Regiocontrolled Annulation of Benzocyclobutenols with Alkynes.

A tandem reaction that involves an unprecedented Rh-catalyzed intramolecular annulation of benzocyclobutenols with alkynes and subsequent ZnCl2-promoted dehydration was developed, offering an efficient approach to 2H-furan-, pyran-, and oxepine-fused naphthalenes. Furthermore, the 2H-furan motif may undergo a ring-opening reaction through Fe-catalyzed reductive C-O bond cleavage. As a consequence, the formal intermolecular annulation of 2-hydroxybenzocyclobutenols with alkynes was realized with complete regioselectivity through a two-step protocol.

WHO grade I meningioma subtypes: MRI features and pathological analysis.

AIMS: WHO grade I meningiomas include several subtypes that differ in terms of surgical planning and prognosis. We aim to analyze the relationship between magnetic resonance imaging (MRI) features and pathological parameters for each WHO grade I meningioma subtype to improve diagnostic value. MATERIALS AND METHODS: Patients with WHO grade I meningiomas underwent pathology pathological examination and surgery at our hospital. MRI findings included signal intensity on T1WI and T2WI and, the enhancement degree in contrast-enhanced, and the degree of peritumoral edema in patients were reviewed. 1H-MRS was performed for the different meningioma subtypes. The correlation between MRI features and pathology was determined using a Kruskal-Wallis H test (P < 0.05). KEY FINDINGS: Angiomatous meningiomas mainly showed a low T1WI signal, a high T2WI signal, a high occurrence rate of peritumoral edema, mainly with moderate or severe peritumoral edema, and homogeneous enhancement. Meningothelial meningiomas mainly showed T1WI and T2WI iso-intense signals, mainly moderate or severe peritumoral edema, and moderate enhancement. Mixed, fibroblastic, and psammomatous meningiomas showed mixed signals, much overlap of the T1WI and T2WI signals, mainly mild or moderate peritumoral edema, and mild or moderate enhancement that could be inhomogeneous. A significant difference was noted in apparent diffusion coefficient (ADC) values and in some 1H-MRS indicators among different meningioma subtypes. SIGNIFICANCE: Angiomatous meningiomas were the most easily identified subtype, followed by meningothelial meningiomas. No obvious difference was observed among the mixed, fibroblastic, and psammomatous meningiomas, but differences were observed between angiomatous and meningothelial meningiomas.

Bu-Shen-Jian-Pi-Yi-Qi Therapy Prevents Alcohol-Induced Osteoporosis in Rats.

Bu-Shen-Jian-Pi-Yi-Qi therapy, which refers to reinforcing kidney, regulating qi, and invigorating spleen, is a traditional Chinese medicine, and we investigated its efficacy in treatment of alcohol-induced osteoporosis and its underlying mechanism. Forty adult male Sprague-Dawley rats were randomly assigned into alcohol-supplemented group, JIAN-GU-LING (JGL) group, calcium D3 + alfacalcidol group, and sham-treated group. Bone mineral density (BMD), bone mineral content (BMC), and bone biomechanical properties were assessed. Biochemical analyses of serum and urine specimens were detected. Reverse transcription-polymerase chain reaction was used to detect the mRNA level of vitamin D receptor (VDR). There were markedly lower bone metabolic markers and biomechanical properties in alcohol-supplemented group compared with sham-treated group (all P < 0.05). BMD, BMC, 25(OH)D3, and 1,25(OH)2D3 were elevated in JGL group relative to calcium D3 + alfacalcidol group (all P < 0.05). U-Ca/Cr and U-P/Cr in JGL group were higher than those in the calcium D3 + alfacalcidol group (all P < 0.05). VDR mRNA level in the JGL group was elevated markedly in comparison with alcohol + calcium D3 + alfacalcidol group (P < 0.05). Based on our results, Bu-Shen-Jian-Pi-Yi-Qi therapy inhibits bone loss, promotes bone formation, and effectively improves bone metabolism in rats with experimental alcoholic osteoporosis. The disease reversal is evidenced by increased BMD and BMC, improved biomechanical properties, elevated VDR mRNA level, enhanced response sensitivity of 1, 25(OH)2D3, and reduced S-Ca/P.

[Vertical Migration Characteristics of Organochlorine Pesticides in Overlying Soil in Karst Terranes and Its Impact on Groundwater].

