Direct Donation Research Articles

Feminism and the Realpolitik of Elite Philanthropy

Feminism and the Realpolitik of Elite Philanthropy Francesca Sawaya (bio) Joan Marie Johnson. Funding Feminism: Monied Women, Philanthropy, and the Women's Movement, 1870–1967. Chapel Hill: University of North Carolina Press, 2017. xi + 303. Illustrations, notes, bibliography, index. $39.95. Molly McClain. Ellen Browning Scripps: New Money and American Philanthropy. Lincoln: University of Nebraska Press, 2017. xi + 303. Illustrations, notes, bibliography, index. $34.95. In recent years, historians have returned to the "paradox," as Steve Fraser and Gary Gerstle put it in Ruling America (2005), that elites rule in our democracy. "Sometimes they seem to rule with the people's interest in mind," Fraser and Gerstle write, "sometimes not" (p. 1). Philanthropy has been one important practice that enables scholars to study that paradox. Because philanthropy is often studied as a ruling class phenomenon, however, scholars have tended to ignore the difference that gender, race, or ethnicity has on this class practice. Both Joan Marie Johnson's Funding Feminism: Monied Women, Philanthropy, and the Women's Movement, 1870–1967 and Molly McClain's Ellen Browning Scripps: New Money and American Philanthropy expand our understanding of twentieth-century philanthropy by focusing specifically on gender—on elite white women's involvement in ruling America. How did wealthy women engage in philanthropy? What did wealthy women's secondary status—at least relative to wealthy men—mean for their philanthropy? Was their philanthropy different than elite men's? Johnson argues directly and McClain suggests that wealthy white women's experiences of (relative) inequality meant that their philanthropy was more progressive and more engaged by the "people's interest" than the philanthropy practiced by elite men. Johnson furthermore redefines philanthropy, reading it as the realpolitik of elite rule in a capitalist democracy. Johnson's book therefore makes an invaluable contribution to the history of both philanthropy and the women's rights movement in the United States, compelling us to confront important questions about the challenges for democracies when money can dictate political outcomes—even democratic outcomes. [End Page 605] Funding Feminism "follows the money" to provide a riveting new vantage point on the fight for women's rights in the twentieth century. Johnson's thesis is that "the women's movement owes its success to the financial backing of [wealthy] women" (p. 5). Arguing that large-scale "scientific philanthropy" emerges simultaneously with "an organized women's rights movement" (p. 4), Johnson asserts that the "timing and success" of the major gains women made in the twentieth century in suffrage, labor, higher education, and birth control were "dependent on the major gifts only the wealthy could give" (p. 14). Considered within the historiography on philanthropy, there is a bit of sleight of hand here: almost none of the women Johnson tracks created nonprofit foundations—the characteristic expression of scientific philanthropy. Furthermore, even recent studies of philanthropy often focus on it as a "third sector" outside of government and business and therefore exclude direct political donations from their purview. Nonetheless, Johnson is usefully polemical here: elite philanthropy is an expression of the money/power nexus in the United States, she argues, and there is no more clear expression of that than political donations. Philanthropy is the top-down realpolitik of capitalist democracy. As Johnson writes, "access to political power" has always depended on "access to funding" (p. 18). The 2010 Citizens United decision, she says, demonstrates how extreme this dependency has become in our own day, but it also demonstrates that "continuity rather than change over time" is what we must track in political donations of elites (p. 11). Johnson, however, usefully complicates her definition of philanthropy as top-down realpolitik in terms of the women's movement. First of all, she points out that wealthy women's philanthropy, as opposed to that of men, was a weapon of the comparatively weak: "At a time when … [women] could not vote and when education, professions, and other opportunities were limited for them, philanthropy offered a unique tool" (p. 7). Indeed, because of elite women's secondary status legally and politically, and especially because of their financial vulnerability, their donations and activism were galvanized, according to Johnson, by a situated and experiential understanding of inequality. Like "many philanthropists...

Near infrared fluorescent dual ligand functionalized Au NCs based multidimensional sensor array for pattern recognition of multiple proteins and serum discrimination

Here, a multidimensional sensor array capable of analyzing various proteins and discriminating between serums from different stages of breast cancer patients were developed based on six kinds of near infrared fluorescent dual ligand functionalized Au NCs (functionalized with different amino acids) as sensing receptors. These six kinds of different amino acids functionalized Au NCs were synthesized for the first time within 2h due to the direct donation of delocalized electrons of electron-rich atoms or groups of the ligands to the Au core. Based on this, ten proteins could be simultaneously and effectively discriminated by this “chemical nose/tongue” sensor array. Linear discrimination analysis (LDA) of the response patterns showed successful differentiation of the analytes at concentrations as low as 10nM with high identification accuracy. Isothermal titration calorimetry (ITC) experiment illustrates that Au NCs interacted with proteins mainly by hydrogen bonding and van der Waals forces. Furthermore, the greatest highlight of this sensor array is demonstrated by successfully discriminating between serums from different stages of breast cancer patients (early, middle and late) and healthy people, suggesting great potential for auxiliary diagnosis.

