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1.
Ann Gastroenterol Surg ; 8(2): 312-320, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38455485

ABSTRACT

Aims: The use of extended criteria donors is a routine practice that sometimes involves extracorporeal membrane oxygenation (ECMO) in donations after cardiac death or brain death. Methods: We performed a retrospective study in a single center from January 2006 to December 2019. The study included 90 deceased donor liver transplants. The patients were divided into three groups: the donation after brain death (DBD) group (n = 58, 64.4%), the DBD with ECMO group (n = 11, 12.2%) and the donation after cardiac death (DCD) with ECMO group (n = 21, 23.3%). Results: There were no significant differences between the DBD with ECMO group and the DBD group. When comparing the DCD with ECMO group and the DBD group, there were statistically significant differences for total warm ischemia time (p < 0.001), total cold ischemia time (p = 0.023), and split liver transplantation (p < 0.001), and there was significantly poor recovery in regard to total bilirubin level (p = 0.027) for the DCD with ECMO group by repeated measures ANOVA. The 5-year survival rates of the DBD, DBD with ECMO, and DCD with ECMO groups were 78.1%, 90.9%, and 75.6%, respectively. The survival rate was not significantly different when comparing the DBD group to either the DBD with ECMO group (p = 0.435) or the DCD with ECMO group (p = 0.310). Conclusions: Using ECMO in donations after cardiac death or brain death is a good technology, and it contributed to 35.6% of the liver graft pool.

2.
ACS Nano ; 15(8): 13085-13093, 2021 Aug 24.
Article in English | MEDLINE | ID: mdl-34313105

ABSTRACT

Strong coupling between light and matter is the foundation of promising quantum photonic devices such as deterministic single photon sources, single atom lasers, and photonic quantum gates, which consist of an atom and a photonic cavity. Unlike atom-based systems, a strong coupling unit based on an emitter-plasmonic nanocavity system has the potential to bring these devices to the microchip scale at ambient conditions. However, efficiently and precisely positioning a single or a few emitters into a plasmonic nanocavity is challenging. In addition, placing a strong coupling unit on a designated substrate location is a demanding task. Here, fluorophore-modified DNA strands are utilized to drive the formation of particle-on-film plasmonic nanocavities and simultaneously integrate the fluorophores into the high field region of the nanocavities. High cavity yield and fluorophore coupling yield are demonstrated. This method is then combined with e-beam lithography to position the strong coupling units on designated locations of a substrate. Furthermore, polariton energy under the detuning of fluorophore embedded nanocavities can fit into a model consisting of three sets of two-level systems, implying vibronic modes may be involved in the strong coupling. Our system makes strong coupling units more practical on the microchip scale and at ambient conditions and provides a stable platform for investigating fluorophore-plasmonic nanocavity interaction.

3.
Exp Clin Transplant ; 19(7): 664-670, 2021 07.
Article in English | MEDLINE | ID: mdl-34085916

ABSTRACT

OBJECTIVES: Neurologic complications are more common in liver transplants than in other solid-organ transplants. One such neurologic complication, peripheral neuropathy, may cause functional limitations for recipients and have a negative effect on posttransplant quality of life. We aimed to examine the risk factors associated with the occurrence of clinical neuropathy after liver transplant and to investigate the frequency of sensory deficits. MATERIALS AND METHODS: In this case-control study, we analyzed factors from medical records of 63 recipients who underwent living donor liver transplant during the period from January 2010 to December 2016. A neuropathy symptom score was assigned to identify the patients who had clinical neuropathy (case group) and the patients without clinical neuropathy (control group). Quantitative sensory testing was performed to measure the warm and cold detection thresholds, and the difference between the 2 groups was examined. RESULTS: Compared with controls, patients with clinical neuropathy were older (61.0 vs 55.4 years; P = .028), had higher rates of diabetes (46.2% vs 16.0%; P = .03), and were taking antiviral agents against hepatitis B (100% vs 62%; P = .006). Patients with neuropathic symptoms had significantly increased frequencies of impairment of warm and cold detection thresholds. In addition, the greater severity of symptoms showed higher detection thresholds of warm (control, 40.7℃; mild-to-moderate, 43.8 ℃; severe, 46.0 ℃; P = .007) and cold (control, 28.8℃ ; mild-to-moderate, 27.0 ℃; severe, 21.8 ℃ ; P = .008). CONCLUSIONS: Our findings show that older age, diabetes, and treatment with oral antiviral agents against hepatitis B virus were more likely to be associated with the occurrence of clinical neuropathy after liver transplant. Early awareness and careful monitoring are warranted.