Five soil profiles and four typical epikarst springs were selected in Nanchuan District, Chongqing Municipality as objects of the study on vertical migration of organochlorine pesticides (OCPs) in the soils and its impact on groundwater. OCPs in soil and epikarst spring water samples were quantitatively analyzed by gas chromatography. The results showed that HCHs and DDTs were detected in all the 5 soil profiles, varying in the range of 0.77-18.3 and 0.34-226 ng · g(-1), and averaging 5.16 and 16 ng · g(-1) in concentration, respectively. The highest concentrations of HCHs and DDTs were found in the subsoil (10-40 cm) in most sampling sites. The detection ratios of HCHs and DDTs in four springs were 100%. The concentrations of HCHs and DDTs fluctuated greatly in epikarst spring water during the one-year observation, and the concentration ranged from 2.09 to 60.1 and from N. D. to 79.8 ng · L(-1), with a mean value of 12 and 9.16 ng · L(-1), respectively. The concentrations of HCHs and DDTs in Hougou, Baishuwan and Lanhuagou spring in rainy season were all. higher than those in dry season in these three epikarst springs. There were no good corresponding relationship between HCHs and DDTs contents in spring water and those in corresponding spring catchment soil. TOC, soil water content, clay content and pH all inhibited the vertical migration of OCPs in Hougou spring catchment, which led to the lowest content of OCPs in spring water, although the OCPs content in Hougou spring catchment soils was the highest in the four spring catchments. However, the four factors didn't inhibit the vertical migration of OCPs in Shuifang spring catchment, which led to higher OCPs content in spring water, although the OCPs content in spring catchment soils was the lowest in the four spring catchments.

Hypermethylation of TGF-ß1 gene promoter in gastric cancer.

AIM: To examine transforming growth factor-ß1 (TGF-ß1) promoter methylation in gastric cancer and to determine if Helicobacter pylori (H. pylori) or interleukin (IL)-1ß could induce TGF-ß1 hypermethylation in vitro. METHODS: We examined the frequency and extent of TGF-ß1 promoter methylation using methylation-specific PCR in the gastric tissues from 47 gastric cancer patients and 39 non-gastric cancer subjects. H. pylori infection was confirmed by a positive result from either a serological test, histological analysis or C¹³ urea breath test. GES-1 and MKN-45 cells co-cultured with H. pylori or treated with IL-1ß for 12, 24 and 48 h in vitro tested the effects of H. pylori or IL-1ß on TGF-ß1. RESULTS: Twenty-four/forty-seven (51%) cases of gastric cancer (GC) tissues showed TGF-ß1 promoter methylation, 15/47 (31.9%) cases of matched non-cancerous gastric mucosa tissues from the GC patients, and 11/39 (28%) case of the normal gastric mucosa tissues from non-GC subjects showed TGF-ß1 promoter methylation (51% vs 28%, P < 0.05). Significantly higher levels of methylation of TGF-ß1 were found in the tumor tissues than in non-tumor tissues from GC patients (0.24 ± 0.06 vs 0.17 ± 0.04, P < 0.05) and normal gastric tissues from non-GC subjects (0.24 ± 0.06 vs 0.15 ± 0.03, P < 0.05). TGF-ß1 methylation was found in 48.3% of H. pylori-positive gastric mucosal tissues whereas only 23.1% of H. pylori-negative gastric mucosal tissues showed TGF-ß1 methylation (48.3% vs 23.1%, P < 0.05). IL-1ß appeared to induce a dose-dependent methylation of TGF-ß1 and the strongest methylation was observed in GES-1 cells treated with 2.5 ng/mL of IL-1ß for 48 h. Further studies showed that pre-treatment of GES-1 cells with 20 ng/mL IL-1RA for 1 h could partially abolish the effect of IL-1ß on TGF-ß1 methylation. Infection of GES-1 cells by H. pylori was not found to induce significant TGF-ß1 promoter methylation. CONCLUSION: Our data revealed that TGF-ß1 promoter is methylated in GC patients. IL-1ß may be an important mediator for H. pylori induced gene methylation during GC development.

[Therapeutic effect of human bone marrow mesenchymal stem cell lysates on rat arthritis induced by collagen].