Sperm Donation and the Right to Privacy

Sperm donation is an increasingly common method of assisted reproduction. In the debate on sperm donation, the right to privacy — construed as a right that refers to the limits of the realm of information to which others have access — plays a pivotal role with regard to two questions. The first question is whether the sperm donor’s right to privacy implies his right to retain his anonymity, the second is whether the gamete recipients’ right to privacy entitles them to withhold information about the circumstances of their conception from their donor-conceived offspring. In this contribution, I tackle these two interrelated questions. In part (1), I defend the view that there is a prima facie right of sperm donors to remain anonymous. Part (2) widens the perspective by taking into consideration the welfare of donor-conceived offspring. I argue that anonymity may harm the child only if the gametes’ recipients decide to disclose information about the circumstances of her birth to the child. Non-disclosure of these circumstances, however, is morally problematic because it may not necessarily harm, but wrong the child. In section (3), I attempt to rebut some arguments in defense of non-disclosure. In part (4), I defend the view that the best practice of sperm donation would be ‘direct donation’, i.e. that the identity of the donor is known from the time of conception. Part (5) concludes.

On the interrelation between the consumption of impure public goods and the provision of direct donations: Theory and empirical evidence

This paper investigates the extent to which the possibility of direct donations to a public good may substitute an individual’s consumption of impure public goods. Theoretically, we derive conditions under which donations may serve as substitutes or complements for the consumption of private and impure public goods. We then empirically test our predictions in the context of climate change mitigation using data from online-representative surveys among citizens in Germany and the U.S. Our empirical results indicate a rather complementary relationship between offsetting and other pro-environmental activities in both countries, although individuals substitute certain clean consumption alternatives by offsetting if they lay a sufficiently large weight on environmental preference or if offsetting is perceived to be relatively effective in providing the public good climate protection.

The Effects of Donation through Corporate Foundations on Consumers

Even with the importance of corporate foundations in corporate social responsibility (CSR hereafter) activities, little research has been conducted in this area. Most of the existing literature on corporate foundations deals with two issues: the reasons that firms set up foundations and activities of the foundations. These studies mainly focus on firms` perspective and investigate the reason why firms set up foundations and what activities these firms do. Most related studies to the present article are CSR governance. Still, these studies do not involve consumers. However, the donation through the corporate foundation is growing fast among activities done by foundations. A Strategic decision on donation should involve consumers. The corporate donation is strongly related to corporate or brand attitude consumers hold. Therefore, it is important to understand how consumers perceive donation through foundation compared to direct donation. In this sense, the present study investigates how consumers perceive foundations. First, an investigation was performed to determine whether donation through foundations influences consumers` attitude toward the founding firm. Next, the donation through foundations and direct donation were compared on two important variables, consumers` attribution of the firm`s motive for CSR and attitude toward the firm. An experiment using scenarios was used to test the hypotheses. To create scenarios, the firm and foundation were selected first. A real company was used because the attitude change (post-attitude - pre-attitude) was used as a dependent variable. Three criteria were used to select and KT & G and KT & G Social Welfare Foundation were used in the scenario. Student sample was used and total 311 responses were used for the analysis. The result revealed that donation through foundations influences consumer attitude toward the firm positively and that it is more influential in bringing positive attribution. Meanwhile, the direct donation is more effective in improving attitude toward the firm. the results have both theoretical and practical implications. Theoretically, this study is most meaningful in that it supported the importance of corporate foundations empirically. Practically, the result of the study gives implications to firms that strategic decision should be made according to the purpose of the donation. Also, the result can be utilized meaningfully for the firm with bad reputations.

Chain Length and Solvent Control over the Electronic Properties of Alkanethiolate-Protected Gold Nanoparticles at the Molecule-to-Metal Transition.

Alkanethiolate protected gold nanoparticles are one of the most widely used systems in modern science and technology, where the emergent electronic properties of the gold core are valued for use in applications such as plasmonic solar cells, photocatalysis, and photothermal heating. Though choice in alkane chain length is not often discussed as a way in which to control the electronic properties of these nanoparticles, we show that the chain length of the alkyl tail exerts clear control over the electronic properties of the gold core, as determined by conduction electron spin resonance spectroscopy. The control exerted by chain length is reported on by changes to the g-factor of the metallic electrons, which we can relate to the average surface potential on the gold core. We propose that the surface potential is modulated by direct charge donation from the ligand to the metal, resulting from the formation of a chemical bond. Furthermore, the degree of charge transfer is controlled by differences between the dielectric constant of the medium and the ligand shell. Together, these observations are used to construct a simple electrostatic model that provides a framework for understanding how surface chemistry can be used to modulate the electronic properties of gold nanoparticles.

