"Three-in-One" Structural-Building-Mode-Based Ti16-Type Titanium Oxo Cluster Entirely Protected by the Ligands Benzoate and Salicylhydroxamate.

Titanium oxo clusters (TOCs) with accurate molecular structures have potential applications in photocatalysis, such as photocatalytic degradation, hydrogen production, and water oxidation. The hydrolytic stability and light absorption ability of TOCs have important impacts on photocatalysis, where the selection of peripheral organic ligands plays a significant role. In this regard, salicylhydroxamic acid (abbreviated as H3L) attracts our attention, acting as a ligand for its multidentate and dye-functional features, which can increase the hydrolytic stability and broaden light absorption for TOCs. Herein, two TOCs were solvothermally synthesized and structurally characterized using H3L, formulated as [Ti8(µ2-O)2(µ3-O)2(OiPr)12(L)4]·2CH3CN (1) and [Ti16(µ2-O)10(µ3-O)4(PhCOO)14(L)6(HL)2]·4CH3CN·2iPrOH (2). Complex 2 was obtained by adding excessive benzoic acid over the reaction system of 1, resulting in enhanced hydrolytic stability via the replacement of all alkoxy ligands by multidentate ligands for protection. Interestingly, for the first time, the "three-in-one" structural building mode with {Ti6} + {Ti4} + {Ti6} by the common subunits in 2 was observed among all reported TOCs. Moreover, complex 2 can strongly absorb visible light reaching up to 700 nm and exhibit obvious activity for the photodegradation of methyl orange.

The microstructures and mechanical properties of nanocrystalline Li2SiO3: molecular dynamics simulations.

The microstructures and mechanical properties of nanocrystalline Li2SiO3 have been investigated via molecular dynamics calculations. The results indicate that the mean atomic mass densities of nanostructured Li2SiO3 with different mean grain size are slightly lower than that of ordinary crystal Li2SiO3. Interestingly, a significant anti-Hall-Petch effect between yield stress and average grain size is observed in the tensile deformation simulation of the samples. In fact, the curve changes linearly until the strain reaches approximately 0.016-0.018. Next, when the strain is between 0.27 and 0.38, the stress of the sample has a small peak in the plastic flow region. Then, all the samples will begin to fracture at a strain of about 0.39-0.41. Moreover, due to the influence of grain boundary sliding and grain rotation, there are a few dislocations in the samples with the small average grain sizes, highlighting the strong influence of the mechanical properties on the overall tensile deformation of the samples.

Exploring the differential mechanisms of carotenoid biosynthesis in the yellow peel and red flesh of papaya.

BACKGROUND: Red-fleshed papaya is a good material to study the different carotenoids accumulation mechanism in the peel and flesh. Although the peel and flesh of papaya closely integrated into one body, the flesh coloration changing from white to red, while the exocarp coloration changing from green to yellow. In this study, the major carotenoids accumulation and the expression patterns of key carotenoid biosynthesis pathway genes in the process of papaya fruit ripening were studied, and the carotenoid biosynthetic pathways in the yellow peel and red flesh of papaya were investigated. RESULTS: The carotenoid composition in papaya flesh and peel were different. The major carotenoids were lutein and ß-carotene in the peel, while lycopene in the flesh. The accumulation of carotenoids, including lycopene, ß-carotene, and ß-cryptoxanthin were considered to cause the orange-red color of papaya cv. 'Daqing No.10' flesh. The color of peel changed from green to yellow because of the fast degradation of chlorophyll and the appearance of carotenoids such as lutein and ß-carotene. Thirteen genes that encode enzymes in the carotenoid biosynthetic pathway were detected in papaya fruit transcriptome: two phytoene synthase (PSY1, PSY2), two phytoene desaturase (PDS1, PDS2), one ζ-carotene desaturase (ZDS), four lycopene cyclase (CYCB, LCYB1, LCYB2, LCYE), one ß-carotene hydroxylase (CHYB), one carotene ε-monooxygenase (LUT1), one violaxanthin de-epoxidase (VDE), and one zeaxanthin epoxidase (ZEP). The results of RNA-Seq and RT-qPCR showed the expression of carotenoid biosynthetic pathway genes was consistent with the change of carotenoid content. Carotenoid biosynthetic pathways in the yellow peel and red flesh of papaya were analysed based on the major carotenoids accumulation and the expression patterns of key carotenoid biosynthesis pathway genes. There was only a ß-branch of carotenoid biosynthesis in the flesh of papaya, while there were both α- and ß-branch of carotenoid biosynthesis in papaya peel. In the process of papaya fruit ripening, the α-branch was inhibited and the ß-branch was enhanced in the peel. CONCLUSIONS: The differential carotenoid accumulation and biosynthesis pathway genes expression in peel and flesh, lay a foundation for further study and provide further insights to control fruit color and improve fruit quality and appearance.

