CONFORMATIONAL PREFERENCES ABOUT Cpy-S BONDS IN DI-2-PYRIDYL DISULFIDE

Abstract

The total energy, dipole moment and electron densities for each possible rotational conformation about the C_py-S bonds of di-2-pyridyl disulfide were evaluated by using the semi-quantitative CNDO/2 method. The conformations in which the pyridine rings are coplanar with the valency plane of the bonded sulfur atom (cis-cis, cis-trans and trans-trans) were predicted to be the most favored ones.

Results of the theoretical study, when compared to some experimental determinations such as dipole moment and variable temperature pmr spectra, provided evidence that easy interconversion between these conformations can occur.     

鸡骨素及其酶解液的美拉德反应产物挥发性风味成分比较分析

利用固相微萃取/气相色谱-质谱(SPME/GC-MS)联用与电子鼻(E-Nose)嗅探技术对鸡骨素美拉德反应产物(MRPs1)及鸡骨素酶解液美拉德反应产物(MRPs2)中的挥发性风味成分进行比较分析。在两种产物中共鉴定出77种挥发性化学成分,其中醇类18种、醛酮类23种、酸类3种、酯类10种、杂环类7种及其他类16种,两种产物中共有成分26种。与MRPs1相比,MRPs2中醛酮、杂环类化合物的相对含量较高,但前者的酯类物质含量更为丰富。(E)-2-辛烯-1-醇、(6Z,9Z)-十五碳二烯-1-醇、苯甲醛、辛醛、6-甲基-5-庚烯-2-酮、2-乙基-3-羟基-4(4H)-吡喃酮、2,3,5-三甲基-6-乙基吡嗪、2-[(甲基二硫基)甲基]呋喃构成了MRPs2的特有成分,γ-丁位十二内酯为MRPs1的特有成分。在两种反应产物中,除4-甲基-5-羟乙基噻唑的相对含量均较高外(MRP1相似文献   

Micro-CT参数对骨质疏松性椎体压缩性骨折术后复发的预测价值

本研究探讨Micro-CT参数对骨质疏松性椎体压缩性骨折(OVCF)患者术后复发的预测价值。选取OVCF患者127例,根据术后6个月骨折复发情况分为复发组(n=41)与未复发组(n=86)。患者均接受Micro-CT检查,对比两组Micro-CT参数,即骨体积分数(BV/TV)、骨小梁厚度(Tb.Th)、骨小梁间隙(Tb.Sp)、结构模型指数(SMI),以及骨密度(BMD)、骨矿含量(BMC),分析各参数与BMD、BMC及术后复发相关性,并评价各参数对术后复发的预测价值。结果显示,复发组骨体积分数(BV/TV)、骨小梁厚度(Tb.Th)低于未复发组,骨小梁间隙(Tb.Sp)、结构模型指数(SMI)高于未复发组(P<0.05);BV/TV、Tb.Th与骨密度(BMD)、骨矿含量(BMC)呈正相关,Tb.Sp、SMI与BMD、BMC呈负相关(P<0.05);将年龄、BMD、BMC等其他因素控制后,BV/TV、Tb.Sp、Tb.Th、SMI与OVCF术后骨折复发显著相关(P<0.05);BV/TV、Tb.Sp、Tb.Th、SMI联合预测OVCF术后骨折复发的曲线下面积(AUC)最大,为0.888(P<0.05)。提示Micro-CT参数在OVCF患者中呈异常表达,采用Micro-CT检查可为临床预测OVCF术后骨折复发提供科学指导。     

In-bone protein digestion followed by LC-MS/MS peptide analysis as a new way towards the routine proteomic characterization of human maxillary and mandibular bone tissue in oral surgery

Proteomic characterization of alveolar bones in oral surgery represents an analytical challenge due to their insoluble character. The implementation of a straightforward technique could lead to the routine use of proteomics in this field. This work thus developed a simple technique for the characterization of bone tissue for human maxillary and mandibular bones. It is based on the direct in-bone tryptic digestion of proteins in both healthy and pathological human maxillary and mandibular bone samples. The released peptides were then identified by the LC-MS/MS. Using this approach, a total of 1120 proteins were identified in the maxillary bone and 1151 proteins in the mandibular bone. The subsequent partial least squares–discrimination analysis (PLS-DA) of protein data made it possible to reach 100% discrimination between the samples of healthy alveolar bones and those of the bone tissue surrounding the inflammatory focus. These results indicate that the in-bone protein digestion followed by the LC-MS/MS and subsequent statistical analysis can provide a deeper insight into the field of oral surgery at the molecular level. Furthermore, it could also have a diagnostic potential in the differentiation between the proteomic patterns of healthy and pathological alveolar bone tissue. Data are available via ProteomeXchange with the identifier PXD026775.     

