiO₂ films prepared by the evaporation‐induced self‐assembly procedure. It was found that the properties of the amphiphilic block copolymers used as templates, namely those of a novel poly(ethylene‐co‐butylene)‐b‐poly(ethylene oxide) polymer (KLE) and commercial Pluronic P123 (HO(CH₂CH₂O)₂₀(CH₂CH(CH₃)O)₇₀(CH₂CH₂O)₂₀H), decisively influence the physicochemical properties of the resulting films. The KLE‐templated films possess a 3D cubic mesoporous structure and are practically amorphous when calcined at temperatures below 450 °C, but treatment at 550–700 °C provides a pure‐phase (anatase), fully crystalline material with intact mesoporous architecture. The electrochemically determined fraction of crystalline anatase increases from 85 to 100 % for films calcined at 550 and 700 °C, respectively. In contrast, the films prepared using Pluronic P123, which also show a 3D cubic pore arrangement, exhibit almost 50 % crystallinity even at a calcination temperature of 400 °C, and their transformation into a fully crystalline material is accompanied by collapse of the mesoporous texture. Therefore, our study revealed the significance of using suitable block‐copolymer templates for the generation of mesoporous metal oxide films. Coupling of both electrochemical and X‐ray diffraction methods has shown to be highly advisable for the correct interpretation of structure properties, in particular the crystallinity, of such sol–gel derived films.     

Integration of Density Multiplication in the Formation of Device‐Oriented Structures by Directed Assembly of Block Copolymer–Homopolymer Blends

Non‐regular, device‐oriented structures can be directed to assemble on chemically nanopatterned surfaces such that the density of features in the assembled pattern is multiplied by a factor of two or more compared to the chemical pattern. By blending the block copolymers with homopolymers and designing the chemical pattern rationally, complicated structures such as bends, jogs, junctions, terminations, and combined structures are fabricated. Previously, directed assembly of block copolymers has been shown to enhance the resolution of lithographic processes for hexagonal arrays of spots and parallel lines, corresponding to the bulk morphologies of block copolymer systems, but this is the first demonstration of enhanced resolution for more complicated, device‐oriented features. This fundamental knowledge broadens the range of technologies that can be served by the directed assembly of block copolymers.     

Linking Group Influences Charge Separation and Recombination in All‐Conjugated Block Copolymer Photovoltaics

All‐conjugated block copolymers bring together hole‐ and electron‐conductive polymers and can be used as the active layer of solution‐processed photovoltaic devices, but it remains unclear how molecular structure, morphology, and electronic properties influence performance. Here, the role of the chemical linker is investigated through analysis of two donor–linker–acceptor block copolymers that differ in the chemistry of the linking group. Device studies show that power conversion efficiencies differ by a factor of 40 between the two polymers, and ultrafast transient absorption measurements reveal charge separation only in block copolymers that contain a wide bandgap monomer at the donor–acceptor interface. Optical measurements reveal the formation of a low‐energy excited state when donor and acceptor blocks are directly linked without this wide bandgap monomer. For both samples studied, it is found that the rate of charge recombination in these systems is faster than in poly­mer–polymer and polymer–fullerene blends. This work demonstrates that the linking group chemistry influences charge separation in all‐conjugated block copolymer systems, and further improvement of photovoltaic performance may be possible through optimization of the linking group. These results also suggest that all‐conjugated block copolymers can be used as model systems for the donor–acceptor interface in bulk heterojunction blends.     

Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, solvent vapor annealing in supported thin films of poly(2‐hydroxyethyl methacrylate)‐block‐poly(methyl methacrylate) [PHEMA‐b‐PMMA] by means of grazing incidence small angle X‐ray scattering (GISAXS) is investigated. A spin‐coated thin film of a lamellar block copolymer is solvent vapor annealed to induce microphase separation and improve the long‐range order of the self‐assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents, which are chosen to be preferential for each block, enables selective formation of ordered lamellae, gyroid, hexagonal, or spherical morphologies from a single‐block copolymer with a fixed volume fraction. The selected microstructure is then kinetically trapped in the dry film by rapid drying. This paper describes what is thought to be the first reported case where in situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram.     

Silica Films with Bimodal Pore Structure Prepared by Using Membranes as Templates and Amphiphiles as Porogens

Extended porous silica films with thicknesses in the range of 60 to 130 μm and pores on both the meso‐ and macroscale have been prepared by simultaneously using porous membrane templates and amphiphilic supramolecular aggregates as porogens. The macropore size is determined by the cellulose acetate or polyamide membrane structure and the mesopores by the chosen ethylene‐oxide‐based molecular self‐assembly (block copolymer or non‐ionic surfactants). Both the template and the porogen are removed during an annealing step leaving the amorphous silica material with a porous structure that results from sol–gel chemistry occurring in the aqueous domains of the amphiphilic liquid‐crystalline phases and casting of the initial template membrane. The surface area and total pore volume of the inorganic films vary from 473 to 856 m² g^–1, and 0.50 to 0.73 cm³ g^–1, respectively, depending on the choice of template and porogen. The combined benefits of both macro‐ and mesopores can potentially be obtained in one film. Such materials are envisaged to have applications in areas of large molecule (biomolecule) separation and catalysis. Enhanced gas and liquid flow rates through such membranes, due to the presence of the larger pores, also makes them attractive as supports for other catalytic materials.     