Subject(s)
Liver Transplantation , Peripheral Nervous System Diseases , Antiviral Agents/therapeutic use , Case-Control Studies , Humans , Liver Transplantation/adverse effects , Living Donors , Peripheral Nervous System Diseases/chemically induced , Peripheral Nervous System Diseases/drug therapy , Quality of Life , Treatment Outcome
4.
Shanghai Kou Qiang Yi Xue ; 29(5): 539-543, 2020 Oct.
Article in Chinese | MEDLINE | ID: mdl-33543224

ABSTRACT

PURPOSE: To investigate the long-term effects of residual bone height (RBH), maxillary sinus membrane perforation, and cavities on survival of implants with lateral maxillary sinus lifting (MSFA). METHODS: Fifty-six patients (98 implants) who underwent MSFA from 2005 to 2009 and followed up till 2019 were enrolled. RBH was assessed using a series of panoramic and periapical X-ray films. Based on the presence of RBH, sinus membrane perforation, cavities, the cumulative survival rate (CSR) were evaluated using log-rank test and risk ratio of implant failure, SPSS 21.0 software package was used to analyze the data. RESULTS: The residual bone height of implants with sinus membrane perforation was significantly larger than those without sinus membrane perforation. The residual bone height of the survival implants was significantly larger than that of the failed implants(P<0.05), but there was no significant difference in the residual bone height between gender, smoking and cavities(P>0.05). The total CSR of 10 years after implantation by MSFA was 94.5%, of which the females was significantly higher than that of males, non-smokers was significantly higher than that of smokers, and RBH≥3 mm was significantly higher than that of RBH<3 mm(P<0.05). However, there was no significant difference in CSR between sinus membrane perforation and non-sinus membrane perforation. CONCLUSIONS: Implants with RBH<3 mm have lower CSR, and the survival is acceptable under proper oral hygiene maintenance conditions. Sinus perforation and cavity do not affect the survival of lateral MSFA implants.


Subject(s)
Dental Implants , Sinus Floor Augmentation , Dental Implantation, Endosseous , Female , Humans , Male , Maxilla/surgery , Maxillary Sinus/diagnostic imaging , Maxillary Sinus/surgery , Treatment Outcome
5.
Sensors (Basel) ; 14(6): 10578-97, 2014 Jun 16.
Article in English | MEDLINE | ID: mdl-24936948

ABSTRACT

Most railway accidents happen at railway crossings. Therefore, how to detect humans or objects present in the risk area of a railway crossing and thus prevent accidents are important tasks. In this paper, three strategies are used to detect the risk area of a railway crossing: (1) we use a terrain drop compensation (TDC) technique to solve the problem of the concavity of railway crossings; (2) we use a linear regression technique to predict the position and length of an object from image processing; (3) we have developed a novel strategy called calculating local maximum Y-coordinate object points (CLMYOP) to obtain the ground points of the object. In addition, image preprocessing is also applied to filter out the noise and successfully improve the object detection. From the experimental results, it is demonstrated that our scheme is an effective and corrective method for the detection of railway crossing risk areas.


Subject(s)
Accidents, Traffic/prevention & control , Image Interpretation, Computer-Assisted/methods , Pattern Recognition, Automated/methods , Railroads , Risk Assessment/methods , Signal Processing, Computer-Assisted , Subtraction Technique , Humans , Regression Analysis , Taiwan
6.
Zhongguo Zhong Yao Za Zhi ; 37(17): 2622-5, 2012 Sep.
Article in Chinese | MEDLINE | ID: mdl-23236764

