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  1. Article ; Online: Long-range proton-coupled electron transfer in the

    Reece, Steven Y / Seyedsayamdost, Mohammad R

    Essays in biochemistry

    2017  Volume 61, Issue 2, Page(s) 281–292

    Abstract: Escherichia ... ...

    Abstract Escherichia coli
    Language English
    Publishing date 2017-05-09
    Publishing country England
    Document type Journal Article ; Review
    ISSN 1744-1358 ; 0071-1365
    ISSN (online) 1744-1358
    ISSN 0071-1365
    DOI 10.1042/EBC20160072
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  2. Article ; Online: Cooled radiofrequency ablation versus standard medical management for chronic sacroiliac joint pain: a multicenter, randomized comparative effectiveness study.

    Cohen, Steven P / Kapural, Leonardo / Kohan, Lynn / Li, Sean / Hurley, Robert W / Vallejo, Richard / Eshraghi, Yashar / Dinakar, Pradeep / Durbhakula, Shravani / Beall, Douglas P / Desai, Mehul J / Reece, David / Christiansen, Sandy / Chang, Min Ho / Carinci, Adam J / DePalma, Michael

    Regional anesthesia and pain medicine

    2024  Volume 49, Issue 3, Page(s) 184–191

    Abstract: Introduction: Low back pain is the leading cause of disability worldwide, with sacroiliac joint pain comprising up to 30% of cases of axial lower back pain. Conservative therapies provide only modest relief. Although placebo-controlled trials show ... ...

    Abstract Introduction: Low back pain is the leading cause of disability worldwide, with sacroiliac joint pain comprising up to 30% of cases of axial lower back pain. Conservative therapies provide only modest relief. Although placebo-controlled trials show efficacy for sacral lateral branch cooled radiofrequency ablation, there are no comparative effectiveness studies.
    Methods: In this randomized, multicenter comparative effectiveness study, 210 patients with clinically suspected sacroiliac joint pain who obtained short-term benefit from diagnostic sacroiliac joint injections and prognostic lateral branch blocks were randomly assigned to receive cooled radiofrequency ablation of the L5 dorsal ramus and S1-S3 lateral branches or standard medical management consisting of pharmacotherapy, injections and integrative therapies. The primary outcome measure was mean reduction in low back pain score on a 0-10 Numeric Rating Scale at 3 months. Secondary outcomes included measures of quality of life and function.
    Results: 3 months post-treatment, the mean Numeric Rating Scale pain score for the cooled radiofrequency ablation group was 3.8±2.4 (mean reduction 2.5±2.5) compared with 5.9±1.7 (mean reduction 0.4±1.7) in the standard medical management group (p<0.0001). 52.3% of subjects in the cooled radiofrequency ablation group experienced
    Conclusions: In patients with sacroiliac joint pain, cooled radiofrequency ablation provided statistically superior improvements across the spectrum of patient outcomes compared with standard medical management.
    Trial registration number: NCT03601949.
    MeSH term(s) Humans ; Arthralgia/diagnosis ; Arthralgia/surgery ; Chronic Pain ; Low Back Pain/diagnosis ; Low Back Pain/surgery ; Quality of Life ; Radiofrequency Ablation ; Sacroiliac Joint/surgery ; Treatment Outcome
    Language English
    Publishing date 2024-03-04
    Publishing country England
    Document type Randomized Controlled Trial ; Multicenter Study ; Journal Article
    ZDB-ID 1425299-5
    ISSN 1532-8651 ; 1098-7339 ; 0146-521X
    ISSN (online) 1532-8651
    ISSN 1098-7339 ; 0146-521X
    DOI 10.1136/rapm-2023-104568
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  3. Article ; Online: Late Outcomes of Patients With Prehospital ST-Segment Elevation and Appropriate Cardiac Catheterization Laboratory Nonactivation.

    Faour, Amir / Pahn, Reece / Cherrett, Callum / Gibbs, Oliver / Lintern, Karen / Mussap, Christian J / Rajaratnam, Rohan / Leung, Dominic Y / Taylor, David A / Faddy, Steven C / Lo, Sidney / Juergens, Craig P / French, John K

    Journal of the American Heart Association

    2022  Volume 11, Issue 13, Page(s) e025602

    Abstract: Background Patients with suspected ST-segment-elevation myocardial infarction (STEMI) and cardiac catheterization laboratory nonactivation (CCL-NA) or cancellation have reportedly similar crude and higher adjusted risks of death compared with those with ... ...

