Functional Supramolecular Gels Based on the Hierarchical Assembly of Porphyrins and Phthalocyanines

Supramolecular gels containing porphyrins and phthalocyanines motifs are attracting increased interests in a wide range of research areas. Based on the supramolecular gels systems, porphyrin or phthalocyanines can form assemblies with plentiful nanostructures, dynamic, and stimuli-responsive properties. And these π-conjugated molecular building blocks also afford supramolecular gels with many new features, depending on their photochemical and electrochemical characteristics. As one of the most characteristic models, the supramolecular chirality of these soft matters was investigated. Notably, the application of supramolecular gels containing porphyrins and phthalocyanines has been developed in the field of catalysis, molecular sensing, biological imaging, drug delivery and photodynamic therapy. And some photoelectric devices were also fabricated depending on the gelation of porphyrins or phthalocyanines. This paper presents an overview of the progress achieved in this issue along with some perspectives for further advances

The abnormal level of HSP70 is related to Treg/Th17 imbalance in PCOS patients

Abstract Background Polycystic ovary syndrome (PCOS) is a disease with chronic nonspecific low-grade inflammation. The imbalance of immune cells exists in PCOS. Several studies have found that heat shock protein 70 (HSP70) may be involved in the immunological pathogenesis of PCOS, but the relationship between HSP70 and Regulatory T cell (Treg)/T helper cell 17(Th17) ratio remains unclear. This study aims to explore the correlation between HSP70 and Treg/Th17 ratio and to provide evidence for the role of HSP70 in the immunological etiology of PCOS. Results There was no significant difference in age and body mass index (BMI) between the two groups. The concentrations of basal estradiol (E2), basal follicle-stimulating hormone (FSH) did not show a significant difference between the two groups. The concentrations of basal luteinizing hormone (LH) (P < 0.01), testosterone (T) (P < 0.01), glucose (P < 0.001) and insulin (P < 0.001) in PCOS patients were significantly higher than those in the control group. The protein levels of HSP70 were significantly higher in serum in the PCOS group (P < 0.001). The percentage of Treg cells was significantly lower (P < 0.01), while the percentage of the Th17 cells of the PCOS group was significantly higher than that of the control group (P < 0.05). The ratio of Treg/Th17 in the PCOS group was significantly lower (P < 0.001). The concentrations of Interleukin (IL)-6, IL-17, and IL-23 were significantly higher, while the levels of IL-10 and Transforming growth factor-β (TGF-β) were significantly lower in the PCOS group (P < 0.001). Spearman rank correlation analysis showed a strong negative correlation of serum HSP70 levels with Treg/Th17 ratio, IL-10, and TGF-β levels. In contrast, HSP70 levels were significantly positively correlated with IL-6, IL-17, IL-23, LH, insulin, and glucose levels. Conclusion The abnormal level of HSP70 is correlated with Treg/Th17 imbalance and corresponding cytokines, which indicates that HSP70 may play an important role in PCOS immunologic pathogenesis

The effect of glutamine on Dehydroepiandrosterone-induced polycystic ovary syndrome rats

Abstract Background Previous studies have shown that chronic inflammation and oxidative stress may play an important role in the pathophysiology of polycystic ovary syndrome (PCOS), and glutamine (Gln) have showed the anti-inflammatory and antioxidant properties. So the aim of this study is to investigate the effect of glutamine supplementation on PCOS rats. Methods Female Sprague–Dawley rats were randomly assigned into four groups (n = 10 /group), control group, PCOS group, PCOS+ 0.5 g/kg Gln group and PCOS+ 1.0 g/kg Gln group. All the PCOS rats were administrated with 6 mg/100 g dehydroepiandrosterone (DHEA) for 20 consecutive days, all the PCOS+Gln groups were intraperitoneal injected glutamine twice in the next morning after the last DHEA injection. All the samples were collected 12 h after the last administration. Ovarian histological examinations were analyzed and the concentration of serum hormone, inflammatory and oxidative stress factors were measured. Results There was no obvious ovarian histological change among the PCOS group and PCOS+Gln groups. All the detected inflammation factors [C-reactive protein, interleukin (IL)-6, IL-18, tumor necrosis factor] showed significantly higher in all the PCOS groups compared to the control group (P < 0.01), and were significantly decreased with the supplementation of 0.5 g/kg glutamine (P < 0.01). Concentrations of superoxide dismutase were significantly lower in all the PCOS groups (P < 0.01) compared to the control group, and increased significantly with the supplementation of 0.5 g/kg glutamine (P < 0.01). Serum concentrations of malondialdehyde, nitric oxide synthase and nitric oxide were significantly higher in PCOS group (P < 0.01) compared with the control group, and significantly decreased to the comparative levels of control group with supplementation of 0.5 g/kg glutamine (P < 0.01). Conclusion There is low-grade inflammation and oxidative stress in DHEA-induced PCOS rats. The supplementation of 0.5 g/kg glutamine could effectively ameliorate the inflammation and oxidative stress conditions of PCOS