L-Arginine/nanofish bone nanocomplex enhances bone regeneration via antioxidant activities and osteoimmunomodulatory properties

In this study,a promising strategy has been developed to promote bone regeneration by combining antioxidant activities and osteoimmunomodulatory properties.Herein,an L-arginine/nanofish bone(Arg/NFB) nanocomplex has been prepared and evaluated in vitro and in vivo.The Arg/NFB nanocomplex possesses good antioxidant activities and could modulate the polarization of non-activated macrophage into different types and induce the secretion of pre-inflammato ry,anti-inflammatory,osteogenic as well as angiogenic cytokines.Additionally,the regulated immune microenvironment can enhance the osteogenic differentiation of mouse embryo osteoblast precursor cells(MC3 T3-E1) and angiogenic capacity of human umbilical vein endothelial cells(HUVECs),leading to the improved formation of mineralized nodules,alkaline phosphatase activity and angiogenic effects.In vivo results with cranial defect models reveal that the treatment of Arg/NFB nanocomplex exhibited significant improvement of new bone formation and angiogenesis.All the results demonstrate Arg/NFB nanocomplex with antioxidant activities and osteoimmunomodulatory properties could be a new idea for developing the next generation of bone regeneration biomaterials.     

The TEM characterization of the lamellar structure of osteoporotic human trabecular bone

The lamellar structure of osteoporotic human trabecular bone was characterized experimentally by means of transmission electron microscopy (TEM). More specifically, the TEM was used to determine if trabecular bone exhibits similar lamellar structural motifs as cortical bone by analyzing unmineralized, mineralized and demineralized bone, and to study the influence of the osteocyte network on the lamellar structure of osteoporotic trabecular bone. Comparison with normal trabecular bone is included. This paper summarizes partial results of a larger study, which addressed the characterization of the hierarchical structure of normal versus osteoporotic human trabecular bone [Rubin, M.A., 2001. Multiscale characterization of the ultrastructure of trabecular bone in osteoporotic and normal humans and in two inbred strains of mice. MS Thesis, Georgia Institute of Technology.] at several structural scales.     

High-affinity integration of hydroxyapatite nanoparticles with chemically modified silk fibroin

Hydroxyapatite (HA)-based nanocomposites were prepared by a co-precipitation method with silk fibroin (SF) serving as organic matrix. Silk fibroin was chemically modified with an alkali solution or an enzyme attempting to improve the interface between the mineral and the organic matrix. The influences of the alkali and enzyme pretreatments on microstructure and physicochemical properties of HA–SF composite were examined and compared. The results reveal that both the two kinds of pretreatments facilitate the formation of highly ordered three-dimensional porous network throughout the composites, increase the microhardness of the composite, and promote the preferential growth of HA crystallites along c-axis. Among all the as-prepared samples, the composite containing the enzyme pretreated SF shows desirable hierarchical microstructure with higher degree of organization and more uniform pore size distribution. Due to the enzyme pretreatment, HA crystallites undergo obvious changes in morphology from rod-like to␣whisker-like and in crystal growth towards more apparent epitaxy along c-axis. The alkali pretreatment induces the stronger chemical interactions between HA and SF and thus to strengthen the inorganic–organic interfacial adhesion. The newly developed HA–SF composites are expected to be attractive biomedical materials for bone repair and remodeling.     

