Large-Area Uniaxially Oriented Sub-5†nm Line Patterns of Hybrid Liquid Crystals Constructed by Perylene Diimide and Oligo(Dimethylsiloxane).

Construction of sub-5 nm long-range ordered structures through self-assembly has received increasing attention. Herein, a series of ODMS-based thermotropic liquid crystals (LCs) containing perylene diimide (PDI) were designed and synthesized. These LCs can form ordered nanostructures with periodic sizes around 5 nm including smectic J (SmJ), oblique columnar (Colob ), and hexagonal columnar (Colh ) phases with change in the volume fraction of ODMS, where the layer spacing of the SmJ phase is less than 5 nm. Thin films with parallel oriented nanolines with line width less than 5 nm can be obtained on PDMS-modified silicon substrates by spin-casting and simple thermal annealing processes. Moreover, owing to the strong π-π interaction between PDI cores, these nanolines are long-range ordered with uniaxial orientation in relatively large areas (1.5×1.5 µm2 ) with over 300 continuous microdomains without pre-patterning. These nanostructures provide the possibility of preparing nanotemplates by oxygen plasma etching.

Sub-5 nm homeotropically aligned columnar structures of hybrids constructed by porphyrin and oligo(dimethylsiloxane).

A series of tetraphenylporphyrin-based thermotropic liquid crystals containing oligo(dimethylsiloxane) were synthesized. These disc-coil hybrids form ordered nanostructures with periodic sizes on the sub-5 nm scale, including oblique columnar, lamellar, and hexagonal columnar phases. Films with sub-5 nm line patterns and homeotropically aligned columnar structures can be obtained by substrate-induced self-assembly.

Diversiform and Transformable Glyco-Nanostructures Constructed from Amphiphilic Supramolecular Metallocarbohydrates through Hierarchical Self-Assembly: The Balance between Metallacycles and Saccharides.

During the past decade, self-assembly of saccharide-containing amphiphilic molecules toward bioinspired functional glycomaterials has attracted continuous attention due to their various applications in fundamental and practical areas. However, it still remains a great challenge to prepare hierarchical glycoassemblies with controllable and diversiform structures because of the complexity of saccharide structures and carbohydrate-carbohydrate interactions. Herein, through hierarchical self-assembly of modulated amphiphilic supramolecular metallocarbohydrates, we successfully prepared various well-defined glyco-nanostructures in aqueous solution, including vesicles, solid spheres, and opened vesicles depending on the molecular structures of metallocarbohydrates. More attractively, these glyco-nanostructures can further transform into other morphological structures in aqueous solutions such as worm-like micelles, tubules, and even tupanvirus-like vesicles (TVVs). It is worth mentioning that distinctive anisotropic structures including the opened vesicles (OVs) and TVVs were rarely reported in glycobased nano-objects. This intriguing diversity was mainly controlled by the subtle structural trade-off of the two major components of the amphiphiles, i.e., the saccharides and metallacycles. To further understand this precise structural control, molecular simulations provided deep physical insights on the morphology evolution and balancing of the contributions from saccharides and metallacycles. Moreover, the multivalency of glyco-nanostructures with different shapes and sizes was demonstrated by agglutination with a diversity of sugar-binding protein receptors such as the plant lectins Concanavalin A (ConA). This modular synthesis strategy provides access to systematic tuning of molecular structure and self-assembled architecture, which undoubtedly will broaden our horizons on the controllable fabrication of biomimetic glycomaterials such as biological membranes and supramolecular lectin inhibitors.

Photoresponsive Chirality-Tunable Supramolecular Metallacycles.

Chirality-tunable supramolecular metallacycles containing two light-responsive dithienylethene units and two chiral 1,1'-bi-2-naphthol (BINOL) units have been successfully constructed via coordination-driven self-assembly. These new metallacycles are well-characterized with 1D multinuclear NMR (1 H and 31 P NMR), 2D 1 H-1 H COSY and DOSY, ESI-TOF-MS, and PM6 semiempirical molecular orbital methods. Interestingly, upon irradiation with ultraviolet and visible light, the conformation of these metallacycles can undergo reversible transformation between ring-open and ring-closed forms accompanied with the obvious change of CD signals. Further investigation reveals that the photoisomerization of the dithienylethene moieties induces the change in the dihedral angle of the binaphthyl rings, thus leading to the chiral modulation of supramolecular metallacycles. Thus, this study provides very few examples of the light-induced chirality-tunable metallosupramolecular assemblies, which may find potential application in mimicking the function of natural systems in the future.