Abnormal expression of HSP70 may contribute to PCOS pathology

Abstract Background The mechanism of the pathological change of polycystic ovary syndrome (PCOS) is still unclear. Previous studies have shown that PCOS is a chronic nonspecific low-grade inflammatory condition, and that heat shock protein (HSP)70 has a potent anti-inflammatory property. So the aim of this study is to investigate the correlation between HSP70 and the hormones and inflammatory factors and to find out the role of HSP70 in the pathogenesis of PCOS. Methods Twenty female Sprague–Dawley (SD) rats (aged 23 days and weighted 80-90 g) were randomly divided into two groups (n = 10 per group), PCOS group and control group. PCOS group were subcutaneously injected with 6 mg/100 g dehydro-epiandrosterone (DHEA) for 20 consecutive days, the control group were subcutaneously injected with a solvent of equivalent amount. All the samples were collected in the morning fasting state, 12 h after the last administration. Histological examinations of ovarian tissues were analyzed. Hormone levels and inflammatory factors levels were measured by enzyme-linked immunosorbent assay (ELISA) kits. Results Serum concentrations of testosterone (T) and luteinizing hormone (LH) were significantly higher in the PCOS group than the control group (P < 0.001), but the concentrations of estradiol (E2), follicle stimulating hormone (FSH) and insulin didn’t show significant difference between these two groups. All the concentrations of inflammatory factors including C-reactive protein (CRP), interleukin (IL)-6, IL-18, and tumor necrosis factor (TNF)-α. were significantly higher in PCOS group than the control group (P < 0.001). The expressions of HSP70 were significantly lower in serum but higher in ovarian tissues in the PCOS group than the control group. Spearman rank correlation analysis showed strong negative correlation of serum HSP70 levels with T, LH and all the detected inflammatory factors. Conclusion The abnormal expression of HSP70 correlated with testosterone and inflammatory factors, which indicates that HSP70 may play an important role in PCOS pathology

Rotation and translation invariants of Gaussian-Hermite moments

Geometric moment invariants are widely used in many fields of image analysis and pattern recognition since their first introduction by Hu in 1962. A few years ago, Flusser has proved how to find the indepen- dent and complete set of geometric moment invariants corresponding to a given order. On the other hand, the properties of orthogonal moments show that they can be recognized as useful tools for image representation and reconstruction. Therefore, derivation of invariants from orthogonal moments becomes an interesting subject and some results have been reported in literature. In this paper, we pro- pose to use a family of orthogonal moments, called Gaussian-Hermite moments and defined with Her- mite polynomials, for deriving their corresponding invariants. The rotation invariants of Gaussian- Hermite moments can be achieved algebraically according to a property of Hermite polynomials. This approach is definitely different from the conventional methods which derive orthogonal moment invari- ants either by image normalization or by an expression as a linear combination of the invariants of geo- metric moments. One significant conclusion drawn is that the rotation invariants of Gaussian-Hermite moments have the identical forms to those of geometric moments. This coincidence is also proved math- ematically in the appendix of the paper. Moreover, the translation invariants could be easily constructed by translating the coordinate origin to the image centroid. The invariants of Gaussian-Hermite moments both to rotation and to translation are accomplished by the combination of these two kinds of invariants. Their rotational and translational invariance is evaluated by a set of transformed gray-level images. The numeric stabilities of the proposed invariant descriptors are also discussed under both noise-free and noisy conditions. The computational complexity and time for implementing such invariants are analyzed as well. In addition to this, the better performance of the Gaussian-Hermite invariants is experimentally demonstrated by pattern matching in comparison with geometric moment invariants

Hierarchical Assembly of l‑Phenylalanine-Terminated Bolaamphiphile with Porphyrin Show Tunable Nanostructures and Photocatalytic Properties