Nanostructured Poly(styrene‐b‐butadiene‐b‐styrene) (SBS) Membranes for the Separation of Nitrogen from Natural Gas

The preparation and characterization of new, tailor‐made polymeric membranes using poly(styrene‐b‐butadiene‐b‐styrene) (SBS) triblock copolymers for gas separation are reported. Structural differences in the copolymer membranes, obtained by manipulation of the self‐assembly of the block copolymers in solution, are characterized using atomic force microscopy, transmission electron microscopy, and the transport properties of three gases (CO₂, N₂, and CH₄). The CH₄/N₂ ideal selectivity of 7.2, the highest value ever reported for block copolymers, with CH₄ permeability of 41 Barrer, is obtained with a membrane containing the higher amount of polybutadiene (79 wt%) and characterized by a hexagonal array of columnar polystyrene cylinders normal to the membrane surface. Membranes with such a high separation factor are able to ease the exploitation of natural gas with high N₂ content. The CO₂/N₂ ideal selectivity of 50, coupled with a CO₂ permeability of 289 Barrer, makes SBS a good candidate for the preparation of membranes for the post‐combustion capture of carbon dioxide.     

J-Aggregation-Driven Supramolecular Assembly of Dye-Conjugated Block Polymers: From Morphological Tailoring to Anticancer Applications

Utilizing the J-stacking of dyes to drive the assembly of amphiphilic polymers can not only construct supramolecular assemblies with novel architectures but also provide a stabilizing solution for dye J-aggregation to promote its biomedical applications. However, tightly entangled hydrophobic segments can disrupt the orderly arrangement of dye molecules, thereby preventing dye stacking-driven supramolecular assembly of block copolymers. Herein, a “molecular glue” strategy is reported that uses the small dye molecule as a molecular glue to restore the J-stacking of the dye moiety immobilized on the polymer, thereby dominating the supramolecular assembly of the polymer matrix. Very interestingly, the yielded nano-assembly exhibits a novel worm-like structure with alternating straight and bent segments. By passing through nanopores, the bent part is disassembled to afford short nanorod NR-J812 mainly composed of crystalline dye J-aggregates. It shows favorable colloidal and optical stability, suitable size, and high photothermal property, and demonstrates high performance in photoacoustic imaging and photothermal treatment of tumors in vivo. This work provides important insights into not only the self-assembly of amphiphilic polymers with novel supramolecular architectures but also the preparation of J-aggregate materials applicable in vivo, which bring great promise to the biomedical fields.     

Mechanical Reinforcement of Polyethylene Using Polyethylene‐Grafted Multiwalled Carbon Nanotubes

The incorporation of carbon nanotubes to a polymer generally improves the stiffness and strength of the polymer, but the ductility and toughness of the polymer are compromised in most cases. Here we report the mechanical reinforcement of polyethylene (PE) using polyethylene‐grafted multiwalled carbon nanotubes (PE‐g‐MWNTs). The stiffness, strength, ductility and toughness of PE are all improved by the addition of PE‐g‐MWNTs. The grafting of PE onto MWNTs enables the well‐dispersion of nanotubes in the PE matrix and improves MWNT/PE interfacial adhesion. The grafting was achieved by a reactive blending process through melt blending of PE containing 0.85 wt % of maleic anhydride and amine‐functionalized MWNTs. The reaction between maleic anhydride and amine groups, as evidenced by X‐ray photoelectron spectroscopy and Raman spectroscopy, leads to the grafting of PE onto the nanotubes.     

Stepwise Drug‐Release Behavior of Onion‐Like Vesicles Generated from Emulsification‐Induced Assembly of Semicrystalline Polymer Amphiphiles

Tailoring unique nanostructures of biocompatible and degradable polymers and the consequent elucidation of shape effects in drug delivery open tremendous opportunities not only to broaden their biomedical applications but also to identify new directions for the design of nanomedicine. Cellular organelles provide the basic structural and functional motif for the development of novel artificial nanoplatforms. Herein, aqueous onion‐like vesicles structurally mimicking multicompartmentalized cellular organelles by exhibiting exquisite control over the molecular assembly of poly(ethylene oxide)‐block‐poly(ε‐caprolactone) (PEO‐b‐PCL) semicrystalline amphiphiles are reported. Compared to in situ self‐assembly, emulsification‐induced assembly endows the resulting nanoaggregates of PEO‐b‐PCL with structural diversity such as helical ribbons and onion‐like vesicles through the molecular packing modification in the hydrophobic core with a reduction of inherent crystalline character of PCL. In particular, onion‐like vesicles composed of alternating walls and water channels are interpreted by nanometer‐scale 3D visualization via cryogenic‐electron tomo­graphy (cryo‐ET). Interestingly, the nature of the multi‐walled vesicles results in high drug‐loading capacity and stepwise drug release through hydrolytic cleavage of the PCL block. The crystalline arrangement of PCL at the molecular scale and the spatial organization of assembled structure at the nanoscale significantly affect the drug‐release behavior of PEO‐b‐PCL nanovehicles.     