Facile construction of organometallic rotaxane-terminated dendrimers using neutral platinum-acetylides as the main scaffold.

We present the successful construction of a new family of organometallic rotaxane-terminated dendrimers using neutral platinum-acetylides as the main scaffold. The fourth generation dendrimer has 24 rotaxane moieties on the surface termini in a monodisperse manner.

Hierarchical Self-Assembly of an Alkynylplatinum(ll) Bzimpy-Functionalized Metallacage via Pt···Pt and π-π Interactions.

A new discrete supramolecular metallacage functionalized with an alkynylplatinum(ll) 2,6-bis(benzimidazole-2'-yl)-pyridine (bzimpy) moiety has been successfully constructed via coordination-driven self-assembly. A study on the hierarchical self-assembly behavior of the obtained metallacage revealed that it displayed a solvent-induced emission switch accompanied by enhancement of the emission intensity as a result of the change in intermolecular Pt···Pt and π-π interactions. More interestingly, the metallacage has been found to spontaneously self-assemble into a transparent metallogel at room temperature without a heating-cooling process.

[Optimizing Color Rendering for Mixed-Color White Light LED].

To optimize color rendering of mixed-color LEDs, the Gaussian model was used to analyze the color-mixed LED's spectrum power distribution. The peak wavelength "λm", spectral half width "Δλ" and amplitude "A" were basic parameters for optimizing color rendering R9, which is very important for objects to be colorful and vivid under the white light LED's'illuminating. The typical methods for color mixing were used to get white light LEDs. Result was that to get the satisfied color rendering index, one of the color primaries should be certain and then other color primaries would be analyzed through changing three basic parameters step by step. It was concluded that the analysis in this paper would be referential to optimize the color-mixed white LED's color rendering.

Supramolecular Chemistry in the Formation of Self-Assembled Nanostructures from a High-Molecular-Weight Rod-Coil Block Copolymer.

The self-assembled nanostructures of a high-molecular-weight rod-coil block copolymer, poly(styrene-block-(2,5-bis[4-methoxyphenyl]oxycarbonyl)styrene) (PS-b-PMPCS), in p-xylene are studied. The cylindrical micelles, long segmental cylindrical micelle associates, spherical micelles, and spherical micelle associates are observed with increased copolymer concentration. The high molecular weight of PS leads to the entanglement between PS chains from different micelles, which is the force for supramolecular interactions. Short cylindrical micelles are connected end-to-end via this supramolecular chemistry to form long segmental cylindrical micelle associates, analogue to the condensation polymerization process, with direction and saturation. On the other hand, spherical micelles assemble via supramolecular chemistry to form spherical micelle associates, yet without any direction due to their isotropic properties.

Using the maximum between-class variance for automatic gridding of cDNA microarray images.

Gridding is the first and most important step to separate the spots into distinct areas in microarray image analysis. Human intervention is necessary for most gridding methods, even if some so-called fully automatic approaches also need preset parameters. The applicability of these methods is limited in certain domains and will cause variations in the gene expression results. In addition, improper gridding, which is influenced by both the misalignment and high noise level, will affect the high throughput analysis. In this paper, we have presented a fully automatic gridding technique to break through the limitation of traditional mathematical morphology gridding methods. First, a preprocessing algorithm was applied for noise reduction. Subsequently, the optimal threshold was gained by using the improved Otsu method to actually locate each spot. In order to diminish the error, the original gridding result was optimized according to the heuristic techniques by estimating the distribution of the spots. Intensive experiments on six different data sets indicate that our method is superior to the traditional morphology one and is robust in the presence of noise. More importantly, the algorithm involved in our method is simple. Furthermore, human intervention and parameters presetting are unnecessary when the algorithm is applied in different types of microarray images.

