Stepwisely Assembled Multicomponent Fiber with High Water Content and Superior Mechanical Properties for Artificial Ligament.

The ligament, which connects bones at the joints, has both high water content and excellent mechanical properties in living organisms. However, it is still challenging to fabricate fibrous materials that possess high water content and ligament-like mechanical characteristics simultaneously. Herein, the design and preparation of a ligament-mimicking multicomponent fiber is reported through stepwise assembly of polysaccharide, calcium, and dopamine. In simulated body fluid, the resulting fiber has a water content of 40 wt%, while demonstrating strength of ≈120 MPa, a Young's modulus of ≈3 GPa, and a toughness of ≈25 MJ m-3. Additionally, the multicomponent fiber exhibits excellent creep and fatigue resistance, as well as biocompatibility to support cell growth in vitro. These findings suggest that the fiber has potential for engineering high-performance artificial ligament.

Genetically predicted immune cells mediate the association between gut microbiota and neuropathy pain.

BACKGROUND: Previous observational studies have indicated a complex association between gut microbiota (GM) and neuropathic pain (NP). Nonetheless, the precise biological mechanisms underlying this association remain unclear. Therefore, we adopted a Mendelian randomization (MR) approach to investigate the causal relationship between GM and neuropathic pain including post-herpetic neuralgia (PHN), painful diabetic peripheral neuropathy (PDPN), and trigeminal neuralgia (TN), as well as to explore the potential mediation effects of immune cells. METHODS: We performed a two-step, two-sample Mendelian randomization study with an inverse variance-weighted (IVW) approach to investigate the causal role of GM on three major kinds of NP and the mediation effect of immune cells between the association of GM and NP. In addition, we determine the strongest causal associations using Bayesian weighted Mendelian randomization (BWMR) analysis. Furthermore, we will investigate the mediating role of immune cells through a two-step Mendelian randomization design. RESULTS: We identified 53 taxonomies and pathways of gut microbiota that had significant causal associations with NP. In addition, we also discovered 120 immune cells that exhibited significant causal associations with NP. According to the BWMR and two-step Mendelian randomization analysis, we identified the following results CD4 on CM CD4 + (maturation stages of T cell) mediated 6.7% of the risk reduction for PHN through the pathway of fucose degradation (FUCCAT.PWY). CD28 + DN (CD4-CD8-) AC (Treg) mediated 12.5% of the risk reduction for PHN through the influence on Roseburia inulinivorans. CD45 on lymphocyte (Myeloid cell) mediated 11.9% of the risk increase for TN through the superpathway of acetyl-CoA biosynthesis (PWY.5173). HLA DR + CD8br %T cell (TBNK) mediated 3.2% of the risk reduction for TN through the superpathway of GDP-mannose-derived O-antigen building blocks biosynthesis (PWY.7323). IgD-CD38-AC (B cell) mediated 7.5% of the risk reduction for DPN through the pathway of thiazole biosynthesis I in E. coli (PWY.6892). DISCUSSION: These findings provided evidence supporting the causal effect of GM with NP, with immune cells playing a mediating role. These findings may inform prevention strategies and interventions directed toward NP. Future studies should explore other plausible biological mechanisms.

Comparison of initial percutaneous balloon compression versus radiofrequency thermocoagulation followed by percutaneous balloon compression in the treatment of trigeminal neuralgia. / 首次经皮球囊压迫术与射频热凝术后再行经皮球囊压迫术治疗三叉神经痛的比较.