ABSTRACT

OBJECTIVE: To investigate the function of VEGF pathway in promoting angiogenesis with Xuefu Zhuyu Tang (XFZYT). METHOD: Serum pharmacology technique was adopted to treat endothelial cells ECV304 with XFZYD containing serum and blank serum with concentrations of 1.25%, 2.5% and 5%. Methyl thiazolyl tetrazolium (MTT) assay, boyden chamber migration assay and in vitro vessel formation assay were used to test endothelial cell proliferation, migration and angiogenesis capacities. ELISA, immunohistochemistry and RT-PCR were used to detect secretion and expression of vascular endothelial growth factor (VEGF) and vascular endothelial growth factor receptor-2 (VEGFR2). RESULT: XFZYT-CS with a concentration of 1.25% only affected angiogenesis capacity in vitro. XFZYT-CS with a concentration of 2. 5% promoted cell proliferation, migration and angiogenesis capacities and significantly increased VEGF level and VEGF/VEGFR2 expressions. XFZYT-CS with a concentration of 5% only up-regulated intracellular VEGF expression and thereby improving endothelial cell proliferation, migration and angiogenesis. CONCLUSION: XFZYT can induce endothelial cell proliferation, migration and angiogenesis by up-regulating VEGF-VEGFR2 pathway, which partially proves its angiogenesis effects.


Subject(s)
Drugs, Chinese Herbal/pharmacology , Neovascularization, Physiologic/drug effects , Vascular Endothelial Growth Factor A/metabolism , Animals , Cell Movement/drug effects , Cell Proliferation/drug effects , Endothelial Cells/cytology , Endothelial Cells/drug effects , Endothelial Cells/metabolism , Female , Humans , Male , Rats , Rats, Sprague-Dawley , Receptors, Vascular Endothelial Growth Factor/genetics , Receptors, Vascular Endothelial Growth Factor/metabolism , Vascular Endothelial Growth Factor A/genetics
7.
Chin J Integr Med ; 18(7): 502-6, 2012 Jul.
Article in English | MEDLINE | ID: mdl-22772912

ABSTRACT

OBJECTIVE: To study the angiogenesis modulation mechanism of Xuefu Zhuyu Decoction () on the endothelial cell line ECV304. METHODS: ECV304 cells were treated with 2.5% Xuefu Zhuyu Decoction-containing serum (XFZYD-CS) for 24 h, 48 h or 72 h. Thiazolyl blue tetrazolium bromide (MTT), fluorescence activating cell sorter (FACS), migration, adhesion and in vitro tube formation assays were conducted to confirm an angiogenesis effect of XFZYD at 3 time points. An analysis of angiogenesis regulator profiles was performed at 3 times with real-time polymerase chain reaction (RT-PCR) superarray. RESULTS: At 48 h, XFZYD-CS induced ECV304 significantly improved cell viability, number in S phase, migration, adhesion and tube formation. At 24 h and 72 h, only cell migration was elevated. Microarray results showed that the expression of 27 angiogenesis-related genes was changed. CONCLUSION: XFZYD-CS treatment induced angiogenesis on ECV304 cells with significant cellcular changes occurring at 48 h and genetic changes as early as 24 h.


Subject(s)
Angiogenesis Inducing Agents/pharmacology , Drugs, Chinese Herbal/pharmacology , Endothelial Cells/drug effects , Endothelial Cells/metabolism , Neovascularization, Physiologic/drug effects , Neovascularization, Physiologic/genetics , Oligonucleotide Array Sequence Analysis/methods , Cell Adhesion/drug effects , Cell Adhesion/genetics , Cell Line , Cell Movement/drug effects , Cell Movement/genetics , Cell Proliferation/drug effects , Cell Survival/drug effects , Cell Survival/genetics , Gene Expression Regulation , Humans
8.
Zhonghua Zhong Liu Za Zhi ; 33(8): 613-5, 2011 Aug.
Article in Chinese | MEDLINE | ID: mdl-22325223