Our previous work has shown that mesenchymal stem cells (MSC) have little therapeutic effect on rat arthritis induced by collagen. This study was aimed to further investigate whether the MSC lysates exhibit beneficial effects on rheumatoid arthritis. Aliquots of cell lysates from 1×10(7) human bone marrow MSC were intraperitoneally injected into collagen-induced arthritis (CIA) Wistar rats weekly for 4 consecutive weeks. Methotrexate at a dose of 1 mg/kg or normal saline was served as positive and negative controls respectively. On week 4 the symptom scores were recorded and the hind joints of the rats were pathologically examined and X-ray examination was performed. The results showed that on week 4, the symptom scores of the rats that received MSC lysates (6.87 ± 0.83) and MTX (6.44 ± 1.13) were significantly lower than that of control rats (7.33 ± 0.77, P < 0.01). Meanwhile, pathological examination on the involved ankle showed that the synovitis and arthritis scores of MSC lysates and control groups were 2.28 ± 0.48 and 2.28 ± 0.55 respectively, significantly higher than that of MTX treatment rats (0.71 ± 0.48, P < 0.05). However, X-ray examination on the ankle joints showed that the injury score of control rats was 4 ± 0.57, greatly higher than those from MSC lysates (2.71 ± 0.75) and MTX treatment groups (2.57 ± 0.78, P < 0.05 for both groups). It is concluded that MSC lysate infusion has beneficial effects on CIA rat, but the effectiveness seems inferior to MTX.

[Effects of tumor necrosis factor-α on immunoregulatory activities of mesenchymal stem cells in vitro and in vivo].

Mesenchymal stem cells (MSC) are characterized by their potent immuno-regulatory activity, however our previous data have shown that MSC have no therapeutic effects on collagen-induced arthritis (CIA). To further clarify the complexity, the effects of tumor necrosis factor-alpha (TNF-α) on the in vitro and in vivo immunoregulatory activity of MSC were investigated in this study, as TNF-α is recognized as the key factor in the development of rheumatoid arthritis. The nuclear translocation of the inflammation-associated factor NF-κB was observed after human umbilical cord MSC were treated with TNF-α and the cell proliferation status was assessed by MTT test. The inhibitory effects of MSC or TNF-α-treated MSC on the mixed lymphocyte reaction, in which Wistar rat spleen mononuclear cells were served as the responders and the splenocytes from SD rat spleens as the stimulators, were also determined by the MTT test. Further, the therapeutic potentials of MSC or TNF-α-treated MSC were observed in a Wistar rat CIA model. The results showed that NF-κB translocated into the nuclei promptly after TNF-α treatment, though TNF-α had little effect on the MSC proliferation. MSC, whether pre-stimulated by TNF-α or not and when different doses were tested, exhibited obviously inhibitory effects on the proliferation of the lymphocytes (P < 0.001 for all groups tested), while MSC-treated by TNF-α displayed more potent suppression especially when low-density were used. Unexpectedly, the infiltration of inflammatory cells into the involved knees was aggravated by cell treatment and the pathological scores were significantly higher than those of controls (P < 0.05). It is concluded that the TNF-α exhibits different effects on immune regulation activity of MSC, and its underlying mechanism needs to further investigate.

Microvesicles derived from human umbilical cord mesenchymal stem cells stimulated by hypoxia promote angiogenesis both in vitro and in vivo.

Although mesenchymal stem cells (MSCs) have been increasingly trialed to treat a variety of diseases, the underlying mechanisms remain still elusive. In this study, human umbilical cord (UC)-derived MSCs were stimulated by hypoxia, and the membrane microvesicles (MVs) in the supernatants were collected by ultracentrifugation, observed under an electron microscope, and the origin was identified with the flow cytometric technique. The results showed that upon hypoxic stimulus, MSCs released a large quantity of MVs of ~100 nm in diameter. The MVs were phenotypically similar to the parent MSCs, except that the majority of them were negative for the receptor of platelet-derived growth factor. DiI-labeling assay revealed that MSC-MVs could be internalized into human UC endothelial cells (UC-ECs) within 8 h after they were added into the culture medium. Carboxyfluorescein succinimidyl ester-labeling technique and MTT test showed that MSC-MVs promoted the proliferation of UC-ECs in a dose-dependent manner. Further, MVs could enhance in vitro capillary network formation of UC-ECs in a Matrigel matrix. In a rat hindlimb ischemia model, both MSCs and MSC-MVs were shown to improve significantly the blood flow recovery compared with the control medium (P<0.0001), as assessed by laser Doppler imaging analysis. These data indicate that MV releasing is one of the major mechanisms underlying the effectiveness of MSC therapy by promoting angiogenesis.