    Abstract Background Patients with suspected ST-segment-elevation myocardial infarction (STEMI) and cardiac catheterization laboratory nonactivation (CCL-NA) or cancellation have reportedly similar crude and higher adjusted risks of death compared with those with CCL activation, though reasons for these poor outcomes are not clear. We determined late clinical outcomes among patients with prehospital ECG STEMI criteria who had CCL-NA compared with those who had CCL activation. Methods and Results We identified consecutive prehospital ECG transmissions between June 2, 2010 to October 6, 2016. Diagnoses according to the Fourth Universal Definition of myocardial infarction (MI), particularly rates of myocardial injury, were adjudicated. The primary outcome was all-cause death. Secondary outcomes included cardiovascular death/MI/stroke and noncardiovascular death. To explore competing risks, cause-specific hazard ratios (HRs) were obtained. Among 1033 included ECG transmissions, there were 569 (55%) CCL activations and 464 (45%) CCL-NAs (1.8% were inappropriate CCL-NAs). In the CCL activation group, adjudicated index diagnoses included MI (n=534, 94%, of which 99.6% were STEMI and 0.4% non-STEMI), acute myocardial injury (n=15, 2.6%), and chronic myocardial injury (n=6, 1.1%). In the CCL-NA group, diagnoses included MI (n=173, 37%, of which 61% were non-STEMI and 39% STEMI), chronic myocardial injury (n=107, 23%), and acute myocardial injury (n=47, 10%). At 2 years, the risk of all-cause death was higher in patients who had CCL-NA compared with CCL activation (23% versus 7.9%, adjusted risk ratio, 1.58, 95% CI, 1.24-2.00), primarily because of an excess in noncardiovascular deaths (adjusted HR, 3.56, 95% CI, 2.07-6.13). There was no significant difference in the adjusted risk for cardiovascular death/MI/stroke between the 2 groups (HR, 1.23, 95% CI, 0.87-1.73). Conclusions CCL-NA was not primarily attributable to missed STEMI, but attributable to "masquerading" with high rates of non-STEMI and myocardial injury. These patients had worse late outcomes than patients who had CCL activation, mainly because of higher rates of noncardiovascular deaths.
    MeSH term(s) Cardiac Catheterization ; Electrocardiography ; Emergency Medical Services/methods ; Humans ; Myocardial Infarction/diagnosis ; Myocardial Infarction/therapy ; ST Elevation Myocardial Infarction/diagnosis ; ST Elevation Myocardial Infarction/therapy ; Stroke
    Language English
    Publishing date 2022-06-29
    Publishing country England
    Document type Journal Article
    ZDB-ID 2653953-6
    ISSN 2047-9980 ; 2047-9980
    ISSN (online) 2047-9980
    ISSN 2047-9980
    DOI 10.1161/JAHA.121.025602
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  4. Article ; Online: Proton-coupled electron transfer in biology: results from synergistic studies in natural and model systems.

    Reece, Steven Y / Nocera, Daniel G

    Annual review of biochemistry

    2009  Volume 78, Page(s) 673–699

    Abstract: Proton-coupled electron transfer (PCET) underpins energy conversion in biology. PCET may occur with the unidirectional or bidirectional transfer of a proton and electron and may proceed synchronously or asynchronously. To illustrate the role of PCET in ... ...

