New unsaturated polyesters as injectable drug carriers

New unsaturated polyesters of poly(fumaric acid-glycol-sebacic acid) copolymers and poly(maleic anhydride-glycol-sebacic acid) copolymers were prepared by melt polycondensation of the corresponding mixed monomers: sebacic anhydride, fumaric acid or maleic anhydride and glycol. Methyl-methacrylate (MMA) was used as crosslinker and dimer acid was used as thinner.In vitro studies showed that those copolymers are degradable in phosphate buffer at 37 °C and poly(fumaric acid-glycol-sebacic acid) has proper drug release rate as drug carriers. The biocompatibility of poly(fumaric acid-glycol-sebacic acid) copolymers under mice skin was also evaluated; macroscopic observation and microscopic analysis demonstrated that the copolymer is biocompatible and well tolerated in vivo. The injected poly(fumaric acid-glycol-sebacic acid) [molar ratio M_{fumaric acid}:M_glycol:M_{sebacic acid} = 1.75:2.20:0.25] containing 5% adriamycin hydrochloride (ADM) in the mice bearing Sarcoma-180 tumor exhibited a good antitumor efficacy. The volume doubling time (VDT) (18 ± 2.5 days) of the tumor growth by this treatment was longer than that (7 ± 0.9 days) by the subcutaneous injection of ADM.     

Controlled release of acetochlor from poly (butyl methacrylate-diacetone acrylamide) based formulation prepared by nanoemulsion polymerisation method and evaluation of the efficacy

Acetochlor is an important herbicide for gramineous weeds and some small seed broadleaf weeds. Controlled-release formulations of herbicide are highly desirable not only for attaining the most effective utilisation of the weed control, but also for reducing environmental pollution. Acetochlor was incorporated in poly (butyl methacrylate-diacetone acrylamide) based formulation to obtain controlled release properties. The acetochlor nanocapsules were characterised by size distribution, infrared spectroscopy (IR) and field emission scanning electron microscopy (FESEM), and factors related to loading efficiency, swelling behaviour of the formulation were investigated. For this controlled-release formulation, the loading efficiency could reach about 50% (w/w). n, the diffusion parameter was indicative of the transport mechanism, and the values for ‘n’ were in the range of 0.28–0.61, which indicated that the release of acetochlor was diffusion-controlled. The time taken for 50% of the active ingredient to be released into water, t₅₀, was also calculated for the comparison of formulations in different conditions. The formulation with higher temperature and more diacetone acrylamide had lower value of t₅₀, which means a quicker release of the active ingredient. This study highlighted some pieces of evidence that improved herbicide incorporation and slower release were linked to potential interactions between the herbicide and the polymer.     

Siloxane polymers containing azo moieties synthesized by click chemistry for photo responsive and liquid crystalline applications

Three new types of siloxane‐based photoactive liquid crystalline polymers containing azo side groups were synthesized through the click chemistry route. The polymers having molecular weight range of 14,000–34,000 g mol^?1 were soluble in most of the polar solvents like chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and dichloromethane. The photoresponsive trans–cis photoisomerization under UV radiation and cis–trans relaxation process in dark for the polymers were studied. The isomerization rate constants were found to be 0.01–0.04 sec^?1 and 1.16*10^?4–4.67*10^?4 sec^?1, respectively. It has been noted that the polymers showed high intensity absorption for n‐π* in chloroform. Both trans and cis forms of azide monomers having azo moiety exhibited molar extinction coefficient ( ? _max) in the range of 22,000–33,000 L mol^?1 cm^?1. The thermotropic behavior of the polymers was studied by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) experiments. Polymer P1 showed liquid crystalline textures of nematic droplets, whereas P2 showed smectic focal conic texture and nematic droplets. Polymer P1 was also studied for photomechanical bending on exposure to UV radiation. The polymers showed initial degradation temperature in the range of 210–275°C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and Photochromic Properties of Configurationally Varied Azobenzene Glycosides

Spatial orientation of carbohydrates is a meaningful parameter in carbohydrate recognition processes. To vary orientation of sugars with temporal and spatial resolution, photosensitive glycoconjugates with favorable photochromic properties appear to be opportune. Here, a series of azobenzene glycosides were synthesized, employing glycoside synthesis and Mills reaction, to allow “switching” of carbohydrate orientation by reversible E/Z isomerization of the azobenzene N=N double bond. Their photochromic properties were tested and effects of azobenzene substitution as well as the effect of anomeric configuration and the orientation of the sugars 2-hydroxy group were evaluated.     