ABSTRACT

OBJECTIVE: To investigate and analyze the variation trends in the pathological composition of thyroid cancer patients treated in Tianjin Cancer Hospital from 1954 to 2009. METHODS: To retrospectively analyze the incidence and clinical features of different pathological types of thyroid cancers in 4342 patients between different time periods from 1954 to 2009. RESULTS: In the four main pathological types of thyroid cancers, the component ratio of papillary thyroid cancer in every period was 68.1%, 78.3%, 81.3%, 82.1%, 85.8%, respectively, while the morbidity of patients with papillary thyroid carcinoma concurrent with Hashimoto's thyroiditis was increased, so was the proportion of tumors in diameter < or = 2 cm. The proportion of follicular thyroid carcinoma and anaplastic thyroid carcinoma was decreasing accordingly; however, the proportion of medullary thyroid carcinoma did not change significantly. CONCLUSIONS: The pathological classification of the thyroid carcinoma patients has significant changes in the 4342 cases treated in our Hospital from 1954 to 2009. The proportion of papillary carcinoma is increased, while that of follicular carcinoma and anaplastic carcinoma is decreased. The reasons might attribute to the improved level of consultations and iodized diet or other factors.


Subject(s)
Carcinoma, Papillary/pathology , Thyroid Neoplasms/pathology , Adenocarcinoma, Follicular/epidemiology , Adenocarcinoma, Follicular/pathology , Carcinoma/epidemiology , Carcinoma/pathology , Carcinoma, Medullary/epidemiology , Carcinoma, Medullary/pathology , Carcinoma, Papillary/epidemiology , China/epidemiology , Female , Hashimoto Disease/complications , Hashimoto Disease/epidemiology , Hashimoto Disease/pathology , Humans , Incidence , Male , Retrospective Studies , Thyroid Neoplasms/complications , Thyroid Neoplasms/epidemiology , Tumor Burden
9.
Zhong Yao Cai ; 33(7): 1129-32, 2010 Jul.
Article in Chinese | MEDLINE | ID: mdl-21137372

ABSTRACT

OBJECTIVE: To observe the effect on EPCs function by Xuefu Zhuyu Decoction. METHODS: After induced by serial concentrations of Xuefu Zhuyu Decoction-contained serum (XZDCS) and blank serum, EPCs proliferation, migration, adhesion and uptake function were detected by MTT, Boyden chamber, adhesion and uptake of ac-LDL respectively. RESULTS: Compared with the control group, 15% and 10% XZDCS could elevate the cell regeneration for 24 h and 48 h respectively. Both concentrations could improve the EPCs migration and adhesion for all 24, 48, 72 h and uptake of ac-LDL only 48 h. But 10% XZDCS could last effect on uptake of ac-LDL to 72 h and 5% XZDCS converted the inhibition of cell adhesion in the first 24 h to promotion in the next 48 - 72 h. CONCLUSION: Xuefu Zhuyu Decoction could induce EPCs differentiation into EC to angiogenesis by promoting its proliferation, migration, adhesion and uptake function.


Subject(s)
Angiogenesis Inducing Agents/pharmacology , Drugs, Chinese Herbal/pharmacology , Endothelium/cytology , Stem Cells/drug effects , Animals , Cell Adhesion/drug effects , Cell Differentiation/drug effects , Cell Movement/drug effects , Cell Proliferation/drug effects , Cells, Cultured , Drugs, Chinese Herbal/isolation & purification , Female , Male , Phagocytosis/drug effects , Plants, Medicinal/chemistry , Random Allocation , Rats , Rats, Sprague-Dawley , Stem Cells/cytology
10.
Zhongguo Zhong Xi Yi Jie He Za Zhi ; 30(2): 153-6, 2010 Feb.
Article in Chinese | MEDLINE | ID: mdl-20462042

ABSTRACT

OBJECTIVE: To study the acting mechanism of endothelial cell line ECV304 in regulating angiogenesis induced by Xuefu Zhuyu Decoction (XFZY). METHODS: The angiogenesis effect of XFZY-contained serum (XFZY-CS) was confirmed by observing its impact on proliferation, cell cycle, migration of ECV304 and on vascular neogenesis in vitro. Then the effect of XFZY on various angiogenesis controlling factors was analyzed with gene chip microarray technique. RESULTS: Treatment of XFZY-CS in 2.5% concentration for 48 h showed evident actions of enhancing ECV304 activity, increasing cell numbers of S phase, inducing cell migration and promoting the in vitro angiogenesis. Meanwhile, expressions of four angiogenesis controlling genes were up-regulated and 10 were down-regulated. CONCLUSION: The angiogenesis mechanism of ECV304 induced by XFZY is complex, it shows a multi-pathway and multi-target feature.