    Abstract Proton-coupled electron transfer (PCET) underpins energy conversion in biology. PCET may occur with the unidirectional or bidirectional transfer of a proton and electron and may proceed synchronously or asynchronously. To illustrate the role of PCET in biology, this review presents complementary biological and model systems that explore PCET in electron transfer (ET) through hydrogen bonds [azurin as compared to donor-acceptor (D-A) hydrogen-bonded networks], the activation of C-H bonds [alcohol dehydrogenase and soybean lipoxygenase (SLO) as compared to Fe(III) metal complexes], and the generation and transport of amino acid radicals [photosystem II (PSII) and ribonucleotide reductase (RNR) as compared to tyrosine-modified photoactive Re(I) and Ru(II) complexes]. In providing these comparisons, the fundamental principles of PCET in biology are illustrated in a tangible way.
    MeSH term(s) Animals ; Electron Transport ; Hydrogen Bonding ; Models, Biological ; Plants/enzymology ; Plants/metabolism ; Protons
    Chemical Substances Protons
    Language English
    Publishing date 2009-04-03
    Publishing country United States
    Document type Journal Article ; Research Support, N.I.H., Extramural ; Review
    ZDB-ID 207924-0
    ISSN 1545-4509 ; 0066-4154
    ISSN (online) 1545-4509
    ISSN 0066-4154
    DOI 10.1146/annurev.biochem.78.080207.092132
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  5. Article ; Online: Nonorganic (Behavioral) Signs and Their Association With Epidural Corticosteroid Injection Treatment Outcomes and Psychiatric Comorbidity in Cervical Radiculopathy: A Multicenter Study.

    Cohen, Steven P / Doshi, Tina L / Dolomisiewicz, Edward / Reece, David E / Zhao, Zirong / Anderson-White, Mirinda / Kasuke, Angelia / Wang, Eric J / Hsu, Annie / Davis, Shelton A / Yoo, Yongjae / Pasquina, Paul F / Moon, Jee Youn

    Mayo Clinic proceedings

    2023  Volume 98, Issue 6, Page(s) 868–882

    Abstract: Objective: To determine the association between cervical nonorganic pain signs and epidural corticosteroid injection outcomes and coexisting pain and psychiatric conditions.: Patients and methods: Seventy-eight patients with cervical radiculopathy ... ...

    Abstract Objective: To determine the association between cervical nonorganic pain signs and epidural corticosteroid injection outcomes and coexisting pain and psychiatric conditions.
    Patients and methods: Seventy-eight patients with cervical radiculopathy who received epidural corticosteroid injection were observed to determine the effects that nonorganic signs have on treatment outcome. A positive outcome was a decrease of 2 or more points in average arm pain, coupled with a score of 5 on a 7-point Patient Global Impression of Change scale 4 weeks after treatment. Nine tests in 5 categories (abnormal tenderness, regional disturbances deviating from normal anatomy, overreaction, discrepancies in examination findings with distraction, and pain during sham stimulation) were modified from previous studies and standardized. Other variables examined for their association with nonorganic signs and outcomes included disease burden, psychopathology, coexisting pain conditions, and somatization.
    Results: Of the 78 patients, 29% (n=23) had no nonorganic signs, 21% (n=16) had signs in 1 category, 10% (n=8) had signs in 2 categories, 21% (n=16) had signs in 3 categories, 10% (n=8) had signs in 4 categories, and 9% (n=7) had signs in 5 categories. The most common nonorganic sign was superficial tenderness (44%; n=34). Mean number of positive nonorganic categories was higher in individuals with negative treatment outcomes (2.5±1.8; 95% CI, 2.0 to 3.1) compared with those with positive outcomes (1.1±1.3; 95% CI, 0.7 to 1.5; P=.0002). Negative treatment outcomes were most strongly associated with regional disturbances and overreaction. Positive associations were noted between nonorganic signs and multiple pain (P=.011) and multiple psychiatric (P=.028) conditions.
    Conclusion: Cervical nonorganic signs correlate with treatment outcome, pain, and psychiatric comorbidities. Screening for these signs and psychiatric symptoms may improve treatment outcomes.
    Trial registration: ClinicalTrials.gov identifier: NCT04320836.
    MeSH term(s) Humans ; Radiculopathy/diagnosis ; Radiculopathy/drug therapy ; Radiculopathy/epidemiology ; Adrenal Cortex Hormones/therapeutic use ; Treatment Outcome ; Neck Pain/diagnosis ; Neck Pain/drug therapy ; Neck Pain/epidemiology ; Comorbidity
    Chemical Substances Adrenal Cortex Hormones
    Language English
    Publishing date 2023-02-15
    Publishing country England
    Document type Multicenter Study ; Journal Article ; Research Support, U.S. Gov't, Non-P.H.S.
    ZDB-ID 124027-4
    ISSN 1942-5546 ; 0025-6196
    ISSN (online) 1942-5546
    ISSN 0025-6196
    DOI 10.1016/j.mayocp.2022.11.022
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  6. Article: Direct tyrosine oxidation using the MLCT excited states of rhenium polypyridyl complexes.