OBJECTIVES: There are a variety of minimally invasive interventional treatments for trigeminal neuralgia, and the efficacy evaluation is different. The preferred treatment scheme is still controversial. This study aims to investigate the differences in treatment effects between patients with primary trigeminal neuralgia (PTN) treated with percutaneous balloon compression (PBC) for the first intervention and patients with pain recurrence after radiofrequency thermocoagulation (RT) who then received PBC for PTN, and to offer clinicians and patients more scientifically grounded and precise treatment alternatives. METHODS: We retrospectively analyzed 103 patients with PTN admitted to the Department of Pain Management of the Second Affiliated Hospital of Guangxi Medical University from January 2020 to December 2021, including 49 patients who received PBC for the first time (PBC group) and 54 patients who received PBC for pain recurrence after RT (RT+PBC group). General information, preoperative pain score, intraoperative oval foramen morphology, oval foramen area, balloon volume, duration of compression, and postoperative pain scores and pain recurrence at each time point on day 1 (T1), day 7 (T2), day 14 (T3), 1 month (T4), 3 months (T5), and 1 year (T6) were collected and recorded for both groups. The differences in treatment effect, complications and recurrence between the 2 groups were compared, and the related influencing factors were analyzed. RESULTS: The differences of general information, preoperative pain scores, foramen ovale morphology, foramen ovale area, T1 to T3 pain scores between the 2 groups were not statistically different (all P>0.05). The balloon filling volume in the PBC group was smaller than that in the RT+PBC group, the pain scores at T4 to T6 and pain recurrence were better than those in the RT+PBC group (all P<0.05). Pain recurrence was positively correlated with pain scores of T2 to T6 (r=0.306, 0.482, 0.831, 0.876, 0.887, respectively; all P<0.01). CONCLUSIONS: The choice of PBC for the first intervention in PTN patients is superior to the choice of PBC after pain recurrence after RT treatment in terms of treatment outcome and pain recurrence.

Direct 3D Bioprinting of Tough and Antifatigue Cell-Laden Constructs Enabled by a Self-Healing Hydrogel Bioink.

Three-dimensional (3D) extrusion bioprinting has emerged as one of the most promising biofabrication technologies for preparing biomimetic tissue-like constructs. The successful construction of cell-laden constructs majorly relies on the development of proper bioinks with excellent printability and cytocompatibility. Bioinks based on gelatin methacryloyl (GelMA) have been widely explored due to the excellent biocompatibility and biodegradability and the presence of the arginine-glycine-aspartic acid (RGD) sequences for cell adhesion. However, such bioinks usually require low-temperature or ionic cross-linking systems to solidify the extruded hydrogel structures, which results in complex processes and limitations to certain applications. Moreover, many current hydrogel-based bioinks, even after chemical cross-linking, hardly possess the required strength to resist the mechanical loads during the implantation procedure. Herein, we report a self-healing hydrogel bioink based on GelMA and oxidized dextran (OD) for the direct printing of tough and fatigue-resistant cell-laden constructs at room temperature without any template or cross-linking agents. Enabled by dynamic Schiff base chemistry, the mixed GelMA/OD solution showed the characteristics of a dynamic hydrogel with shear-thinning and self-supporting behavior, which allows bridging the 5 mm gap and efficient direct bioprinting of complex constructs with high shape fidelity. After photo-cross-linking, the resulting tissue constructs exhibited excellent low cell damage, high cell viability, and enhanced mechanical strength. Moreover, the GelMA/OD construct could resist up to 95% compressive deformation without any breakage and was able to maintain 80% of the original Young's modulus during long-term loading (50 cycles). It is believed that our GelMA/OD bioink would expand the potential of GelMA-based bioinks in applications such as tissue engineering and pharmaceutical screening.

Trends and Opportunities in Organic Synthesis: Global State of Research Metrics and Advances in Precision, Efficiency, and Green Chemistry.

Organic synthesis continues to drive a broad range of research advances in chemistry and related sciences. Another clear trend in organic synthesis research is the increasing desire to target improvements in the quality of life of humankind, new materials, and product specificity. Here, a landscape view of organic synthesis research is provided by analysis of the CAS Content Collection. Three emerging research directions, enzyme catalysis, photocatalysis, and green chemistry in organic synthesis, were identified and featured based on the publication trend analysis.

Solvent-Free Templated Synthesis of Core-Crosslinked Star-Shaped Polymers in Supramolecular Body-Centered Cubic Phase.

This study reports the exploration of a solvent-free supramolecular templated synthesis strategy toward highly core-cross-linked star-shaped polymers (CSPs). To achieve this, a kind of cross-linkable giant surfactant, based on a functionalized polyhedral oligomeric silsesquioxanes (POSS) head tethered with a diblock copolymer tail containing reactive benzocyclobutene groups, is designed and prepared. By varying the volume fraction of linear block copolymer tail, these giant surfactants can self-assemble into a body-centered cubic (BCC) structure in bulk, in which the supramolecular spheres are composed of a core of POSS cages, a middle shell of crosslinkable poly(4-vinylbenzocyclobutene) (PBCB) blocks, and a corona of inert polystyrene (PS) blocks. The solvent-free thermally induced cross-linking reaction of the benzocyclobutene groups can be finished in 5 min upon heating, resulting in well-defined polymeric spheres with over 90 linear chains surrounding the cross-linked cores. The outer PS blocks serve as the protection corona to ensure that cross-linking of giant surfactants occurs in each supramolecular spherical domain. Given the modular design and diversity of the POSS-based giant surfactants, it is believed that the strategy may enable access to a wide range of CSPs.