Subject(s)
Angiogenesis Inducing Agents , Drugs, Chinese Herbal/pharmacology , Endothelial Cells/drug effects , Gene Expression Regulation/drug effects , Animals , Cell Line , Female , Male , Neovascularization, Physiologic/drug effects , Rats , Rats, Sprague-Dawley
11.
Chin J Integr Med ; 16(1): 50-3, 2010 Feb.
Article in English | MEDLINE | ID: mdl-20131036

ABSTRACT

OBJECTIVE: To observe the effect of Xuefu Zhuyu Decoction ()-containing serum (XFZYD-CS) on endothelial progenitor cell (EPC) tube formation in vitro. METHODS: Mononuclear cells from rat bone marrow were prepared in a Ficoll density gradient centrifuge. EPCs were separated by the differential attachment method, and observed with inverted microscope for the effect of XFZYD-CS on EPC tube formation. RESULTS: After one day, EPCs exposed to the serum containing 5%, 10% and 15% XFZYD-CS formed typical tubes or vessel networks. The tube formation time was two days ahead of the control group and the size of most tubes in the serum groups was smaller than in the control group. CONCLUSION: XFZYD-CS could induce EPC angiogenesis and hasten tube formation, especially in capillary vessels. The study provides experimental evidence for the plausibility of Xuefu Zhuyu Decoction in the treatment of ischemic diseases.


Subject(s)
Drugs, Chinese Herbal/pharmacology , Endothelial Cells/drug effects , Neovascularization, Physiologic/drug effects , Stem Cells/drug effects , Angiogenesis Inducing Agents/pharmacology , Animals , Cell Differentiation/drug effects , Cell Shape/drug effects , Cell Shape/physiology , Cells, Cultured , Drug Evaluation, Preclinical , Endothelial Cells/cytology , Endothelial Cells/physiology , Rats , Rats, Sprague-Dawley , Stem Cells/cytology , Stem Cells/physiology
12.
J Recept Signal Transduct Res ; 29(2): 107-12, 2009.
Article in English | MEDLINE | ID: mdl-19519175

ABSTRACT

The objective of this study was to determine if a functional heterodimer of prolactin receptor (PRLR) and growth hormone receptor (GHR) can be formed in humans. A novel ligand was designed that is composed of a GHR antagonist (B2036) and a PRLR antagonist (G129R) fused in tandem (B2036-G129R). Because both B2036 and G129R are binding site 2 inactive antagonists, the B2036-G129R fusion protein, in theory contains only two functional binding site 1s: one for GHR and one for PRLR. We examined the behavior of this chimeric ligand in cell lines known to express GHR, PRLR, or both receptors. The data presented show that B2036-G129R is inactive in IM-9 cells that express only GHR or Nb2 cells that express PRLR. In T-47D cells that coexpress PRLR and GHR, B2036-G129R activates JAK2/STAT5 signaling. These findings provide evidence that B2036-G129R is able to activate signal transduction through a heterodimer of PRLR and GHR in humans.


Subject(s)
Janus Kinase 2/metabolism , Receptors, Prolactin/metabolism , Receptors, Somatotropin/metabolism , Recombinant Fusion Proteins/pharmacology , STAT5 Transcription Factor/agonists , Animals , Cell Line, Tumor , Humans , Ligands , Phosphorylation/drug effects , Protein Multimerization , Rats , Recombinant Fusion Proteins/metabolism , STAT5 Transcription Factor/drug effects , STAT5 Transcription Factor/metabolism , Signal Transduction
13.
Inorg Chem ; 42(8): 2783-8, 2003 Apr 21.
Article in English | MEDLINE | ID: mdl-12691589

