Direct observation of the intermediate in an ultrafast isomerization.

Using a combination of two-dimensional infrared (2D IR) and variable temperature Fourier transform infrared (FTIR) spectroscopies the rapid structural isomerization of a five-coordinate ruthenium complex is investigated. In methylene chloride, three exchanging isomers were observed: (1) square pyramidal equatorial, (1); (2) trigonal bipyramidal, (0); and (3) square pyramidal apical, (2). Exchange between 1 and 0 was found to be an endergonic process (ΔH = 0.84 (0.08) kcal mol-1, ΔS = 0.6 (0.4) eu) with an isomerization time constant of 4.3 (1.5) picoseconds (ps, 10-12 s). Exchange between 0 and 2 however was found to be exergonic (ΔH = -2.18 (0.06) kcal mol-1, ΔS = -5.3 (0.3) eu) and rate limiting with an isomerization time constant of 6.3 (1.6) ps. The trigonal bipyramidal complex was found to be an intermediate, with an activation barrier of 2.2 (0.2) kcal mol-1 and 2.4 (0.2) kcal mol-1 relative to the equatorial and apical square pyramidal isomers respectively. This study provides direct validation of the mechanism of Berry pseudorotation - the pairwise exchange of ligands in a five-coordinate complex - a process that was first described over fifty years ago. This study also clearly demonstrates that the rate of pseudorotation approaches the frequency of molecular vibrations

Revealing Hidden Vibration Polariton Interactions by 2D IR Spectroscopy

We report the first experimental two-dimensional infrared (2D IR) spectra of novel molecular photonic excitations - vibrational-polaritons. The application of advanced 2D IR spectroscopy onto novel vibrational-polariton challenges and advances our understanding in both fields. From spectroscopy aspect, 2D IR spectra of polaritons differ drastically from free uncoupled molecules; from vibrational-polariton aspects, 2D IR uniquely resolves hybrid light-matter polariton excitations and unexpected dark states in a state-selective manner and revealed hidden interactions between them. Moreover, 2D IR signals highlight the role of vibrational anharmonicities in generating non-linear signals. To further advance our knowledge on 2D IR of vibrational polaritons, we develop a new quantum-mechanical model incorporating the effects of both nuclear and electrical anharmonicities on vibrational-polaritons and their 2D IR signals. This work reveals polariton physics that is difficult or impossible to probe with traditional linear spectroscopy and lays the foundation for investigating new non-linear optics and chemistry of molecular vibrational-polaritons

A development cooperation Erasmus Mundus partnership for capacity building in earthquake mitigation science and higher education

Successful practices have shown that a community’s capacity to manage and reduce its seismic risk relies on capitalization on policies, on technology and research results. An important role is played by education, than contribute to strengthening technical curricula of future practitioners and researchers through university and higher education programs. EUNICE is a European Commission funded higher education partnership for international development cooperation with the objective to build capacity of individuals who will operate at institutions located in seismic prone Asian Countries. The project involves five European Universities, eight Asian universities and four associations and NGOs active in advanced research on seismic mitigation, disaster risk management and international development. The project consists of a comprehensive mobility scheme open to nationals from Afghanistan, Bangladesh, China, Nepal, Pakistan, Thailand, Bhutan, India, Indonesia, Malaysia, Maldives, North Korea, Philippines, and Sri Lanka who plan to enroll in school or conduct research at one of five European partner universities in Italy, Greece and Portugal. During the 2010-14 time span a total number of 104 mobilities are being involved in scientific activities at the undergraduate, masters, PhD, postdoctoral and academic-staff exchange levels. Researchers, future policymakers and practitioners build up their curricula over a range of disciplines in the fields of earthquake engineering, seismology, disaster risk management and urban planning

EU-NICE, Eurasian University Network for International Cooperation in Earthquakes

