A Synthetic Dynamic Polyvinyl Alcohol Photoresin for Fast Volumetric Bioprinting of Functional Ultrasoft Hydrogel Constructs

Tomographic volumetric bioprinting (VBP) enables fast photofabrication of cell-laden hydrogel constructs in one step, addressing the limitations of conventional layer-by-layer additive manufacturing. However, existing biomaterials that fulfill the physicochemical requirements of VBP are limited to gelatin-based photoresins of high polymer concentrations. The printed microenvironments are predominantly static and stiff, lacking sufficient capacity to support 3D cell growth. Here a dynamic resin based on thiol–ene photo-clickable polyvinyl alcohol (PVA) and thermo-sensitive sacrificial gelatin for fast VBP of functional ultrasoft cell-laden hydrogel constructs within 7–15 s is reported. Using gelatin allows VBP of permissive hydrogels with low PVA contents of 1.5%, providing a stress-relaxing environment for fast cell spreading, 3D osteogenic differentiation of embedded human mesenchymal stem cells and matrix mineralization. Additionally, site-specific immobilization of molecules-of-interest inside a PVA hydrogel is achieved by 3D tomographic thiol–ene photopatterning. This technique may enable spatiotemporal control of cell-material interactions and guides in vitro tissue formation using programmed cell-friendly light. Altogether, this study introduces a synthetic dynamic photoresin enabling fast VBP of functional ultrasoft hydrogel constructs with well-defined physicochemical properties and high efficiency.     

高支化含无机粒子的巯基硅氧烷溶胶的制备及结构表征

用溶胶-凝胶法制备了一种新型的多功能巯基硅氧烷溶胶,其结构用1H-NM R,FT-IR和M S进行了表征,巯基硅氧烷溶胶的无机粒子粒径大小与分布用小角度光散射仪(SALS)进行了测定。这种新型巯基硅氧烷溶胶能够提高改性亚麻籽油体系自由基聚合速率。     

基于香豆素-茚满二酮共轭物的硫醇比色探针

基于硫醇对α,β-不饱和双键的亲核加成,设计合成了一种香豆素-1,3-茚满二酮加合物的比色硫醇探针.硫醇与探针发生迈克尔加成,打断了分子内的共轭体系,阻止了香豆素向缺电子的1,3-茚满二酮基团的分子内电荷转移,引起了吸收光谱上的蓝移和溶液颜色的变化(由紫蓝色变为无色).研究结果表明:在DMSO-PBS buffer(0.01M,pH=7.4,9∶1,v/v)体系中,探针1能够用于半胱氨酸(Cys),同型半胱氨酸(Hcy)和还原型谷胱甘肽(GSH)的高选择性裸眼识别,Cys的检出限为6.9×10-7mol/L.     

Photocrosslinking of functionalized rubbers. X. Butadiene–acrylonitrile copolymers

The photocrosslinking of polyacrylonitrile‐block‐polybutadiene‐block‐polyacrylonitrile (ABA) was shown to proceed within seconds at ambient temperature upon UV exposure in the presence of an acylphosphine oxide photoinitiator. The curing process was followed by infrared spectroscopy, insolubilization, and hardness measurements. Complete insolubilization could not be achieved with the neat ABA rubber because of the poor reactivity of the 2‐butene double bond and the low vinyl content of the polybutadiene chain. The addition of multifunctional acrylate monomers (20 wt %) causes a substantial increase of both the reaction rate and the crosslink density of the polymer, which becomes completely insoluble in toluene in less than 1 s upon UV irradiation. An even greater effect was observed by using small amounts (1 wt %) of a trifunctional thiol crosslinker. Both the thiol and the photoinitiator concentrations were shown to affect the kinetics of the thiol–ene polymerization and the polymer network crosslink density. A direct relationship was found to exist between the swelling degree of the UV‐cured rubber and the interchain molecular weight of the network. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2204–2216, 2001     

Thiol Redox and pKa Properties of Mycothiol,the Predominant Low‐Molecular‐Weight Thiol Cofactor in the Actinomycetes

The thiol pK_a and standard redox potential of mycothiol, the major low‐molecular‐weight thiol cofactor in the actinomycetes, are reported. The measured standard redox potential reveals substantial discrepancies in one or more of the other previously measured intracellular parameters that are relevant to mycothiol redox biochemistry.     

温度对巯基封端液态聚硫橡胶结构的影响

利用凝胶渗透色谱和核磁共振波谱分析,通过研究聚硫橡胶在温度变化时分子结构发生的变化,推断出温度变化时聚硫橡胶链交换反应模式。     

Are disulphide bonds formed during acid gelation of preheated milk?

The role of thiol/disulphide exchanges during acid gelation of preheated milk was studied with milk samples with or without N‐ethylmaleimide (NEM), a thiol‐blocking agent, and acidified to pH 4 by the addition of glucono‐delta‐lactone at 20 °C. Active or total thiol groups, particle size with light scattering measurements in a dissociating solvent or by SDS‐agarose electrophoresis were determined on acidified milk samples. Diffusing wave spectroscopy and rheology in low strain were applied during acidification of sample, while rheology in large strain was applied on final acid gels. The only effect of the presence of NEM was a reduced firmness of acid gels as measured at large strain and a reduced tendency to form large aggregates at pH<5.5. In conclusions, thiol/disulphide exchanges during acidification of milk played only a minor role in the building of acid gel networks from heated milk.     

1-磺甲基四氮唑-5-硫醇双钠盐的合成

研究了头孢尼西的侧链１－磺甲基四氮唑－５－硫醇双钠盐的合成。以亚硫酸氢钠、甲醛、氨水为原料，经五步反应可制备１－磺甲基四氮唑－５－硫醇双钠盐，五步反应总收率为１０．８％ 。在原文献的基础上，作了一些改进，最主要的是第三步的烷基化试剂由溴乙烷替代碘甲烷，降低了工业成本，使本工艺易于工业化。     

噻虫嗪的合成技术

以2,3-二氯丙烯和硫氰酸钠为起始原料,首先生成中间体2-氯丙烯硫代异氰酸酯(1),(1)再与苄基硫醇加成,环合生成中间体2-苄硫基-5-氯甲基噻唑(2);(2)与3-甲基-4-硝基亚胺-1,3,5-恶二嗪反应生成中间体苄硫基噻虫嗪(3);(3)与氯气反应生成目标化合物噻虫嗪,合成总收率达到50.6%。研究了噻虫嗪的合成工艺,分析并实验优化了主要的合成工艺参数。该合成路线原料易得,反应过程稳定,收率高,产品质量好,有利于工业化生产。