Non-equilibrium Nanoassemblies Constructed by Confined Coordination on a Polymer Chain.

Biological systems employ non-equilibrium self-assembly to create ordered nanoarchitectures with sophisticated functions. However, it is challenging to construct artificial non-equilibrium nanoassemblies due to lack of control over assembly dynamics and kinetics. Herein, we design a series of linear polymers with different side groups for further coordination-driven self-assembly based on shape-complementarity. Such a design introduces a main-chain confinement which effectively slows down the assembly process of side groups, thus allowing us to monitor the real-time evolution of lychee-like nanostructures. The function related to the non-equilibrium nature is further explored by performing photothermal conversion study. The ability to observe and capture non-equilibrium states in this supramolecular system will enhance our understanding of the thermodynamic and kinetic features as well as functions of living systems.

Precise Synthesis of Concentric Ring, Helicoid, and Ladder Metallo-Polymers with Chevron-Shaped Monomers.

Molecular geometry represents one of the most important structural features and governs physical properties and functions of materials. Nature creates a wide array of substances with distinct geometries but similar chemical composition with superior efficiency and precision. However, it remains a formidable challenge to construct abiological macromolecules with various geometries based on identical repeating units, owing to the lack of corresponding synthetic approaches for precisely manipulating the connectivity between monomers and feasible techniques for characterizing macromolecules at the single-molecule level. Herein, we design and synthesize a series of tetratopic monomers with chevron stripe shape which serve as the key precursors to produce four distinct types of metallo-macromolecules with well-defined geometries, viz., the concentric hexagon, helicoid polymer, ladder polymer, and cross-linked polymer, via platinum-acetylide couplings. Concentric hexagon, helicoid, and ladder metallo-polymers are directly visualized by transmission electron microscopy, atomic force microscopy, and ultra-high-vacuum low-temperature scanning tunneling microscopy at the single-molecule level. Finally, single-walled carbon nanotubes (SWCNTs) are selected as the guest to investigate the structure-property relationship based on such macromolecules, among which the helicoid metallo-polymer shows high efficiency in wrapping SWCNTs with geometry-dependent selectivity.

Construction of metallo-helicoids with high antimicrobial activity via intermolecular coordination.

Metallo-helicoids are constructed by intermolecular coordination interactions between covalent linear polymer and tritopic/hexatopic molecular templates. These metallo-polymers with helicoidal conformation exhibit high antimicrobial activities against both Gram-positive and Gram-negative pathogens.

Cephalometric analysis in obese and nonobese patients with obstructive sleep apnea syndrome.

STUDY OBJECTIVES: The aims of this study were to comprehensively evaluate the cephalometric features of patients with obstructive sleep apnea syndrome (OSAS), and to elucidate the relationship between cephalometric variables and severity of the apnea-hypopnea index (AHI). PATIENTS: The study population consisted of 62 male patients with OSAS, classified into 33 obese patients (body mass index [BMI] >or= 27) and 29 nonobese patients (BMI < 27), and 13 male simple snorers (AHI < 5 events per hour). METHOD: and measurements: Diagnostic polysomnography and measurements of 22 cephalometric variables were carried out for all patients and simple snorers. RESULTS: Patients with OSAS in both subgroups showed several significant cephalometric features compared with simple snorers: (1) inferiorly positioned hyoid bone, (2) enlarged soft palate, and (3) reduced upper airway width at soft palate. More extensive and severe soft-tissue enlargements including anteriorly positioned hyoid bone and a longer tongue were found in the obese patients. In the nonobese patients, the anteroposterior distances of the bony nasopharynx and oropharynx were significantly smaller than those of simple snorers and obese patients. Stepwise regression analysis showed that anterior displacement of the hyoid bone and retroposition of the mandible were the dominant overall determinants for AHI in patients with OSAS, and that narrowing of the bony oropharynx and inferior displacement of the hyoid bone were dominant determinants for AHI in nonobese patients. A significant regression model for AHI using cephalometric variables could not be obtained for the obese patients, but the BMI proved to be the most significant determinant. CONCLUSION: Characteristics of the craniofacial bony structure such as narrowing of the nasopharynx and oropharynx and enlargement of the soft tissue in the upper airway may be important risk factors for the development of OSAS in nonobese patients. In obese patients, the deposition of adipose tissue in the upper airway may aggravate the severity of OSAS.

Enhanced gene delivery using biodegradable poly(ester amine)s (PEAs) based on low-molecular-weight polyethylenimine and poly(epsilon-caprolactone)-pluronic-poly(epsilon-caprolactone).

In this paper, the poly(ester amine)s (PEAs) were successfully prepared from low-molecular-weight PEI (Mn = 2000) and Poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol)-poly(epsilon-caprolactone) (PCFC) copolymers using isophorone diisocyanate (IPDI) as cross-linker. The obtained PEAs copolymers are biodegradable and water-soluble. The PEAs/DNA complexes showed effective and stable DNA condensation with the particle size < or = 200 nm and zeta potential > or =10 mV, indicating its potential for intracellular delivery. Compared to the unmodified low-molecular-weight PEI, PEAs displayed similarly low cytotoxicity in all two cell lines (293T: Human kidney carcinoma, HUVEC: Human umbilical vein Endothelial cell) and revealed much higher transfection efficiency in 293T cell lines. Therefore these PEAs might be a novel safe and efficient polymeric gene delivery vectors.