Thermoresponsive and Self-Healing Hydrogel Based on Chitosan Derivatives and Polyoxometalate as an Antibacterial Coating.

Hospital-acquired infections are a serious threat to the recovery of patients. To prevent such infections, an antibacterial coating is an effective method to eliminate bacterial colonization on healthcare-related surfaces. Herein, we report an antibacterial hydrogel composed of silver-containing polyoxometalate (AgP5W30 POM) and carboxymethyl chitosan (CMC). The silver ion is encapsulated inside the POM cage and demonstrates long-lasting bacteriostasis after repeated exposure to both Gram-positive and Gram-negative bacteria. The chemical structure of chitosan derivatives, as well as the concentration and pH, is studied to tune the mechanical properties of the hydrogel. The hydrogel undergoes a gel-sol transition above the critical temperature and possesses self-healing ability. This hydrogel can be readily coated on the surface of versatile bulk materials, which is especially convenient for porous objects and resists the growth of Staphylococcus aureus, Escherichia coli, and methicillin-resistant S. aureus (MRSA). In summary, we envision that the AgP5W30-CMC hydrogel has great potential to serve as an antibacterial coating to decrease the prevalence of hospital-acquired infections.

Crystallization Induced Self-Assembly: A Strategy to Achieve Ultra-Small Domain Sizes.

Achieving self-assembled nanostructures with ultra-small feature sizes (e. g., below 5 nm) is an important prerequisite for the development of block copolymer lithography. In this work, the preparation and self-assembly of a series of giant molecules composed of vinyl polyhedral oligomeric silsesquioxane (VPOSS) tethered with monodispersed oligo(L-lactide) chains are presented. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) results demonstrate that ultra-small domain sizes (down to 3 nm) of phase separated lamellar morphology are achieved in bulk, driven by the strong tendency and fast kinetics for crystallization of VPOSS moieties. Moreover, upon gamma ray radiation, VPOSS cages in the lamellar structure can be crosslinked via polymerization of the vinyl groups. After pyrolysis at high temperature, ultra-thin two-dimensional nano-silica sheets can be obtained.

Controlling the Periodically Ordered Nanostructures in Ceramics: A Macromolecule-Guided Strategy.

Microscopic structures have a significant influence on the properties of ceramics. The development of macromolecular self-assembly has allowed for control over microscopic structures of ceramics to prepare ceramics with diverse compositions and ordered nanostructures. Herein, recent progress in the preparation of ceramics with periodically ordered nanostructures guided by phase-separated macromolecules are reviewed, which can be summarized as a general strategy termed the "macromolecule-guided strategy." Moreover, two different subcategories, namely, the macromolecule-templated method and the macromolecule-precursor method, are illustrated. In the former method, amphiphilic macromolecules are used as templates to guide the assembly of inorganic species into ordered nanostructures, which are subsequently converted into ceramics; in the latter method, amphiphilic macromolecules containing non-volatile elements are used as the single-source precursors for ordered ceramics. It is believed that the unique diversity and tunable features of macromolecular self-assembly might offer unprecedented opportunities in the development of functional ceramics for various applications.

A Tumor-on-a-Chip System with Bioprinted Blood and Lymphatic Vessel Pair.