    Reece, Steven Y / Nocera, Daniel G

    Journal of the American Chemical Society

    2005  Volume 127, Issue 26, Page(s) 9448–9458

    Abstract: ... of tyrosyl radical. Tyrosine (Y) and phenylalanine (F) have each been separately appended to a conventional ... resolved emission quenching and transient absorption spectra of Re(bpy-Y)(CO)(3)CN and Re(bpy-F)(CO)(3)CN ... show that Y is oxidized only upon its deprotonation at pH 12. In an effort to redirect ...

    Abstract Rhenium(I) polypyridyl complexes have been designed for the intramolecular photogeneration of tyrosyl radical. Tyrosine (Y) and phenylalanine (F) have each been separately appended to a conventional Re(I)(bpy)(CO)(3)CN framework via an amide linkage to the bipyridine (bpy) ligand. Comparative time-resolved emission quenching and transient absorption spectra of Re(bpy-Y)(CO)(3)CN and Re(bpy-F)(CO)(3)CN show that Y is oxidized only upon its deprotonation at pH 12. In an effort to redirect electron transport so that it is more compatible with intramolecular Y oxidation, polypyridyl Re(I) complexes have been prepared with the amide bond functionality located on a pendant phosphine ligand. A [Re(phen)(PP-Bn)(CO)(2)](PF(6)) (PP = bis(diphenylphosphino)ethylene) complex has been synthesized and crystallographically characterized. Electrochemistry and phosphorescence measurements of this complex indicate a modest excited-state potential for tyrosine oxidation, similar to that for the (bpy)Re(I)(CO)(3)CN framework. The excited-state oxidation potential can be increased by introducing a monodentate phosphine to the Re(I)(NN)(CO)(3)(+) framework (NN = polypyridyl). In this case, Y is oxidized at all pHs when appended to the triphenylphosphine (P) of [Re(phen)(P-Y)(CO(3))](PF(6)). Analysis of the pH dependence of the rate constant for tyrosyl radical generation is consistent with a proton-coupled electron transfer (PCET) quenching mechanism.
    MeSH term(s) Amides/chemistry ; Electrochemistry ; Electron Transport ; Ethylenes/chemistry ; Free Radicals/chemistry ; Free Radicals/radiation effects ; Hydrogen-Ion Concentration ; Luminescent Measurements ; Organometallic Compounds/chemical synthesis ; Oxidation-Reduction ; Phenylalanine/chemistry ; Phosphines/chemistry ; Photochemistry ; Protons ; Pyridines/chemistry ; Rhenium/chemistry ; Spectrophotometry ; Tyrosine/chemistry ; Tyrosine/radiation effects
    Chemical Substances Amides ; Ethylenes ; Free Radicals ; Organometallic Compounds ; Phosphines ; Protons ; Pyridines ; tyrosine radical ; Tyrosine (42HK56048U) ; Phenylalanine (47E5O17Y3R) ; Rhenium (7440-15-5) ; ethylene (91GW059KN7)
    Language English
    Publishing date 2005-07-06
    Publishing country United States
    Document type Comparative Study ; Journal Article ; Research Support, N.I.H., Extramural ; Research Support, U.S. Gov't, P.H.S.
    ZDB-ID 3155-0
    ISSN 1520-5126 ; 0002-7863
    ISSN (online) 1520-5126
    ISSN 0002-7863
    DOI 10.1021/ja0510360
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  7. Article ; Online: Synthesis of nitric oxide by the NOS-like protein from deinococcus radiodurans: a direct role for tetrahydrofolate.

    Reece, Steven Y / Woodward, Joshua J / Marletta, Michael A

    Biochemistry

    2009  Volume 48, Issue 23, Page(s) 5483–5491

    Abstract: Genes encoding for proteins with high sequence homology to the heme-containing, oxygenase domain of mammalian nitric oxide synthase (NOS) have been identified in a number of bacteria. Many of these species of bacteria do not contain the genes that encode ...