Syntheses, crystal-solution structures and magnetic properties of a series of decanuclear heterometallic [LnCoCo] (Ln = Eu, Gd, Tb, Dy) clusters.

Four unprecedented decanuclear heterometallic [Ln2CoII4CoIII4] clusters based on a diethanolamine ligand (H2dea), namely [Eu2CoII4CoIII4(dea)8(HCOO)4(OH)2(Cl)2(CH3OH)2]Cl2·4CH3OH·2H2O (1), [Gd2CoII4CoIII4(dea)8(HCOO)4(OH)2(Cl)2(CH3OH)2]Cl2·4CH3OH·2H2O (2), [Tb2CoII4CoIII4(dea)8(HCOO)4(OH)2(Cl)2(CH3OH)2]Cl2·2CH3OH·4H2O (3) and [Dy2CoII4CoIII4(dea)8(HCOO)4(OH)2(Cl)2(CH3OH)2]Cl2·2CH3OH·4H2O (4) were synthesized through a facile solution method. Single-crystal X-ray diffraction analyses reveal that complexes 1-4 consist of a [Ln2CoII4CoIII4] core, which is constructed by bridging a quasi-double cuboidal [Ln2CoII2CoIII2] core with two [CoIICoIII] units. Electrospray ionization mass spectrometry (ESI-MS) using methanol solution reveals that complexes 1-4 are stable in the solution, and the clusters undergo three different substitution reactions (Cl- replaced by OH-, OH- replaced by CH3O- and HCOO- replaced by OH-/CH3O-) at the same time in the ionization state. Magnetic susceptibilities reveal ferromagnetic couplings within complexes 3 and 4, and the magnetocaloric effect (MCE) for 2 was also evaluated and the maximum entropy change (-ΔSm) value reaches 16.3 J kg-1 K-1 at about 3 K and 5 T.

Isolation of ripening-related genes from ethylene/1-MCP treated papaya through RNA-seq.

BACKGROUND: Since papaya is a typical climacteric fruit, exogenous ethylene (ETH) applications can induce premature and quicker ripening, while 1-methylcyclopropene (1-MCP) slows down the ripening processes. Differential gene expression in ETH or 1-MCP-treated papaya fruits accounts for the ripening processes. To isolate the key ripening-related genes and better understand fruit ripening mechanisms, transcriptomes of ETH or 1-MCP-treated, and non-treated (Control Group, CG) papaya fruits were sequenced using Illumina Hiseq2500. RESULTS: A total of 18,648 (1-MCP), 19,093 (CG), and 15,321 (ETH) genes were detected, with the genes detected in the ETH-treatment being the least. This suggests that ETH may inhibit the expression of some genes. Based on the differential gene expression (DGE) and the Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment, 53 fruit ripening-related genes were selected: 20 cell wall-related genes, 18 chlorophyll and carotenoid metabolism-related genes, four proteinases and their inhibitors, six plant hormone signal transduction pathway genes, four transcription factors, and one senescence-associated gene. Reverse transcription quantitative PCR (RT-qPCR) analyses confirmed the results of RNA-seq and verified that the expression pattern of six genes is consistent with the fruit senescence process. Based on the expression profiling of genes in carbohydrate metabolic process, chlorophyll metabolism pathway, and carotenoid metabolism pathway, the mechanism of pulp softening and coloration of papaya was deduced and discussed. We illustrate that papaya fruit softening is a complex process with significant cell wall hydrolases, such as pectinases, cellulases, and hemicellulases involved in the process. Exogenous ethylene accelerates the coloration of papaya changing from green to yellow. This is likely due to the inhibition of chlorophyll biosynthesis and the α-branch of carotenoid metabolism. Chy-b may play an important role in the yellow color of papaya fruit. CONCLUSIONS: Comparing the differential gene expression in ETH/1-MCP-treated papaya using RNA-seq is a sound approach to isolate ripening-related genes. The results of this study can improve our understanding of papaya fruit ripening molecular mechanism and reveal candidate fruit ripening-related genes for further research.

[Effect of stiletto needle intervention combined with massage on dysfunction and pain of knee-joints in patients with knee osteoarthrosis].