ABSTRACT

Dinuclear iron(II)-cyanocarbonyl complex [PPN](2)[Fe(CN)(2)(CO)(2)(mu-SEt)](2) (1) was prepared by the reaction of [PPN][FeBr(CN)(2)(CO)(3)] and [Na][SEt] in THF at ambient temperature. Reaction of complex 1 with [PPN][SEt] produced the triply thiolate-bridged dinuclear Fe(II) complex [PPN][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)] (2) with the torsion angle of two CN(-) groups (C(5)N(2) and C(3)N(1)) being 126.9 degrees. The extrusion of two sigma-donor CN(-) ligands from Fe(II)Fe(II) centers of complex 1 as a result of the reaction of complex 1 and [PPN][SEt] reflects the electron-rich character of the dinuclear iron(II) when ligated by the third bridging ethylthiolate. The Fe-S distances (2.338(2) and 2.320(3) A for complexes 1 and 2, respectively) do not change significantly, but the Fe(II)-Fe(II) distance contracts from 3.505 A in complex 1 to 3.073 A in complex 2. The considerably longer Fe(II)-Fe(II) distance of 3.073 A in complex 2, compared to the reported Fe-Fe distances of 2.6/2.62 A in DdHase and CpHase, was attributed to the presence of the third bridging ethylthiolate, instead of pi-accepting CO-bridged ligand as observed in [Fe] hydrogenases. Additionally, in a compound of unusual composition ([Na.(5)/(2)H(2)O][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)])(n)((1)/(2)O(Et)(2))(n) (3), the Na(+) cations and H(2)O molecules combining with dinuclear [(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)](-) anions create a polymeric framework wherein two CN(-) ligands are coordinated via CN(-)-Na(+)/CN(-)-(Na(+))(2) linkages, respectively.


Subject(s)
Ferrous Compounds/chemical synthesis , Hydrogenase/chemistry , Iron-Sulfur Proteins/chemistry , Iron/chemistry , Binding Sites , Carbon Monoxide/chemistry , Crystallography, X-Ray , Cyanides/chemistry , Ferrous Compounds/chemistry , Ligands , Models, Molecular , Molecular Conformation
14.
Clin Cancer Res ; 8(4): 1196-205, 2002 Apr.
Article in English | MEDLINE | ID: mdl-11948133

ABSTRACT

The aim of this study is to combine endocrine therapy [human prolactin (hPRL) antagonist, G129R] and immune therapy [interleukin 2 (IL2)] in the design of a fusion protein, G129R-IL2, to treat human breast cancer. This novel approach uses the specific interaction between the G129R and hPRL receptors (PRLRs), thus directly targeting the fusion protein to the malignant breast tissues that have previously been shown to contain high levels of PRLR. The localized bifunctional fusion protein is designed to block signal transduction induced by hPRL as well as to activate T lymphocytes near the tumor site. A bacterial expression system was used to produce G129R-IL2 fusion protein that maintained both G129R and IL2 activities as demonstrated by cell-based assays such as signal transducer(s) and activator(s) of transcription (STAT)5 phosphorylation, breast cancer cell proliferation, and T-cell proliferation. The antitumor activities of G129R-IL2 were demonstrated in vivo using a syngeneic model system with BALB/c mice and EMT6-hPRLR breast cancer cells. After daily injection (i.p.) of G129R-IL2 (100 microg/mouse) for 18 days, the tumor growth in the G129R-IL2-treated group was only one-third the size as compared with that of the control group. The growth rate in the G129R-IL2-treated group is also significantly slower than that of the group treated with G129R alone (200 microg/mouse/day). We hope that this novel bifunctional protein will contribute significantly to human breast cancer therapy.


Subject(s)
Breast Neoplasms/drug therapy , Interleukin-2/pharmacology , Milk Proteins , Prolactin/antagonists & inhibitors , Prolactin/pharmacology , Animals , Breast Neoplasms/pathology , Cell Division/drug effects , Cell Line , DNA-Binding Proteins/drug effects , DNA-Binding Proteins/metabolism , Dose-Response Relationship, Drug , Drug Design , Female , Humans , Interleukin-2/genetics , Interleukin-2/therapeutic use , Mammary Neoplasms, Experimental/drug therapy , Mammary Neoplasms, Experimental/pathology , Mice , Mice, Inbred BALB C , Neoplasm Transplantation , Phosphorylation/drug effects , Prolactin/genetics , Prolactin/therapeutic use , Recombinant Fusion Proteins/genetics , Recombinant Fusion Proteins/pharmacology , Recombinant Fusion Proteins/therapeutic use , STAT5 Transcription Factor , Time Factors , Trans-Activators/drug effects , Trans-Activators/metabolism , Tumor Cells, Cultured/drug effects , Tumor Cells, Cultured/metabolism
15.
J Am Chem Soc ; 124(8): 1680-8, 2002 Feb 27.
Article in English | MEDLINE | ID: mdl-11853444