Current in vitro anti-tumor drug screening strategies are insufficiently portrayed lacking true perfusion and draining microcirculation systems, which may post significant limitation in reproducing the transport kinetics of cancer therapeutics explicitly. Herein, we report the fabrication of an improved tumor model consisting of bioprinted hollow blood vessel and lymphatic vessel pair, hosted in a three-dimensional (3D) tumor microenvironment-mimetic hydrogel matrix, termed as the tumor-on-a-chip with bioprinted blood and lymphatic vessel pair (TOC-BBL). The bioprinted blood vessel was perfusable channel with opening on both ends while the bioprinted lymphatic vessel was blinded on one end, both of which were embedded in a hydrogel tumor mass, with vessel permeability individually tunable through optimization of the composition of the bioinks. We demonstrated that systems with different combinations of these bioprinted blood/lymphatic vessels exhibited varying levels of diffusion profiles for biomolecules and anti-cancer drugs. Our TOC-BBL platform mimicking the natural pathway of drug-tumor interactions would have the drug introduced through the perfusable blood vessel, cross the vascular wall into the tumor tissue via diffusion, and eventually drained into the lymphatic vessel along with the carrier flow. Our results suggested that this unique in vitro tumor model containing the bioprinted blood/lymphatic vessel pair may have the capacity of simulating the complex transport mechanisms of certain pharmaceutical compounds inside the tumor microenvironment, potentially providing improved accuracy in future cancer drug screening.

Geometry induced sequence of nanoscale Frank-Kasper and quasicrystal mesophases in giant surfactants.

Frank-Kasper (F-K) and quasicrystal phases were originally identified in metal alloys and only sporadically reported in soft materials. These unconventional sphere-packing schemes open up possibilities to design materials with different properties. The challenge in soft materials is how to correlate complex phases built from spheres with the tunable parameters of chemical composition and molecular architecture. Here, we report a complete sequence of various highly ordered mesophases by the self-assembly of specifically designed and synthesized giant surfactants, which are conjugates of hydrophilic polyhedral oligomeric silsesquioxane cages tethered with hydrophobic polystyrene tails. We show that the occurrence of these mesophases results from nanophase separation between the heads and tails and thus is critically dependent on molecular geometry. Variations in molecular geometry achieved by changing the number of tails from one to four not only shift compositional phase boundaries but also stabilize F-K and quasicrystal phases in regions where simple phases of spheroidal micelles are typically observed. These complex self-assembled nanostructures have been identified by combining X-ray scattering techniques and real-space electron microscopy images. Brownian dynamics simulations based on a simplified molecular model confirm the architecture-induced sequence of phases. Our results demonstrate the critical role of molecular architecture in dictating the formation of supramolecular crystals with "soft" spheroidal motifs and provide guidelines to the design of unconventional self-assembled nanostructures.

Role of Rho-Associated Coiled-Coil Forming Kinase Isoforms in Regulation of Stiffness-Induced Myofibroblast Differentiation in Lung Fibrosis.

Fibrosis is a major cause of progressive organ dysfunction in several chronic pulmonary diseases. Rho-associated coiled-coil forming kinase (ROCK) has been shown to be involved in myofibroblast differentiation driven by altered matrix stiffness in a fibrotic state. There are two known ROCK isoforms in humans, ROCK1 and ROCK2, but the specific role of each isoform in myofibroblast differentiation in lung fibrosis remains unknown. To study this, we developed a gelatin methacryloyl hydrogel-based culture system with different stiffness levels relevant to healthy and fibrotic lungs. We have shown that stiff matrix, but not soft matrix, can induce myofibroblast differentiation with high smooth muscle actin isoform (αSMA) expression. Furthermore, our data confirmed that the inhibition of ROCK signaling by a pharmacological inhibitor (i.e., Y27632) attenuates stiffness-induced αSMA expression and fiber assembly in myofibroblasts. To assess the role of ROCK isoforms in this process, we used short interfering RNA to knock down the expression of each isoform. Our data showed that knocking down either ROCK1 or ROCK2 did not result in a reduction in αSMA expression in myofibroblasts on stiff matrix, as opposed to soft matrix, where αSMA expression was reduced significantly. Paradoxically, on stiff matrix, the absence of one isoform (particularly ROCK2) exaggerated αSMA expression and led to thick fiber assembly. Moreover, complete loss of αSMA fiber assembly was seen only in the absence of both ROCK isoforms, suggesting that both isoforms are implicated in this process. Overall, our results indicate the differential role of ROCK isoforms in myofibroblast differentiation on soft and stiff matrices.

Spatially and Temporally Controlled Hydrogels for Tissue Engineering.