    Abstract Genes encoding for proteins with high sequence homology to the heme-containing, oxygenase domain of mammalian nitric oxide synthase (NOS) have been identified in a number of bacteria. Many of these species of bacteria do not contain the genes that encode for the synthetic machinery to produce tetrahydrobiopterin (H(4)B), a cofactor of NOS required for NO synthesis. These bacteria have the genes for the synthesis of tetrahydrofolate (H(4)F) which contains the redox-active pteridine ring of H(4)B. These observations led us to investigate whether H(4)F could be used for the synthesis of NO by NOS-like enzymes from bacteria that cannot make H(4)B. The NOS gene from one such bacterium, Deinococcus radiodurans, was cloned and expressed (deiNOS) in Escherichia coli and then purified and characterized. The K(D) of deiNOS for the NOS substrate arginine (0.9 +/- 0.1 mM) drops by over 2 orders of magnitude in the presence of H(4)F (7.4 +/- 0.1 microM). Further, NO is synthesized from the NOS substrate N-hydroxy-l-arginine (NHA) by deiNOS in the presence of H(4)F. Stopped-flow spectroscopic data reveal that H(4)F accelerates the rate of decay of the ferrous-oxy/ferric-superoxo species in substrate turnover. These data strongly suggest that H(4)F may be used by D. radiodurans to replace H(4)B as a redox-active cofactor for nitric oxide synthesis.
    MeSH term(s) Bacterial Proteins/chemistry ; Bacterial Proteins/metabolism ; Binding Sites ; Deinococcus/enzymology ; Deinococcus/metabolism ; Hydrogen Peroxide/chemistry ; Hydrogen Peroxide/metabolism ; Kinetics ; Nitric Oxide/biosynthesis ; Nitric Oxide Synthase/chemistry ; Nitric Oxide Synthase/metabolism ; Protein Conformation ; Tetrahydrofolates/metabolism
    Chemical Substances Bacterial Proteins ; Tetrahydrofolates ; Nitric Oxide (31C4KY9ESH) ; Hydrogen Peroxide (BBX060AN9V) ; Nitric Oxide Synthase (EC 1.14.13.39)
    Language English
    Publishing date 2009-06-16
    Publishing country United States
    Document type Journal Article ; Research Support, Non-U.S. Gov't
    ZDB-ID 1108-3
    ISSN 1520-4995 ; 0006-2960
    ISSN (online) 1520-4995
    ISSN 0006-2960
    DOI 10.1021/bi900385g
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  8. Article ; Online: Guidelines for Diagnosis and Management of Infective Endocarditis in Adults: A WikiGuidelines Group Consensus Statement.

    McDonald, Emily G / Aggrey, Gloria / Tarik Aslan, Abdullah / Casias, Michael / Cortes-Penfield, Nicolas / Dong, Mei Qin Denise / Egbert, Susan / Footer, Brent / Isler, Burcu / King, Madeline / Maximos, Mira / Wuerz, Terence C / Azim, Ahmed Abdul / Alza-Arcila, Jhongert / Bai, Anthony D / Blyth, Michelle / Boyles, Tom / Caceres, Juan / Clark, Devin /
    Davar, Kusha / Denholm, Justin T / Forrest, Graeme / Ghanem, Bassam / Hagel, Stefan / Hanretty, Alexandra / Hamilton, Fergus / Jent, Philipp / Kang, Minji / Kludjian, Geena / Lahey, Tim / Lapin, Jonathan / Lee, Rachael / Li, Timothy / Mehta, Dhara / Moore, Jessica / Mowrer, Clayton / Ouellet, Georges / Reece, Rebecca / Ryder, Jonathan H / Sanctuaire, Alexandre / Sanders, James M / Stoner, Bobbi Jo / So, Jessica M / Tessier, Jean-François / Tirupathi, Raghavendra / Tong, Steven Y C / Wald-Dickler, Noah / Yassin, Arsheena / Yen, Christina / Spellberg, Brad / Lee, Todd C

    JAMA network open

    2023  Volume 6, Issue 7, Page(s) e2326366

    Abstract: Importance: Practice guidelines often provide recommendations in which the strength of the recommendation is dissociated from the quality of the evidence.: Objective: To create a clinical guideline for the diagnosis and management of adult bacterial ... ...