ABSTRACT

The dicyanodicarbonyliron(II) thiolate complexes trans,cis-[(CN)(2)(CO)(2)Fe(S,S-C-R)](-) (R = OEt (2), N(Et)(2) (3)) were prepared by the reaction of [Na][S-C(S)-R] and [Fe(CN)(2)(CO)(3)(Br)](-) (1). Complex 1 was obtained from oxidative addition of cyanogen bromide to [Fe(CN)(CO)(4)](-). In a similar fashion, reaction of complex 1 with [Na][S,O-C(5)H(4)N], and [Na][S,N-C(5)H(4)] produced the six-coordinate trans,cis-[(CN)(2)(CO)(2)Fe(S,O-C(5)H(4)N)](-) (6) and trans,cis-[(CN)(2)(CO)(2)Fe(S,N-C(5)H(4))](-) (7) individually. Photolysis of tetrahydrofuran (THF) solution of complexes 2, 3, and 7 under CO led to formation of the coordinatively unsaturated iron(II) dicyanocarbonyl thiolate compounds [(CN)(2)(CO)Fe(S,S-C-R)](-) (R = OEt (4), N(Et)(2) (5)) and [(CN)(2)(CO)Fe(S,N-C(5)H(4))](-) (8), respectively. The IR v(CN) stretching frequencies and patterns of complexes 4, 5, and 8 have unambiguously identified two CN(-) ligands occupying cis positions. In addition, density functional theory calculations suggest that the architecture of five-coordinate complexes 4, 5, and 8 with a vacant site trans to the CO ligand and two CN(-) ligands occupying cis positions serves as a conformational preference. Complexes 2, 3, and 7 were reobtained when the THF solution of complexes 4, 5, and 8 were exposed to CO atmosphere at 25 degrees C individually. Obviously, CO ligand can be reversibly bound to the Fe(II) site in these model compounds. Isotopic shift experiments demonstrated the lability of carbonyl ligands of complexes 2, 3, 4, 5, 7, and 8. Complexes [(CN)(2)(CO)Fe(S,S-C-R)](-) and NiA/NiC states [NiFe] hydrogenases from D. gigas exhibit a similar one-band pattern in the v(CO) region and two-band pattern in the v(CN) region individually, but in different positions, which may be accounted for by the distinct electronic effects between [S,S-C-R](-) and cysteine ligands. Also, the facile formations of five-coordinate complexes 4, 5, and 8 imply that the strong sigma-donor, weak pi-acceptor CN(-) ligands play a key role in creating/stabilizing five-coordinate iron(II) [(CN)(2)(CO)Fe(S,S-C-R)](-) complexes with a vacant coordination site trans to the CO ligand.


Subject(s)
Ferrous Compounds/chemical synthesis , Hydrogenase/chemistry , Sulfhydryl Compounds/chemical synthesis , Binding Sites , Carbon Monoxide/chemistry , Crystallography, X-Ray , Cyanides/chemical synthesis , Cyanides/chemistry , Ferrous Compounds/chemistry , Models, Molecular , Spectroscopy, Fourier Transform Infrared , Sulfhydryl Compounds/chemistry
16.
Article in English | MEDLINE | ID: mdl-12058184

ABSTRACT

Adenylyl cyclase(AC)activity was determined by directly quantifying the product cAMP with ion-exchange HPLC. When AC reaction was terminated, the reaction mixture was kept at 0 degrees for 2 h to remove residual ATP utilizing the action of ATP-hydrolyzing enzymes existed in the crude AC preparation of membrane pellet. Papaverine was removed by the dichloromethane extraction, and cAMP was quantified by chromatography on a WAX-1 HPLC column with baseline-resolution. It was found that cAMP was linearly formed within 10 min of the reaction, and the amount of cAMP formed was proportional to the amount of enzyme. Mouse brain AC activity determined by this method was 42 nmol/min per gram of protein, similar to that obtained by the classical [(3)H] labeled ATP method. This ion-exchange HPLC was more rapid and convenient.

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