A new acylated flavonoid glycoside from the flowers of Camellia nitidissima and its effect on the induction of apoptosis in human lymphoma U937 cells.

From the EtOH extract of the flowers of Camellia nitidissima Chi, a new acylated flavonoid glycoside, quercetin 7-O-(6"-O-E-caffeoyl)-ß-D-glucopyranoside (1), has been isolated, together with three known flavonoids: quercetin (2), quercetin 3-O-ß-D-glucopyranoside (3), and quercetin 7-O-ß-D-glucopyranoside (4). Their structures were elucidated on the basis of spectroscopic analysis. Compound 1 was shown to inhibit proliferation and to induce apoptosis of human lymphoma U937 cells.

[Human bone marrow mesenchymal stem cells have little preventive or therapeutic effect on rat arthritis induced by collagen].

The aim of this study was to investigate if transfusion of mesenchymal stem cells (MSC) could exhibit beneficial effects on rheumatoid arthritis. Human bone marrow MSC were intraperitoneally injected into Wistar rats with collagen-induced arthritis at a dose of 10(7) on the next day (preventive group) or 2 weeks (treatment group) after collagen II induction, once a week for 2 weeks (preventive group) or 4 weeks (treatment group). The control group was given normal saline (NS) at corresponding time. The symptom scorings were documented weekly from the second week of the induction. On week 6, the hind joints of the rats were pathologically examined and the activation status of splenocytes was analyzed by flow cytometry. The results showed that all the rats developed arthritis and subsequent joint abnormality. On the sixth week, symptom scores of the rats that received MSC preventive (9.5 ± 0.5) or therapeutic (9.4 ± 0.6) infusions had no significant difference between each other, but were significantly greater than those of the NS controls (7.6 ± 0.6, P < 0.05). Consistently, pathological examination on the involved knees showed that the synovitis and arthritis scorings of MSC treated rats were greatly elevated compared with NS controls. Furthermore, the ratios of CD86(+) cells in the spleens of MSC prevention, MSC treatment and NS control groups were (4.16 ± 1.48), (4.06 ± 1.97) and (4.15 ± 2.04) respectively, while those of CD11b/c(+)CD86(+) cells were (1.04 ± 0.68), (0.95 ± 0.56) and (0.98 ± 0.44), all of which were significantly higher than those of healthy controls [(0.97 ± 0.18) and (0.30 ± 0.17), P < 0.05 for both parameters]. It is concluded that MSC infusion has little beneficial effects on collagen-induced arthritis in rats, conversely, MSC therapy aggravated the damage of the involved joints, its underlying mechanisms need to be further investigated.

Three new secolignan glycosides from Urtica fissa E. Pritz.

Three new secolignan glycosides {3,4-trans-4-[bis(3,4-dimethoxyphenyl)methyl]-2-oxotetrahydrafuran-3-yl}methyl-O-ß-glucopyranoside (1), {3,4-trans-4-[(3-methoxy-4-hydroxyphenyl)(3,4-dimethoxyphenyl)methyl]-2-oxotetrahydrafuran-3-yl}methyl-O-ß-glucopyranoside (2) and {3,4-cis-4-[(3-methoxy-4-hydroxyphenyl)(3,4-dimethoxyphenyl)methyl]-2-oxotetrahydrafuran-3-yl}methyl-O-ß-glucopyranoside (3) were isolated from the roots of Urtica fissa E. Pritz. Their structures were identified by spectral methods including 1D NMR, 2D NMR and HR-EI-MS.

Two new 3-oxo-α-ionol glucosides from Urtica laetevirens Maxim.

Two new 3-oxo-α-ionol glucoside isomers, (6R,9R)-3-oxo-α-ionol-9-O-ß-D-glucopyranosyl (1 → 2)-ß-D-glucopyranoside (1) and (6S,9R)-3-oxo-α-ionol-9-O-ß-D-glucopyranosyl (1 → 2)-ß-D-glucopyranoside (2) were isolated from the aerial parts of Urtica laetevirens Maxim. Their structures, including stereochemistry, were established by spectral analyses (HR-ESI-MS, NMR and CD). Also, 3-oxo-α-ionol glucosides were isolated from Urtica species for the first time.

Lignan and flavonoid glycosides from Urtica laetevirens Maxim.