    Abstract Importance: Practice guidelines often provide recommendations in which the strength of the recommendation is dissociated from the quality of the evidence.
    Objective: To create a clinical guideline for the diagnosis and management of adult bacterial infective endocarditis (IE) that addresses the gap between the evidence and recommendation strength.
    Evidence review: This consensus statement and systematic review applied an approach previously established by the WikiGuidelines Group to construct collaborative clinical guidelines. In April 2022 a call to new and existing members was released electronically (social media and email) for the next WikiGuidelines topic, and subsequently, topics and questions related to the diagnosis and management of adult bacterial IE were crowdsourced and prioritized by vote. For each topic, PubMed literature searches were conducted including all years and languages. Evidence was reported according to the WikiGuidelines charter: clear recommendations were established only when reproducible, prospective, controlled studies provided hypothesis-confirming evidence. In the absence of such data, clinical reviews were crafted discussing the risks and benefits of different approaches.
    Findings: A total of 51 members from 10 countries reviewed 587 articles and submitted information relevant to 4 sections: establishing the diagnosis of IE (9 questions); multidisciplinary IE teams (1 question); prophylaxis (2 questions); and treatment (5 questions). Of 17 unique questions, a clear recommendation could only be provided for 1 question: 3 randomized clinical trials have established that oral transitional therapy is at least as effective as intravenous (IV)-only therapy for the treatment of IE. Clinical reviews were generated for the remaining questions.
    Conclusions and relevance: In this consensus statement that applied the WikiGuideline method for clinical guideline development, oral transitional therapy was at least as effective as IV-only therapy for the treatment of IE. Several randomized clinical trials are underway to inform other areas of practice, and further research is needed.
    MeSH term(s) Adult ; Humans ; Consensus ; Endocarditis/diagnosis ; Endocarditis/therapy ; Endocarditis, Bacterial/prevention & control ; Prospective Studies ; Practice Guidelines as Topic
    Language English
    Publishing date 2023-07-03
    Publishing country United States
    Document type Journal Article ; Research Support, Non-U.S. Gov't
    ISSN 2574-3805
    ISSN (online) 2574-3805
    DOI 10.1001/jamanetworkopen.2023.26366
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  9. Article: pH Dependence of charge transfer between tryptophan and tyrosine in dipeptides.

    Reece, Steven Y / Stubbe, Joanne / Nocera, Daniel G

    Biochimica et biophysica acta

    2005  Volume 1706, Issue 3, Page(s) 232–238

    Abstract: ... of charge transfer in W-Y and Ac-W-Y dipeptides as a function of pH. Excitation with 266-nm nanosecond ... laser pulses produces both W (or [WH](+), depending on pH) and Y. Between pH 6 and 10, W to was found ... to oxidize Y with k(X)=9.0x10(4) s(-1) and 1.8x10(4) s(-1) for the W-Y and Ac-W-Y dipeptide systems ...