Recent years have seen tremendous advances in the field of hydrogel-based biomaterials. One of the most prominent revolutions in this field has been the integration of elements or techniques that enable spatial and temporal control over hydrogels' properties and functions. Here, we critically review the emerging progress of spatiotemporal control over biomaterial properties towards the development of functional engineered tissue constructs. Specifically, we will highlight the main advances in the spatial control of biomaterials, such as surface modification, microfabrication, photo-patterning, and three-dimensional (3D) bioprinting, as well as advances in the temporal control of biomaterials, such as controlled release of molecules, photocleaving of proteins, and controlled hydrogel degradation. We believe that the development and integration of these techniques will drive the engineering of next-generation engineered tissues.

Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering.

The engineering of structures across different length scales is central to the design of novel materials with controlled macroscopic properties. Herein, we introduce a unique class of self-assembling materials, which are built upon shape- and volume-persistent molecular nanoparticles and other structural motifs, such as polymers, and can be viewed as a size-amplified version of the corresponding small-molecule counterparts. Among them, "giant surfactants" with precise molecular structures have been synthesized by "clicking" compact and polar molecular nanoparticles to flexible polymer tails of various composition and architecture at specific sites. Capturing the structural features of small-molecule surfactants but possessing much larger sizes, giant surfactants bridge the gap between small-molecule surfactants and block copolymers and demonstrate a duality of both materials in terms of their self-assembly behaviors. The controlled structural variations of these giant surfactants through precision synthesis further reveal that their self-assemblies are remarkably sensitive to primary chemical structures, leading to highly diverse, thermodynamically stable nanostructures with feature sizes around 10 nm or smaller in the bulk, thin-film, and solution states, as dictated by the collective physical interactions and geometric constraints. The results suggest that this class of materials provides a versatile platform for engineering nanostructures with sub-10-nm feature sizes. These findings are not only scientifically intriguing in understanding the chemical and physical principles of the self-assembly, but also technologically relevant, such as in nanopatterning technology and microelectronics.

Two-dimensional nanocrystals of molecular Janus particles.

This paper describes a rational strategy to obtain self-assembled two-dimensional (2D) nanocrystals with definite and uniform thickness from a series of molecular Janus particles based on molecular nanoparticles (MNPs). MNPs are 3D framework with rigid shapes. Three different types of MNPs based on derivatives of polyhedral oligomeric silsesquioxane (POSS), [60]fullerene (C60), and Lindqvist-type polyoxometalate (POM) are used as building blocks to construct these amphiphilic molecular Janus particles by covalently connecting hydrophobic crystalline BPOSS with a charged hydrophilic MNP. The formation of 2D nanocrystals with an exact thickness of double layers of molecules is driven by directional crystallization of the BPOSS MNP and controlled by various factors such as solvent polarity, number of counterions, and sizes of the MNPs. Strong solvating interactions of the ionic MNPs in polar solvents (e.g., acetonitrile and dimethylformamide) are crucial to provide repulsive interactions between the charged outlying ionic MNPs and suppress further aggregation along the layer normal direction. The number of counterions per molecule plays a major role in determining the self-assembled morphologies. Size matching of the hydrophobic and ionic MNPs is another critical factor in the formation of 2D nanocrystals. Self-assembly of rationally designed molecular Janus particles provides a unique "bottom-up" strategy to engineer 2D nanostructures.

Self-assembly of fullerene-based janus particles in solution: effects of molecular architecture and solvent.

Two molecular Janus particles based on amphiphilic [60]fullerene (C60 ) derivatives were designed and synthesized by using the regioselective Bingel-Hirsh reaction and the click reaction. These particles contain carboxylic acid functional groups, a hydrophilic fullerene (AC60 ), and a hydrophobic C60 in different ratios and have distinct molecular architectures: 1:1 (AC60 -C60 ) and 1:2 (AC60 -2C60 ). These molecular Janus particles can self-assemble in solution to form aggregates with various types of micellar morphology. Whereas vesicular morphology was observed for both AC60 -C60 and AC60 -2C60 in tetrahydrofuran, in a mixture of N,N-dimethylformamide (DMF)/water, spherical micelles and cylindrical micelles were observed for AC60 -C60 and AC60 -2C60 , respectively. A mechanism of formation was tentatively proposed based on the effects of molecular architecture and solvent polarity on self-assembly.

Effects of molecular geometry on the self-assembly of giant polymer-dendron conjugates in condensed state.