A new compound named pinoresinol 4-O-alpha-L-rhamnopyranosyl (1-->2)-beta-D-glucopyranoside (1) together with six known compounds, isolariciresinol 9-O-beta-D-glucopyranoside (2), apigenin 6,8-di-C-beta-D-glucopyranoside (3), luteolin 7-O-neohesperidoside (4), luteolin 7-O-beta-D-glucopyranoside (5), 5-methoxyluteolin 7-O-beta-D-glucopyranoside (6), and rutin (7), were isolated from the aerial parts of Urtica laetevirens Maxim. All of the above compounds were isolated from this plant for the first time.

New chemical constituents of roots of Urtica triangularis HAND-MASS.

Studies on the chemical constituents of roots of Urtica triangularis HAND-MASS have led to the isolation of four new compounds. The structures, including the absolute configurations, of these constituents have been elucidated through spectral studies including (1)H-NMR, (13)C-NMR, 2D-NMR experiments (heteronuclear single-quantum coherence, heteronuclear multiple bonding connectivity and nuclear Overhauser effect spectroscopy), high resolution mass spectroscopy (HR-MS) and circular dichroism as (-)-4-methoxy-8'-acetyl olivil, (-)-4-methoxy-8'-acetyl olivil-4-O-alpha-arabinopyronosyl-(1-->6)-beta-glucopyranoside, (-)-olivil-9-O-beta-glucopyranoside and cyclo-olivil-9-O-beta-glucopyranoside.

[Studies on phenolic compounds from Stellera chamaejasme].

OBJECTIVE: To study the chemical constituents of the roots of Stellera chamaejasme. METHOD: The chemical constituents were separated and purified by chromatographic method after solvent extraction and were identified by spectroscopic analysis. RESULT: Two phenolic compounds were obtained and determined as stelleranol (1) and umbelliferone-7-O-glucoside (2). CONCLUSION: Compound 1 was a new compound, and compound 2 was isolated from this plant for the first time.

[Study on the theraputic effect of plants of Camellia genus on osteoporosis].

OBJECTIVE: To observe anti-osteoporotic effect of Plants of Camelia genus induced by retinoic acid in rats, in adqulis crude drug dosage, and to compare activities of them. METHODS: Extracts of Camellia japonica and Camellia oleifera were given to rats with osteoporosis induced by retinoic acid, some indexes of rats were measured and compared with those of modle group, control group and positive control group, including weight/length (G/L), bone density, earth and calcium content of bone, morphology change and serum calcium, tartrate-resistant acid phosphatase and alkaline phosphatase. We also compared effective intensity between different groups in adqulis crude drug dosage. RESULTS: Ethanol extracts of seed from Camellia japonica 0.51 g/kg could markedly enhance weight/length (G/L), bone density of femur, serum calcium and alkaline phosphatase level, with the decreasing of anti-tartaric acid tartrate-resistant acid phosphatase level. Meanwhile, they were accompanied by a significant increase of morphologic observed sclerotomal cell and by a significant decrease of osteoclast. Moreover, it was observed greatly that bone trabecula transformateed to normal morphous. The results of this study indicated that effects of ethanol extracts of seed from Camellia japonica on anti-osteoporosis with retinoic acid were the strongest. Ethanol extracts of seed from Camellia japonica , ethanol extracts of leaves from Camellia Oleifera, and aqueous extracts of leaves from Camellia Oleifera were stronger than positive control drug. The other extracts didnt show obvious anti-osteoporotic effects. Eventually the strength order of each group on anti-osteoporosis was as following: ethanol extracts of seed from Camellia japonica > ethanol extracts of leaves from Camellia Oleifera > aqueous extracts of leaves from Camellia Oleifera > aqueous extracts of seed from Camellia Oleifera > positive control drug > aqueous extracts of seed from Camellia Japonica. CONCLUSION: Plants of Camellia genus have different degree anti-osteoporosis effect, which can offer significant theory basis for progressive investigation and exploitation of them.

Sinapic acid derivatives from the seeds of Raphanus nussatirus L.

A new disulfide glycoside, raphthioglucoside (1), and a new sinapic acid derivative, sinapic acid 5-hydroxymethylfurfural ester (2), together with sinapic acid (3) have been isolated from the seeds of Raphanus nussatirus L. The structures of compounds 1-3 were determined based on chemical analysis and spectroscopic methods (UV, 1D and 2D NMR, HRFABMS, HREIMS and elemental analysis).