Improving the computational efficiency of recursive cluster elimination for gene selection.

The gene expression data are usually provided with a large number of genes and a relatively small number of samples, which brings a lot of new challenges. Selecting those informative genes becomes the main issue in microarray data analysis. Recursive cluster elimination based on support vector machine (SVM-RCE) has shown the better classification accuracy on some microarray data sets than recursive feature elimination based on support vector machine (SVM-RFE). However, SVM-RCE is extremely time-consuming. In this paper, we propose an improved method of SVM-RCE called ISVM-RCE. ISVM-RCE first trains a SVM model with all clusters, then applies the infinite norm of weight coefficient vector in each cluster to score the cluster, finally eliminates the gene clusters with the lowest score. In addition, ISVM-RCE eliminates genes within the clusters instead of removing a cluster of genes when the number of clusters is small. We have tested ISVM-RCE on six gene expression data sets and compared their performances with SVM-RCE and linear-discriminant-analysis-based RFE (LDA-RFE). The experiment results on these data sets show that ISVM-RCE greatly reduces the time cost of SVM-RCE, meanwhile obtains comparable classification performance as SVM-RCE, while LDA-RFE is not stable.

Mesogen-jacketed liquid crystalline polymers.

This critical review covers the recent progress in the research of mesogen-jacketed liquid crystalline polymers (MJLCPs), special side-on side-chain liquid crystalline polymers with very short spacers or without spacers. MJLCPs can self-organize into supramolecular columnar phases with the polymer chains aligned parallel to one another or smectic phases with the backbones embedded in the smectic layers. The semi-rigid rod-like MJLCP with a tunable rod shape in both length and diameter provides an excellent building block in designing novel rod-coil liquid crystalline block copolymers which can self-assemble into hierarchical supramolecular nanostructures depending on the competition between liquid crystal formation and microphase separation (229 references).

Hierarchical supramolecular ordering with biaxial orientation of a combined main-chain/side-chain liquid-crystalline polymer obtained from radical polymerization of 2-vinylterephthalate.

The liquid-crystalline (LC) phase structures and transitions of a combined main-chain/side-chain LC polymer (MCSCLCP) 1 obtained from radical polymerization of a 2-vinylterephthalate, poly(2,5-bis{[6-(4-butoxy-4'-oxybiphenyl) hexyl]oxycarbonyl}styrene), were studied using differential scanning calorimetry, one- and two-dimensional wide-angle X-ray diffraction (1D and 2D WAXD), and polarized light microscopy. We have found that 1 with sufficiently high molecular weight can self-assemble into a hierarchical structure with double orderings on the nanometer and subnanometer scales at low temperatures. The main chains of 1, which are rodlike as a result of the "jacketing" effect generated by the central rigid portion of the side chains laterally attached to every second carbon atom along the polyethylene backbone, form a 2D centered rectangular scaffold. The biphenyl-containing side chains fill the space between the main chains, forming a smectic E (SmE)-like structure with the side-chain axis perpendicular to that of the main chain. This biaxial orientation of 1 was confirmed by our 2D WAXD experiments through three orthogonal directions. The main-chain scaffold remains when the SmE-like packing is melted at elevated temperatures. Further heating leads to a normal smectic A (SmA) structure followed by the isotropic state. We found that when an external electric field was applied, the main-chain scaffold greatly inhibited the motion of the biphenyls. While the main chains gain a sufficiently high mobility in the SmA phase, macroscopic orientation of 1 can be achieved using a rather weak electric field, implying that the main and side chains with orthogonal directions can move cooperatively. Our work demonstrates that when two separate components, one offering the "jacketing" effect to the normally flexible backbone and the other with mesogens that form surrounding LC phases, are introduced simultaneously into the side chains, the polymer obtained can be described as an MCSCLCP with a fascinating hierarchically ordered structure.

Integrated application of uniform design and least-squares support vector machines to transfection optimization.