Self Encapsulated Poly(3‐hexylthiophene)‐poly(fluorinated alkyl methacrylate) Rod‐Coil Block Copolymers with High Field Effect Mobilities on Bare SiO2

Conjugated rod‐coil block copolymers provide an interesting route towards enhancing the properties of the conjugated block due to self‐assembly and the interplay of rod‐rod and rod‐coil interactions. Here, we demonstrate the ability of an attached semi‐fluorinated block to significantly improve upon the charge carrier properties of regioregular poly(3‐hexyl thiophene) (rr‐P3HT) materials on bare SiO₂. The thin film hole mobilities on bare SiO₂ dielectric surfaces of poly (3‐hexyl thiophene)‐block‐polyfluoromethacrylates (P3HT‐b‐PFMAs) can approach up to 0.12 cm² V^?1 s^?1 with only 33 wt% of the P3HT block incorporated in the copolymer, as compared to rr‐P3HT alone which typically has mobilities averaging 0.03 cm² V^?1 s^?1. To our knowledge, this is the highest mobility reported in literature for block copolymers containing a P3HT. More importantly, these high hole mobilities are achieved without multistep OTS treatments, argon protection, or post‐annealing conditions. Grazing incidence wide‐angle x‐ray scattering (GIWAX) data revealed that in the P3HT‐b‐PFMA copolymers, the P3HT rod block self‐assembles into highly ordered lamellar structures, similar to that of the rr‐P3HT homopolymer. Grazing incidence small‐angle x‐ray scattering (GISAXS) data revealed that lamellar structures are only observed in perpendicular direction with short PFMA blocks, while lamellae in both perpendicular and parallel directions are observed in polymers with longer PFMA blocks. AFM, GIWAXS, and contact angle measurements also indicate that PFMA block assembles at the polymer thin film surface and forms an encapsulation layer. The high charge carrier mobilities and the hydrophobic surface of the block copolymer films clearly demonstrates the influence of the coil block segment on device performance by balancing the crystallization and microphase separation in the bulk morphological structure.     

Ultrathin 2D‐Layered Cyclodextrin Membranes for High‐ Performance Organic Solvent Nanofiltration

Synthetic membranes with a high selectivity for demanding molecular separations and high permeance have a large potential for the reduction of energy consumption in separation processes. Herein, for the first time, the fabrication of an ultrathin layered macrocycle membrane for molecular separation in organic solvent nanofiltration using per‐6‐amino‐β‐cyclodextrin as a monomer for membrane manufacturing by interfacial polymerization is reported. Compared to a regular nonfunctionalized cyclodextrin, a higher reactivity is observed, enabling a very fast membrane formation under mild conditions. The formed membrane is composed of a layered structure of polymerized cyclodextrin, which shows high stability in different organic solvents. The membrane exhibits excellent separation performance for organic solvent nanofiltration, both with nonpolar and polar solvents. Most importantly, this new membrane type can discriminate between molecules with nearly identical molecular weights but different shapes. The unmatched high permeance and shape selectivity of the membranes can be attributed to the ultralow thickness, controlled microporosity, as well as the layered macrocycle structure, which makes the membranes promising for high‐performance molecular separation in the chemical and biochemistry industry.     

One‐Step Hierarchical Assembly of Spheres‐in‐Lamellae Nanostructures from Solvent‐Annealed Thin Films of Binary Diblock Copolymer Micelles

Hierarchical assemblies of dissimilar block copolymers (BCPs) can reveal interesting perspectives on material properties and device performance by providing multiple functionalities. Up to now, hierarchical assemblies of BCPs have been mostly prepared by stepwise assembling methods, in which the first type of BCP nanodomains is used as predefined patterns to guide the second‐level assembly of another BCP. On the other hand, single‐step blending methods suffer from a dilemma in the creation of hierarchical patterns because blending dissimilar BCPs typically induces either macrophase separation of component BCPs or chain‐level hybridization into a single morphology. The present study is designed to overcome this apparent dilemma in polymer blends by exploiting a solvent annealing method. In particular, hierarchically assembled spheres‐in‐lamellae structures from a solvent‐annealed blended film of binary polystyrene‐block‐poly(2‐vinylpyrdine) and polystyrene‐block‐poly(4‐vinyl pyridine) micelles are prepared. The focus of the current study is to understand the different effects of solvent vapor on the component BCPs and the molecular mechanism for the one‐step assembling process. By addressing this issue, the parallelism in the phase behavior of BCP micelles and inorganic nanoparticles is highlighted, the underlying physical processes of which could be suggested as a one‐step assembly principle for hierarchical superstructures beyond the previously reported multistep methods.