Despite the remarkable scientific advancements of earthquake engineering and seismology in many countries, seismic risk is still growing at a high rate in the world’s most vulnerable communities. Successful practices have shown that a community’s capacity to manage and reduce its seismic risk relies on capitalization on policies, on technology and research results. An important role is played by education, than contribute to strengthening technical curricula of future practitioners and researchers through university and higher education programmes. In recent years an increasing number of initiatives have been launched in this field at the international and global cooperation level. Cooperative international academic research and training is key to reducing the gap between advanced and more vulnerable regions. EU-NICE is a European Commission funded higher education partnership for international development cooperation with the objective to build capacity of individuals who will operate at institutions located in seismic prone Asian Countries. The project involves five European Universities, eight Asian universities and four associations and NGOs active in advanced research on seismic mitigation, disaster risk management and international development. The project consists of a comprehensive mobility scheme open to nationals from Afghanistan, Bangladesh, China, Nepal, Pakistan, Thailand, Bhutan, India, Indonesia, Malaysia, Maldives, North Korea, Philippines, and Sri Lanka who plan to enrol in school or conduct research at one of five European partner universities in Italy, Greece and Portugal. During the 2010-14 time span a total number of 104 mobilities are being involved in scientific activities at the undergraduate, masters, PhD, postdoctoral and academic-staff exchange levels. This high number of mobilities and activities is selected and designed so as to produce an overall increase of knowledge that can result in an impact on earthquake mitigation. Researchers, future policymakers and practitioners build up their curricula over a range of disciplines in the fields of engineering, seismology, disaster risk management and urban planning. Specific educational and research activities focus on earthquake risk mitigation related topics such as: anti-seismic structural design, structural engineering, advanced computer structural collapse analysis, seismology, experimental laboratory studies, international and development issues in disaster risk management, social-economical impact studies, international relations and conflict resolution

Induced Pluripotent Stem Cells-Derived Mesenchymal Stem Cells Attenuate Cigarette Smoke-Induced Cardiac Remodeling and Dysfunction

The strong relationship between cigarette smoking and cardiovascular disease (CVD) has been well-documented, but the mechanisms by which smoking increases CVD risk appear to be multifactorial and incompletely understood. Mesenchymal stem cells (MSCs) are regarded as an important candidate for cell-based therapy in CVD. We hypothesized that MSCs derived from induced pluripotent stem cell (iPSC-MSCs) or bone marrow (BM-MSCs) might alleviate cigarette smoke (CS)-induced cardiac injury. This study aimed to investigate the effects of BM-MSCs or iPSC-MSCs on CS-induced changes in serum and cardiac lipid profiles, oxidative stress and inflammation as well as cardiac function in a rat model of passive smoking. Male Sprague-Dawley rats were randomly selected for exposure to either sham air (SA) as control or 4% CS for 1 h per day for 56 days. On day 29 and 43, human adult BM-MSCs, iPSC-MSCs or PBS were administered intravenously to CS-exposed rats. Results from echocardiography, serum and cardiac lipid profiles, cardiac antioxidant capacity, cardiac pro- and anti-inflammatory cytokines and cardiac morphological changes were evaluated at the end of treatment. iPSC-MSC-treated group showed a greater effect in the improvement of CS-induced cardiac dysfunction over BM-MSCs-treated group as shown by increased percentage left ventricular ejection fraction and percentage fractional shortening, in line with the greater reversal of cardiac lipid abnormality. In addition, iPSC-MSCs administration attenuated CS-induced elevation of cardiac pro-inflammatory cytokines as well as restoration of anti-inflammatory cytokines and anti-oxidative markers, leading to ameliorate cardiac morphological abnormalities. These data suggest that iPSC-MSCs on one hand may restore CS-induced cardiac lipid abnormality and on the other hand may attenuate cardiac oxidative stress and inflammation via inhibition of CS-induced NF-κB activation, leading to improvement of cardiac remodeling and dysfunction. Thus, iPSC-MSCs may be a promising candidate in cell-based therapy to prevent cardiac complications in smokers