BACKGROUND: Transfection in mammalian cells based on liposome presents great challenge for biological professionals. To protect themselves from exogenous insults, mammalian cells tend to manifest poor transfection efficiency. In order to gain high efficiency, we have to optimize several conditions of transfection, such as amount of liposome, amount of plasmid, and cell density at transfection. However, this process may be time-consuming and energy-consuming. Fortunately, several mathematical methods, developed in the past decades, may facilitate the resolution of this issue. This study investigates the possibility of optimizing transfection efficiency by using a method referred to as least-squares support vector machine, which requires only a few experiments and maintains fairly high accuracy. RESULTS: A protocol consists of 15 experiments was performed according to the principle of uniform design. In this protocol, amount of liposome, amount of plasmid, and the number of seeded cells 24 h before transfection were set as independent variables and transfection efficiency was set as dependent variable. A model was deduced from independent variables and their respective dependent variable. Another protocol made up by 10 experiments was performed to test the accuracy of the model. The model manifested a high accuracy. Compared to traditional method, the integrated application of uniform design and least-squares support vector machine greatly reduced the number of required experiments. What's more, higher transfection efficiency was achieved. CONCLUSION: The integrated application of uniform design and least-squares support vector machine is a simple technique for obtaining high transfection efficiency. Using this novel method, the number of required experiments would be greatly cut down while higher efficiency would be gained. Least-squares support vector machine may be applicable to many other problems that need to be optimized.

Shape-persistent elliptic macrocycles composed of polycyclic aromatic hydrocarbons: synthesis and photophysical properties.

Bimolecular coupling/unimolecular cyclization strategies, including McMurry- and Glaser-type homocoupling reactions, were utilized to synthesize two shape-persistent elliptic macrocycles, which consist of polycyclic aromatic hydrocarbon units. The identity and purity of both macrocycles MC1 and MC2 were verified by 1H and 13C NMR, elemental analysis, as well as MALDI-TOF MS. The photophysical properties of MC1 and MC2 in dilute solution were also investigated.

Competition between liquid crystallinity and block copolymerself-assembly in core-shell rod-coil block copolymers.

Core-shell type of architecture revealed the subtle competition between liquid-crystalline ordering and block copolymer (BCP) self-assembly in a rod-coil BCP system.

ABA type liquid crystalline triblock copolymers by combination of living cationic polymerizaition and ATRP: synthesis and self-assembly.

Lamellar and hexagonal-coil-cylinder self-assembled structures of ABA type triblock copolymers containing mesogen-jacketed liquid crystalline polymer (MJLCP) as the rod block, and polyisobutylene (PIB) as the coil middle block were discovered. PIB was synthesized by living cationic polymerization of isobutylene initiated by 1,4-bis(2-chloro-2-propyl)benzene (p-DCC), and then a small amount of styrene was introduced at the end of the PIB chains to form the difunctional PIB macroinitiator with -CH2CH(C6H5)Cl end groups for further atom transfer radical polymerization (ATRP). 2,5-Bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS) was block-copolymerized from the difunctional PIB macroinitiators at 110 °C. The molecular characterization of the triblock copolymers was performed with 1H NMR, 13C NMR, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Their phase structures and transitions were investigated by differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), and polarized optical microscopy experiments. It was demonstrated that the triblock copolymers formed lamellar structures at moderate rod fractions and hexagonal coil cylinders in the rod matrix at high rod fractions. The d-spacing of the microphase-separated structures was influenced by the liquid crystalline phase of rod-like PMPCS blocks.

Molecular wires based on thienylethynylene: synthesis, photophysical properties, and excited-state lifetime.

A series of pi-conjugated molecular wires based on thienylethynylene units have been developed to understand the effect of the molecular structures on their photophysical properties. The investigation of their photophysical properties indicates that the formation of aggregates at the ground state is effectively suppressed by the incorporation of truxene units. The excited-state lifetimes are observed to be biexponential for these molecular wires.

Synthesis of giant rigid pi-conjugated dendrimers.

A novel family of giant pi-conjugated dendrimers (G0, G1, and G2) solely constructed by 5,5,10,10,15,15-hexahexyltruxene units has been developed in a convergent manner through a Suzuki cross-coupling reaction. The overall yields to such large rigid conjugated dendrimers are quite satisfying. The structures and purity of these nanosize rigid dendrimers are verified by 1H and 13C NMR, MALDI-TOF MS, and elemental analysis.