PPH加Block术与单纯Block术治疗直肠前突的临床比较研究

目的 探讨吻合器痔上黏膜环切术（PPH 术）加直肠闭式修补术（Block 术）治疗直肠前突的临床疗效。方法 近9年来对女性直肠前突患者先后采用Block 术（36 例）和PPH+Block 术（41 例）治疗,分析两组患者的临床资料,观察并比较其术后第1 天出血量、术后并发症的发生率及疗效。结果 两组患者术后第1 天出血量及术后并发症发生率的差异均无统计学意义（均P＞0.05）。术后3、6、12个月PPH+Block 术组与Block 术组的痊愈率分别为85.4%、82.9%、82.9%和58.3%、52.8%、52.8%,差异均有统计学意义（均P＜0.05）。结论 PPH+Block 术治疗直肠前突较单纯Block 术疗效更好,值得推广应用。     

Sulfur and Azobenzenes,a Profitable Liaison: Straightforward Synthesis of Photoswitchable Thioglycosides with Tunable Properties

Azobenzene photoswitches are valuable tools for controlling properties of molecular systems with light. We have been investigating azobenzene glycoconjugates to probe carbohydrate-protein interactions and to design glycoazobenzene macrocycles with chiroptical and physicochemical properties modulated by light irradiation. To date, direct conjugation of glycosides to azobenzenes was performed by reactions providing target compounds in limited yields. We therefore sought a more effective and reliable coupling method. In this paper, we report on a straightforward thioarylation of azobenzene derivatives with glycosyl thiols as well as other thiols, thereby increasing the scope of azobenzene conjugation. Even challenging unsymmetrical conjugates can be achieved in good yields via sequential or one-pot procedures. Importantly, red-shifted azoswitches, which are addressed with visible light, were easily functionalized. Additionally, by oxidation of the sulfide bridge to the respective sulfones, both the photochromic and the thermal relaxation properties of the core azobenzene can be tuned. Utilizing this option, we realized orthogonal three-state photoswitching in mixtures containing two distinct azobenzene thioglycosides.     

Synthesis and Surface‐Spectroscopic Characterization of Photoisomerizable glyco‐SAMs on Au(111)

Photoisomerizable glyco‐SAMs (self‐assembled monolayers), utilizing synthetic azobenzene glycoside derivatives were fabricated. The ultimate goal of this project is to assay the influence of the 3D arrangement of sugar ligands on cell adhesion, and eventually make cell adhesion photoswitchable. However, it is a prerequisite for any biological study on the spatial conditions of carbohydrate recognition, that photoisomerization of the surface molecules can be verified. Here, we employed IRRAS and XPS to spectroscopically characterize glyco‐SAMs. In particular and unprecedented to date, we prove reversible E→Z→E isomerization of azobenzene glycoside‐terminated SAMs.     

甲氨蝶呤/层状双金属氢氧化物的性能调控及细胞生物实验研究

在乙醇-水混合体系中,以氨水为沉淀剂共沉淀合成了甲氨蝶呤/层状双金属氢氧化物(MTX/LDH)纳米复合物,采用控制水热处理时间的方式来调控其性能。利用X-射线衍射(XRD)、透射电镜(TEM)和红外光谱(FT-IR)等表征手段,对其结构及形貌进行了表征。研究表明:MTX分子以单层倾斜或垂直方式插入LDH层间,随着水热处理时间的不同,MTX在层间的倾斜角度发生了变化;水热处理时间对产物的结晶度、粒径和层间排列方式都有影响,当水热处理时间为12h时,得到的MTX/LDH纳米复合物的结晶度最高,单分散性最好。在磷酸缓冲液中考察了MTX/LDH纳米复合物的缓释性能,结果表明样品均呈现出良好的缓释性能,释放速率先快后慢。重点考察了这几种MTX/LDH纳米复合物作用于肺癌细胞A549的细胞生物实验,研究表明这几种复合物对肺癌细胞A549都具有良好的抑制作用,其效果与纳米复合物的单分散性和粒径有密切的关系,单分散性越好,粒径分布越均匀,对A549癌细胞的抑制效果越好。     

Photochromic Free MOF‐Based Near‐Infrared Optical Switch

We demonstrate herein an all‐optical switch based on stimuli‐responsive and photochromic‐free metal–organic framework (HKUST‐1). Ultrafast near‐infrared laser pulses stimulate a reversible 0.4 eV blue shift of the absorption band with up to 200 s^?1 rate due to dehydration and concomitant shrinking of the structure‐forming [Cu₂C₄O₈] cages of HKUST‐1. Such light‐induced switching enables the remote modulation of intensities of photoluminescence of single crystals of HKUST‐1 as well visible radiation passing through the crystal by 2 order of magnitude. This opens up the possibility of utilyzing stimuli‐responsive MOFs for all‐optical data processing devices.