OBJECTIVE: To observe the effectiveness of stiletto needle stimulation combined with massage in the treatment of dysfunction and pain of knee joints in knee osteoarthrosis (KOA) patients. METHODS: One hundred KOA outpatients and inpatients were randomly and equally divided into treatment and control groups. Patients of the treatment group were treated by using stiletto needle stimulation of 5-10 tender-points (at the medial collateral ligament, internal condyle of femur, medial condyle of femur, etc.) in combination with massage on the bilateral sides of the patella ligament, digital pressing of Liangqiu (ST 34), Xuehai (SP 10), Neixiyan (EX-LE 4), Weizhong (BL 40), etc. Patients of the control group were treated by using massage therapy alone (the same to those mentioned above). Elasticity of the soft tissue[displacement value under 500 g pressure exerted on the tender-point surface; the banana area, i. e. , the absorbed energy of the soft tissue] was measured by using Soft-tissue Tension Detector. Dysfunction scores of the knee-joint (cure:91 -99 points; marked improvement: 75-90 points; improvement: 60- 74 points; invalid: no improvement) were assessed according to Jiang's method, and the therapeutic effect was evaluated in the light of "Criteria for Diagnosis and Therapeutic Effect Assessment of Illnesses or Clinical Conditions of Chinese Medicine" issued in 1994 in China. RESULTS: Comparison between pre- and post-treatment in the same one group showed that the displacement values and scores of pain, joint-movement and malformation, and total scores were increased significantly and the banana area reduced considerably in these two groups after the treatment (P < 0. 05), and the effects of the treatment group were apparently superior to those of the control group (P < 0. 05). Of the two 50 cases in the control and treatment groups, 10 (20%) and 33 (66%) had marked improvement, 33 (66%) and 14 (28%) were improved, and 7 (14%) and 3 (6%) invalid, with the effective rates being 86% and 94% , respectively. The markedly effective rate of the treatment group was apparently higher than that of the control group (P< 0. 05). No significant differences were found between the two groups in the scores of initiative extension range, walking abi-lity and daily life activities (P>0.05). CONCLUSION: Stiletto needle intervention in combination with massage can effectively relieve dysfunction and pain of the knee joint in KOA patients.

[Treatment of lumbar disc herniation combine with buttock tender node with Pizhen].

OBJECTIVE: To observe the therapeutic effects of Pizhen in treating lumbar disc herniation combined with buttock tender node. METHODS: From August 2009 to February 2010,83 patients (29 males and 54 females) with lumbar disc herniation combined with buttock tender node were randomly divided into the Pizhen group and acupuncture group. Pizhen group were treated with Pizhen manipulation, inserting needle by vertical prick with quacking inserting and quick withdrawing the needle, no rotating and the depth was through the surface of fascia, two times as a course of treatment; acupuncture group were treated with acupuncture, inserting Ashi-point, retaining the needle 20 min, ten times as a course of treatment. VAS scoring at the end of treatment and B ultrasonic image at 3d after treatment was carried out to observe the therapeutic effects. RESULTS: B ultrasonic image of buttock tender node showed inflammation reaction or ellipse. The width of the inflammation reaction decreased after treatment, but there has no statistical significance (P=0.635). There was no significant difference between two groups (P=0.813). CONCLUSION: Pizhen manipulation is better than acupuncture. B ultrasonic image gives morphological performance of buttock tender node, the content is inflammatory infiltrates. B ultrasound has certainly significance in diagnosing, treating and evaluating the clinical effect of Pizhen manipulation on treating buttock tender node.

[Effect of Chinese medicinal massage on endocrinal function in women with climacteric syndrome].