Demands related to clean energy and environmental protection promote the development of novel supramolecular assemblies for photocatalysis. Because of the distinctive aggregation behaviors, bolaamphiphiles with two hydrophilic end groups could be theoretically the right candidates for the fabrication of high-performance photocatalysis. However, photocatalytic applications based on bolaamphiphilic assemblies were still rarely investigated. Especially, the relationship between diverse assembled nanostructures and the properties for different applications is urgently needed to be studied. Herein, we demonstrate that using the hierarchical assembly of bolaamphiphiles could correctly induce the porphyrin supramolecular architectures with much better photocatalytic performances than the aggregations containing 450 times of the porphyrin molecules, even though both molecular structures as well as the J-aggregations of porphyrin building blocks are same in two different systems. Thus, the co-assembly of l-phenylalanine terminated bolaamphiphile (Bola-F) and the porphyrin containing four hydroxyl groups (tetrakis-5,10,15,20-(4-hydroxyphenyl)­porphyrin) can form microtube in methanol and forms fibers/spheres in methanol/water mixture. For catalyzing the photodegradation of rhodamine B, the small amount of J-aggregated porphyrin within Bola-F microtubes show much better photocatalytic performance comparing with that of huge porphyrin J-aggregations in fibers/spheres. The supramolecular assemblies as well as the photocatalysis were thoroughly characterized by different spectroscopies and electron microscopy. It is demonstrated that the co-assembly with bolaamphiphiles could inhibit the energy transfer of porphyrin aggregation and subsequently benefit the electron transfer and corresponding photocatalysis under photo-irradiation. This work is not only useful for further understanding the hierarchically supramolecular assembly but also provides a new strategy for making novel functional supramolecular architectures based on the assembly of bolaamphiphiles and porphyrins

Phthalocyanine-Triggered Helical Dipeptide Nanotubes with Intense Circularly Polarized Luminescence

Nanotubes with circularly polarized luminescence (CPL) are attracting much attention due to many potential applications, such as chiroptical materials, displays, and sensing. However, it remains a challenge to change the assemblies of ordinarily molecular building blocks into CPL supramolecular nanotubes. Herein, the regulation of quite common dipeptide (Fmoc-FF) assemblies into unprecedented helical nanotubes exhibiting intense CPL is reported by simply doping a few phthalocyanine (octakis(carboxyl)phthalocyaninato zinc complex (Pc)) molecules. Interestingly, altering the Fmoc-FF/Pc molar ratios over a wide range cannot change the nanotubes structures according to transmission electron microscopy (TEM) and atomic force microscope (AFM) measurements. Although molecular dynamics simulations suggest that the noncovalent interactions between Fmoc-FF and Pc are quite weak, few Pc molecules can still change the secondary structures of a large number of Fmoc-FF assemblies, which hierarchically form helical supramolecular nanotubes with long-range ordered molecular packing, leading to intense CPL signals with large luminescence dissymmetry factor (g(lum) = 0.04). Consequently, the chiral reorganization of Fmoc-FF assemblies is dependent on the coassembly between Pc molecule and Fmoc-FF supramolecular architectures. These results open the possibility for the fine-tuning of helix and supramolecular nanotubes with CPL properties by using a small number of cofactors

Triazole-linked transition state analogs as selective inhibitors against V. cholerae sialidase.

Sialidases or neuraminidases are enzymes that catalyze the cleavage of terminal sialic acids from oligosaccharides and glycoconjugates. They play important roles in bacterial and viral infection and have been attractive targets for drug development. Structure-based drug design has led to potent inhibitors against neuraminidases of influenza A viruses that have been used successfully as approved therapeutics. However, selective and effective inhibitors against bacterial and human sialidases are still being actively pursued. Guided by crystal structural analysis, several derivatives of 2-deoxy-2,3-didehydro-N-acetylneuraminic acid (Neu5Ac2en or DANA) were designed and synthesized as triazole-linked transition state analogs. Inhibition studies revealed that glycopeptide analog E-(TriazoleNeu5Ac2en)-AKE and compound (TriazoleNeu5Ac2en)-A were selective inhibitors against Vibrio cholerae sialidase, while glycopeptide analog (TriazoleNeu5Ac2en)-AdE selectively inhibited Vibrio cholerae and A. ureafaciens sialidases