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        Thermodynamic profile for urea photo-release from a N-(2-nitrobenzyl) caged urea compound

        Dhulipala, Gangadhar,Rubio, Marisa,Michael, Katja,Miksovska, Jaroslava Korean Society of Photoscience 2009 Photochemical & photobiological sciences Vol.8 No.8

        Photoactivable bioactive molecules, often termed "caged" compounds, have attracted significant attention as useful tools for photo-regulating enzymatic activity. Here we examine the mechanism associated with photo-release of urea from a caged urea compound, N-(2-nitrobenzyl)urea, using photothermal beam deflection and time-resolved absorption spectroscopy. Photodissociation of the caged urea results in the prompt formation of an aci-nitro intermediate that decays to nitrosobenzaldehyde by releasing urea with the rate constant of $4.5{\times}10^3s^{-1}$. Appearance of the aci-nitro intermediate is associated with a volume contraction of $-13{\pm}1$ mL $mol^{-1}$ and a negligible change in enthalpy (${\Delta}H=6{\pm}4$ kcal $mol^{-1}$). On the microsecond time-scale, the conversion of the aci-nitro intermediate and concomitant release of urea result in a volume expansion of $6{\pm}2$ mL $mol^{-1}$ and a negative enthalpy change of $-25{\pm}5$ kcal $mol^{-1}$. No additional processes were observed on the timescale up to 100 ms suggesting that the breakdown of the aci-nitro intermediate is the rate-limiting step for urea photo-release. These results suggest a similar mechanism for caged urea photo release as determined previously for the caged ATP compound.

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        Biomechanical Comparison of Fixed- versus Variable-Angle Locking Screws for Distal Humerus Comminuted Fractures

        Ali Nourbakhsh,Adam G. Hirschfeld,Sravan Dhulipala,William Hutton,Timothy Ganey,Luis Lozada,Daniel Schlatterer,Gary Mark Lourie 대한정형외과학회 2019 Clinics in Orthopedic Surgery Vol.11 No.3

        Background: To compare the stability of fixed- versus variable-angle locking constructs for the comminuted distal humerus fracture (AO/OTA 13-A3). Methods: Eight pairs of complete humeri harvested from eight fresh frozen cadavers were used for the study. We fixed the intact humeri using 2.7-mm/3.5-mm locking VA-LCP stainless steel distal humerus posterolateral (nine-hole) and medial (seven-hole) plates. An oscillating saw was used to cut a 1-cm gap above the olecranon fossa. The specimens were loaded in axial mode with the rate of 1 mm per 10 seconds to failure, and stress-strain curves were compared in each pair. The mode of failure was recorded as well as the load needed for 2- and 4-mm displacement at the lateral end of the gap. Results: The stiffness of the constructs, based on the slope of the stress-strain curve, did not show any difference between the fixed- versus variable-angle constructs. Likewise, there was no difference between the force needed for 2- or 4-mm displacement at the lateral gap between the fixed- and variable-angle constructs. The mode of failure was bending of both plates in all specimens and screw pull-out in four specimen pairs in addition to the plate bending. Conclusions: Our results did not show any difference in the biomechanical stability of the fixed- versus variable-angle constructs. There was not any screw breakage or failure of the plate-screw interface.

      • Novel Mononuclear Ruthenium(II) Compounds in Cancer Therapy

        Anchuri, Shyam Sunder,Thota, Sreekanth,Yerra, Rajeshwar,Devarakonda, Krishna Prasad,Dhulipala, Satyavati Asian Pacific Journal of Cancer Prevention 2012 Asian Pacific journal of cancer prevention Vol.13 No.7

        The present study was conducted to evaluate in vivo anticancer activity of two novel mononuclear ruthenium(II) compounds, namely Ru(1,10-phenanthroline)$_2$(2-nitro phenyl thiosemicarbazone)$Cl_2$(Compound $R_1$) and Ru (1,10-phenanthroline)$_2$(2-hydroxy phenyl thiosemicarbazone)$Cl_2$(Compound $R_2$) against Ehrlich ascites carcinoma (EAC) mice and in vitro cytotoxic activity against IEC-6 (small intestine) cell lines and Artemia salina nauplii using MTT [(3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide)] and BLT [brine shrimp lethality] assays respectively. The tested ruthenium compounds at the doses 2 and 4 mg/kg body weight showed promising biological activity especially in decreasing the tumor volume, viable ascites cell counts and body weights. These compounds prolonged the life span (% ILS), mean survival time (MST) of mice bearing-EAC tumor. The results for in vitro cytotoxicity against IEC-6 cells showed the ruthenium compound $R_2$ to have significant cytotoxic activity with a $IC_{50}$ value of $20.0{\mu}g/mL$ than $R_1$ ($IC_{50}=78.8{\mu}g/mL$) in the MTT assay and the $LC_{50}$ values of $R_1$ and $R_2$ compounds were found to be 38.3 and $43.8{\mu}g/mL$ respectively in the BLT assay. The biochemical and histopathological results revealed that there was no significant hepatotoxicity and nephrotoxicity associated with the ruthenium administration to mice.

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