In Vivo Delivery of Gremlin siRNA Plasmid Reveals Therapeutic Potential against Diabetic Nephropathy by Recovering Bone Morphogenetic Protein-7

Diabetic nephropathy is a complex and poorly understood disease process, and our current treatment options are limited. It remains critical, then, to identify novel therapeutic targets. Recently, a developmental protein and one of the bone morphogenetic protein antagonists, Gremlin, has emerged as a novel modulator of diabetic nephropathy. The high expression and strong co-localization with transforming growth factor- β1 in diabetic kidneys suggests a role for Gremlin in the pathogenesis of diabetic nephropathy. We have constructed a gremlin siRNA plasmid and have examined the effect of Gremlin inhibition on the progression of diabetic nephropathy in a mouse model. CD-1 mice underwent uninephrectomy and STZ treatment prior to receiving weekly injections of the plasmid. Inhibition of Gremlin alleviated proteinuria and renal collagen IV accumulation 12 weeks after the STZ injection and inhibited renal cell proliferation and apoptosis. In vitro experiments, using mouse mesangial cells, revealed that the transfect ion of gremlin siRNA plasmid reversed high glucose induced abnormalities, such as increased cell proliferation and apoptosis and increased collagen IV production. The decreased matrix metalloprotease level was partially normalized by transfection with gremlin siRNA plasmid. Additionally, we observed recovery of bone morphogenetic protein-7 signaling activity, evidenced by increases in phosphorylated Smad 5 protein levels. We conclude that inhibition of Gremlin exerts beneficial effects on the diabetic kidney mainly through maintenance of BMP-7 activity and that Gremlin may serve as a novel therapeutic target in the management of diabetic nephropathy

Pregnancy length and health in giant pandas: what can metabolic and urinary endocrine markers unveil?

Mature female giant pandas usually ovulate once a year. This is followed by an obligatory luteal phase, consisting of a long-lasting corpus luteum dormancy phase (CLD; primary increase in progestogens) and a much shorter active luteal phase (AL; secondary increase in progestogens). Varying duration of both the dormant (embryonic diapause) and AL (post-embryo reactivation) phases has hampered unambiguous pregnancy length determination in giant pandas until today. Additionally, progestogen profiles have been considered not to differ between pregnant and pseudopregnant cycles. Only ceruloplasmin, 13,14-dihydro-15-keto-PGF2α (PGFM) and – more recently – estrogens have been assigned diagnostic power so far. Our study investigated the competence of metabolic (fecal output) and Urinary Specific Gravity (USpG)-normalized urinary endocrine (progestogens, PGFM, glucocorticoids (GCM) and ceruloplasmin) markers for pregnancy monitoring including defining the duration of the AL phase length. Research on 24 (6 pregnant, 8 pseudopregnant and 10 non-birth) cycles of 6 giant pandas revealed a fixed AL phase length of 42 days in giant pandas, e.g. representing 6 weeks of post- diapause development in case of pregnancy. Progestogen concentrations were significantly higher in pregnant cycles throughout the majority of the AL phase, with significant higher values during the AL phase in healthy twin compared to singleton pregnancies. GCM concentrations were also markedly higher in giant pandas expecting offspring, with a clear increase towards birth in the final 2 weeks of pregnancy. This increase in GCM was running in parallel with elevating estrogen and PGFM concentrations, and decreasing progestogens. In addition, during the AL phase, a more pronounced decrease in fecal output was obvious for pregnant females. The combined profiles of non-invasive metabolic and endocrine markers, the latter normalized based on USpG, showed a true pregnancy signature during the AL phase. The findings of this study are applicable to retrospective evaluations of non-birth cycles facilitating categorizing those into pseudopregnant or lost pregnancies, with USpG-normalization of the urinary endocrine markers as a prerequisite