The N- and C-terminal domains of parathyroid hormone-related protein affect differently the osteogenic and adipogenic potential of human mesenchymal stem cells

Parathyroid hormone-related protein (PTHrP) is synthesized by diverse tissues, and its processing produces several fragments, each with apparently distinct autocrine and paracrine bioactivities. In bone, PTHrP appears to modulate bone formation in part through promoting osteoblast differentiation. The putative effect of PTH-like and PTH-unrelated fragments of PTHrP on human mesenchymal stem cell (MSCs) is not well known. Human MSCs were treated with PTHrP (1-36) or PTHrP (107-139) or both (each at 10 nM) in osteogenic or adipogenic medium, from the start or after 6 days of exposure to the corresponding medium, and the expression of several osteoblastogenic and adipogenic markers was analyzed. PTHrP (1-36) inhibited adipogenesis in MSCs and favoured the expression of osteogenic early markers. The opposite was observed with treatment of MSCs with PTHrP (107-139). Moreover, inhibition of the adipogenic differentiation by PTHrP (1-36) prevailed in the presence of PTHrP (107-139). The PTH/PTHrP type 1 receptor (PTH1R) gene expression was maximum in the earlier and later stages of osteogenesis and adipogenesis, respectively. While PTHrP (107-139) did not modify the PTH1R overexpression during adipogenesis, PTHrP (1-36) did inhibit it; an effect which was partially affected by PTHrP (7-34), a PTH1R antagonist, at 1 µM. These findings demonstrate that both PTHrP domains can exert varying effects on human MSCs differentiation. PTHrP (107-139) showed a tendency to favor adipogenesis, while PTHrP (1-36) induced a mild osteogenic effect in these cells, and inhibited their adipocytic commitment. This further supports the potential anabolic action of the latter peptide in humans.     

Effects of thermoultrasonic treatment on characteristics of micro-nano particles and flavor in Greenland halibut bone soup

In order to investigate the effects of thermoultrasonic treatment (TUT) on the formation of colloidal micro-nano particles (MNPs) and the quality of halibut bone soup, nutrients, particle characteristics, and flavor characteristics were analyzed. The morphology of MNPs was studied using an optical microscope. Results showed that TUT could increase the nutrient content (total sugars, 22.15 mg/100 mL; water soluble proteins, 173.24 mg/mL; fatty acids, 1779.7 mg/100 mL; solids, 3.16 g/100 mL), reduce the particle size (605.92 nm) and interfacial tension. Meanwhile, TUT make the halibut bone soup has better emulsifying characteristics and stability. The contents of flavor substances, such as esters, 5′-nucleotides, organic acids in the halibut bone soup were more abundant, while the contents of hexanal and 1-octen-3-ol and fishy off-flavor were reduced in TUT group. The overall odor and taste outline were more harmonious. Therefore, TUT can be used in the production of high quality fish bone soup, and TUT could be considered as a good deep processing technology for halibut bone and improve economic efficiency.     

BMP-6 Loaded Polyelectrolyte Complex Nanoparticles Inducing Osteogenic Differentiation and Apoptosis of Malignant Plasma Cells for Local Treatment of Multiple Myeloma

In the malignant plasma cell disease multiple myeloma (MM), bone lesions and resulting fractures caused by MM cell (MMC) accumulation represent a major cause of morbidity and mortality. Despite recent advantages in systemic treatment, residual MMCs remain, especially in bone lesions. Therefore an interfacial delivery system for local treatment of MM and induced bone disease based on polyelectrolyte complex nanoparticles (PEC NP) loaded with bone morphogenetic protein 6 (BMP-6) inducing de-novo bone formation and MMC apoptosis is presented herein. BMP-6 loaded PEC NP are fabricated by defined mixing bio-related cationic and anionic polysaccharides and BMP-6 according to molar ratio of BMP-6/PEC-NP of 1/3. BMP-6/PEC NP bound to a model substrate releases 10% BMP-6 sustainably within two weeks as accessed by infrared spectroscopy. BMP-6 loaded PEC NP adheres to cell membranes of MMCs and MSCs and activated phosphorylation of Smad 1/5. Osteogenic differentiation (ALP-concentration) is enhanced in MSCs (p < 0.05). All patient samples (10/10) of MMCs show significant induction of apoptosis (median 84%, p < 0.05). Finally, BMP-6/PEC NP are successfully integrated in a commercial hyaluronic acid based hydrogel material revealing MMC death as principal proof for the local treatment of MM induced bone lesions.