OBJECTIVE: To explore the therapeutic effect of Chinese medicinal massage with nourishing-Shen and activating-blood manipulation in treating women with climacteric syndrome and its influence on endocrinal function. METHODS: Sixty patients were assigned to two groups, the 40 patients in the treated group were treated by Chinese medicinal massage for 20 min once every other day; the 20 patients in the control group were treated by hormone replacement therapy with Premarin 0.625 g, once daily by oral taking. The therapeutic efficacy was evaluated after two-month treatment by changes of serum levels of estradiol (E2), follicular stimulating hormone (FSH), luteinizing hormone (LH), and Kupperman index before and after treatment. RESULTS: Kupperman index showed that the total symptom score in the treated group was improved from 30.71 +/- 8.43 scores before treatment to 8.21 +/- 5.14 scores after treatment, with a decrement of 22.50 +/- 8.14 scores, which was higher than that in the control group, from 24.32 +/- 5.44 scores to 5.92 +/- 3.58 scores, with a decrement of 18.40 +/- 4.50 scores, the difference between them was statistically significant (t = 2.52, P = 0.014). The serum level of E2 increased in both groups significantly after treatment, from 20.23 +/- 20.78 ng/L to 54.34 +/- 24.26 ng/L in the treated group (t= -2.73, P = 0.006), and from 16.15 +/- 24.40 ng/L to 40.61 +/- 81.54 ng/L in the control group (t = -1.72, P = 0.086), but the difference between groups was statistical insignificant (t= -1.120, P = 0.263). As for levels of FSH and LH, their decrements in the control group (13.16 +/- 11.29 mlU/mL and 10.37 +/- 9.21 mlU/mL) were larger than those in the treated group (4.92 +/- 4.26 mlU/mL and 0.17 +/- 2.42 mlU/mL), respectively (t = - 2.49, P = 0.013; t = - 2.38, P = 0.017). CONCLUSION: Chinese medicinal massage manipulation could improve the Kupperman index of all the 13 symptoms in women with climacteric syndrome, and increase the E2 level in serum.

Risk factors for HPV infection and cervical cancer among unscreened women in a high-risk rural area of China.

We report a prevalence rate of 23.6% human papillomavirus (HPV) infection with oncogenic subtypes and 2.4% cervical intraepithelial neoplasia (CIN) III and cervical cancer (CC) in rural middle-aged women in 2 counties with the highest CC mortality in Shanxi Province, China. We examined the association of risk factors to HPV infection and to CIN III and CC in 8,798 unscreened women aged 35-50 years. Multivariate odds ratios (OR) and 95% confidence intervals (CI) for each endpoint were obtained for risk factors after adjustment for covariates. The OR of oncogenic HPV were: 1.41 (95% CI = 1.25-1.60) and 1.42 (95% CI = 1.24-1.61) for the participant and her husband having multiple sexual partners, respectively; 1.67 (95% CI = 1.37-2.04), 1.15 (95% CI = 1.04-1.26), and 0.82 (95% CI = 0.72-0.94) for ever (vs. never) diagnosed with tuberculosis, cervical inflammation and vaginal trichomoniasis, respectively; while bathing in a public (v. private) facility had an OR of 1.23 (95% CI =1.11-1.35). Seasonal fluctuations in HPV infection, but not CC, appeared in Xiangyuan County, with OR of 1.23 (95% CI = 1.14-1.33) and 1.51 (95% CI = 1.35-1.67) in Spring and Winter compared to Summer, respectively. The OR of CIN III and CC in the HPV positives were: 2.03 (95% CI = 1.63-2.53) for ages > or =45 years (vs. <40); and 4.01 (95% CI = 1.46-11.0) for > or =3 (vs. no) home births. Public health interventions and control strategies for improving the reproductive health of women in these rural populations need to be developed to reduce risk of HPV and subsequent CC.

[Population-based study of human papillomavirus infection in high-risk area for cervical cancer in Shanxi Province, China].

OBJECTIVES: To investigate the prevalence of oncogenic type of human papillomavirus (HPV) infection and identify the high risk population for conducting immuno/chemoprevention of cervical cancer. METHODS: All married women aged 30 to 50 with no history of hysterectomy, pelvic radiation and non-pregnant from certain villages of Xiangyuan and Yangcheng County were invited. This study was conducted through two phases. In phase one, subjects sampled the vaginal secretions using the collectors after signing the informed consent. And physicians sampled exfoliated cells from cervix in the phase two. All the specimens were tested with the Hybrid Capture 2 test. The data was managed and analyzed by VFP and SPSS software. RESULTS: There were 9,683 women participated in this study. Local women welcomed this study and population compliance rate was 75.4%. In tested population, we found 2,666 subjects of HPV DNA positive and HPV prevalence was 27.5%. The rates of different age group were 24.5% (30-34 yrs), 27.4% (35-39 yrs), 28.2% (40-44 yrs), 27.4% (45-50 yrs) respectively and had no significant differences (P = 0.604). The rates were slightly increased with the higher education level and had no differences (P = 0.106). The rate in mountain areas was higher than that in half-mountain areas (P = 0.001). CONCLUSIONS: The prevalence of HPV infection is indeed high in this region. Local women and health professionals welcome the activities of cervical cancer screening and prevention. It is an emergent task to improve their sanitary condition and prevent them from cervical cancer in these women. A women health cohort is established successfully among high HPV exposed women in rural China. The extensive biologic specimen repository has been successfully established to simultaneously study the etiology, early detection, and immuno/chemoprevention of cervical cancer.