A series of giant polymer-dendron conjugates with a dendron head and a linear polymer tail were synthesized via"click" chemistry between azide-functionalized polystyrene (PS(N), N: degree-of-polymerization) and t-butyl protected, alkyne-functionalized second generation dendron (tD), followed by a deprotection process to generate a dendron termini possessing nine carboxylic acid groups. The molecular structures were confirmed by nuclear magnetic resonance, size-exclusion chromatographic analyses, and matrix-assisted laser desorption ionization time-of-flight mass spectra. These well-defined conjugates can serve as a model system to study the effects of the molecular geometries on the self-assembly behaviour, as compared with their linear analogues. Four phase morphologies found in flexible linear diblock copolymer systems, including lamellae, bicontinuous double gyroids, hexagonal packed cylinders, and body-centred cubic packed spheres, were observed in this series of conjugates based on the results of small angle X-ray scattering and transmission electron microscopy. All of the domain sizes in these phase separated structures were around or less than 10 nm. A 'half' phase diagram was constructed based on the experimental results. The geometrical effect was found not only to enhance the immiscibility between the PS(N) tail and dendron head, but also systematically shift all of the phase boundaries towards higher volume fractions of the PS(N) tails, resulting in an asymmetrical phase diagram. This study may provide a pathway to the construction of ordered patterns of sub-10 nm feature size using polymer-dendron conjugates.

High-sensitivity and ultralow-hysteresis fluorine-rich ionogel strain sensors for multi-environment contact and contactless sensing.

Information transduction via soft strain sensors under harsh conditions such as marine, oily liquid, vacuum, and extreme temperatures without excess encapsulation facilitates modern scientific and military exploration. However, most reported soft strain sensors struggle to meet these requirements, especially in complex environments. Herein, a class of fluorine-rich ionogels with tunable ultimate strain, high conductivity, and multi-environment tolerance are designed. Abundant ion-dipole and dipole-dipole interactions lead to excellent miscibility between the hydrophobic ionic liquid and the fluorinated polyacrylate matrix, as well as adhesion to diverse substrates in amphibious environments. The ionogel-based sensors, even in encapsulation-free form, exhibit stable operation with a negligible hysteresis (as low as 0.119%) and high sensitivity (gauge factor of up to 6.54) under amphibious conditions. Multi-environment sensing instances in contact and even contactless forms are also demonstrated. This study opens the door for the artificial syntheses of multi-environment tolerance ionic skins with robust sensing applications in soft electronics and robotics.

High-entropy oxides: an emerging anode material for lithium-ion batteries.

High entropy oxides (HEOs) have gained significant attention in multiple research fields, particularly in reversible energy storage. HEOs with rock-salt and spinel structures have shown excellent reversible capacity and longer cycle spans compared to traditional conversion-type anodes. However, research on HEOs and their electrochemical performance remains at an early stage. In this highlight, we review recent progress on HEO materials in the field of lithium-ion batteries (LIBs). Firstly, we introduce the synthesis methods of HEOs and some factors that affect the morphology and electrochemical properties of the synthesized materials. We then elaborate on the structural evolution of HEOs with rock-salt and spinel structures in lithium energy storage and summarize the relationship between morphology, pseudocapacitance effect, oxygen vacancy, and electrochemical performance. In the end, we give the challenges of HEO anodes for LIBs and present our opinions on how to guide the further development of HEOs for advanced anodes.

Sequence-Isomerism-Controlled Macromolecular Self-Assembly in Dendritic Rod-Like Molecules.

Although in Nature sequence control is widely adopted to tune the structure and functions of biomacromolecules, it remains challenging and largely unexplored in synthetic macromolecular systems due to the difficulties in a precision synthesis, which impedes the understanding of the structure-property relationship in macromolecular sequence isomerism. Herein, we report the sequence-controlled macromolecular self-assembly enabled by a pair of rationally designed isomeric dendritic rod-like molecules. With an identical chemical formula and molecular topology, the molecular solid angle of the dendron isomers was determined by the sequence of the rod building blocks tethered with side chains of different lengths. As a result, entirely different supramolecular motifs of discs and spheres were generated, which were further packed into a hexagonally packed cylinder phase and a dodecagonal quasicrystalline sphere phase, respectively. Given the efficient synthesis and modular structural variations, it is believed that the sequence-isomerism-controlled self-assembly in dendritic rod-like molecules might provide a unique avenue toward rich nanostructures in synthetic macromolecules.