    Abstract Time-resolved absorption spectroscopy has been employed to study the directionality and rate of charge transfer in W-Y and Ac-W-Y dipeptides as a function of pH. Excitation with 266-nm nanosecond laser pulses produces both W (or [WH](+), depending on pH) and Y. Between pH 6 and 10, W to was found to oxidize Y with k(X)=9.0x10(4) s(-1) and 1.8x10(4) s(-1) for the W-Y and Ac-W-Y dipeptide systems, respectively. The intramolecular charge transfer rate increases as the pH is lowered over the range 6>pH>2. For 10<pH<12, the rate of radical transport for the W-<mark>Y dipeptide decreases and becomes convoluted with other radical decay processes, the timescales of which have been identified in studies of control dipeptides Ac-F-Y and W-F. Further increases in pH prompt the reverse reaction to occur, W-Y-->W-Y(-) (Y(-), tyrosinate anion), with a rate constant of k(X)=1.2x10(5) s(-1). The dependence of charge transfer directionality between W and Y on pH is important to the enzymatic function of several model and natural biological systems as discussed here for ribonucleotide reductase.
    MeSH term(s) Dipeptides/chemistry ; Hydrogen-Ion Concentration ; Nuclear Magnetic Resonance, Biomolecular ; Protons ; Spectrophotometry, Ultraviolet ; Tryptophan/chemistry ; Tyrosine/chemistry
    Chemical Substances Dipeptides ; Protons ; Tyrosine (42HK56048U) ; Tryptophan (8DUH1N11BX)
    Language English
    Publishing date 2005-02-17
    Publishing country Netherlands
    Document type Journal Article ; Research Support, U.S. Gov't, P.H.S.
    ZDB-ID 60-7
    ISSN 1879-2596 ; 1879-260X ; 1872-8006 ; 1879-2642 ; 1879-2618 ; 1879-2650 ; 0006-3002 ; 0005-2728 ; 0005-2736 ; 0304-4165 ; 0167-4838 ; 1388-1981 ; 0167-4889 ; 0167-4781 ; 0304-419X ; 1570-9639 ; 0925-4439 ; 1874-9399
    ISSN (online) 1879-2596 ; 1879-260X ; 1872-8006 ; 1879-2642 ; 1879-2618 ; 1879-2650
    ISSN 0006-3002 ; 0005-2728 ; 0005-2736 ; 0304-4165 ; 0167-4838 ; 1388-1981 ; 0167-4889 ; 0167-4781 ; 0304-419X ; 1570-9639 ; 0925-4439 ; 1874-9399
    DOI 10.1016/j.bbabio.2004.11.011
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  10. Article: Photoactive peptides for light-initiated tyrosyl radical generation and transport into ribonucleotide reductase.

    Reece, Steven Y / Seyedsayamdost, Mohammad R / Stubbe, Joanne / Nocera, Daniel G

    Journal of the American Chemical Society

    2007  Volume 129, Issue 27, Page(s) 8500–8509

    Abstract: ... mer peptide bound to alpha2. This peptide, Y-R2C19, is identical to the C-terminal peptide tail ... radical (*-BPA), and Y* photoproducts on (i) BPA-Y and Anq-Y dipeptides and (ii) BPA/Anq-Y-R2C19 peptides ...

    Abstract The mechanism of radical transport in the alpha2 (R1) subunit of class I E. coli ribonucleotide reductase (RNR) has been investigated by the phototriggered generation of a tyrosyl radical, *Y356, on a 20-mer peptide bound to alpha2. This peptide, Y-R2C19, is identical to the C-terminal peptide tail of the beta2 (R2) subunit and is a known competitive inhibitor of binding of the native beta2 protein to alpha2. *Y356 radical initiation is prompted by excitation (lambda >or= 300 nm) of a proximal anthraquinone, Anq, or benzophenone, BPA, chromophore on the peptide. Transient absorption spectroscopy has been employed to kinetically characterize the radical-producing step by time resolving the semiquinone anion (Anq*-), ketyl radical (*-BPA), and Y* photoproducts on (i) BPA-Y and Anq-Y dipeptides and (ii) BPA/Anq-Y-R2C19 peptides. Light-initiated, single-turnover assays have been carried out with the peptide/alpha2 complex in the presence of [14C]-labeled cytidine 5'-diphosphate substrate and ATP allosteric effector. We show that both the Anq- and BPA-containing peptides are competent in deoxycytidine diphosphate formation and turnover occurs via Y731 to Y730 to C439 pathway-dependent radical transport in alpha2. Experiments with the Y730F mutant exclude a direct superexchange mechanism between C439 and Y731 and are consistent with a PCET model for radical transport in which there is a unidirectional transport of the electron and proton transport among residues of alpha2.
    MeSH term(s) Free Radicals ; Light ; Peptides/chemistry ; Photochemistry ; Ribonucleotide Reductases/chemistry ; Tyrosine/chemistry
    Chemical Substances Free Radicals ; Peptides ; Tyrosine (42HK56048U) ; Ribonucleotide Reductases (EC 1.17.4.-)
    Language English
    Publishing date 2007-07-11
    Publishing country United States
    Document type Journal Article ; Research Support, N.I.H., Extramural
    ZDB-ID 3155-0
    ISSN 1520-5126 ; 0002-7863
    ISSN (online) 1520-5126
    ISSN 0002-7863
    DOI 10.1021/ja0704434
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