MECHANISMS FOR THE FORMATION OF FIVE-MEMBERED RINGS IN ETHENE ADDITION REACTIONS WITH AZOMETHINE YLIDE AND ALLYL ANION

The mechanisms of pyrrolidine and cyclopentyl anion formation from ethene and allyl anion, azomethine ylide, as well as their electron-rich and electron-poor derivatives was studied for a wide range of systems by ab initio calculations using the MP2/6-311++G(d,p) basis set. The calculations showed that during the interaction of allyl anion with ethene the five-center intermediate species with C S symmetry was stabilized by direct electron donation effect, while in the case of azomethine ylide it was simultaneously affected by direct and reverse donation mechanisms. The introduction of electron-withdrawing substituents at the central position of allyl anion enabled a concerted synchronous cycloaddition process, while the reaction proceeded by single-step mechanism in the case of azomethine ylide having electron-donating or electron-withdrawing substituents at the nitrogen atom, except with sterically congested reactants. Authors: Mikhail E. Kletskii*, Oleg N. Burov, Nikita S. Fedik, Sergey V. Kurbatov

Mechanisms for the formation of five-membered rings in ethene addition reactions with azomethine ylide and allyl anion

The mechanisms of pyrrolidine and cyclopentyl anion formation in the ethene addition reactions to allyl anion and azomethine ylide, as well as to their derivatives with π-electron-donating and π-electron-withdrawing substituents was studied for a wide range of systems by ab initio calculations using the MP2/6-311++G(d,p) basis set. The calculations showed that during the interaction of allyl anion with ethene the five-center intermediate species with CS symmetry was stabilized by direct π-electron donation effect, while in the case of azomethine ylide it was simultaneously affected by direct and reverse π-donation mechanisms. The introduction of π-electronwithdrawing substituents at the central position of allyl anion enabled a concerted synchronous cycloaddition process, while the reaction proceeded by single-step mechanism in the case of azomethine ylide having π-electron-donating or π-electron-withdrawing substituents at the nitrogen atom, except with sterically hindered reactants.

Auditor Specialization in the Nonprofit Sector

While Big 4 has been an effective audit quality measure in many industries, it has had mixed results in the nonprofit sector. This paper considers the use of industry specialization as an audit quality measure and investigates the determinants and effects of selecting an industry specialist on nonprofit organizations in the United States. Our results indicate that the determinants and consequences of selecting an industry specialist auditor vary significantly from those associated with Big 4 audit firm selection but are similar to those of industry specialist auditor selection in the public company sector. We find industry specialist auditor choice is associated with higher governance quality (higher governance index, larger boards, and more independent boards) and higher financial risk, indicating auditor selection is a complement in the overall governance system of nonprofit organizations. Moreover, specialist auditors have a shorter audit report lag than both non-specialist auditors and Big 4 auditors, an indicator of higher auditor reporting quality. Nonprofits audited by specialist auditors also see a future increase in direct donations and a decrease in government grants for funding their operations. We conclude that specialist auditors help nonprofits diversify their revenue streams, important as it helps strengthen their financial position, stability and viability.

Managing a Corporate Brand in a Challenging Stakeholder Environment: Charity Branding

The modern charity is increasingly forced to contend with a limited pool of resources to carry out its core social mission. Decline in government support (Hibbert and Horne 1995) and direct donations (Williamson 2003), as well as the growing number of charities (Liao, Foreman, and Sargeant 2001), has seen the charity industry become increasingly competitive. This has led to a redefinition of what it means to be a charity in terms of the internal structure of the organization and the resultant complexity of the stakeholder environment. To better appreciate the fundamental tensions inherent in modern religious charity organizations and how these challenges affect their corporate branding strategies, the institutional logics framework is used to interpret the underlying pressures. The impact of these pressures is a complex stakeholder environment where the expectations of two somewhat disparate groups—those who need care and provide care, and those who provide the resources to enable that care to continue—must be contemplated. The implications of this institutional pluralism (Kraatz and Block 2008) and consequent complex stakeholder environment for the management of corporate branding of charities are exemplified using the case of a religious charity that changed its corporate brand name.

Multiple Information Signals in the Market for Charitable Donations

AbstractWe find evidence indicating that donors use third‐party rating information when they donate to U.S. nonprofit organizations (nonprofits). Specifically, using a sample of over 3,800 unique nonprofits rated by the three largest charity rating organizations in 2007, and over 12,000 unrated control nonprofits, we find that rated nonprofits have significantly higher direct donations than unrated charities. We also hypothesize and find that nonprofits with ratings from multiple rating organizations receive incrementally higher levels of donations. In addition, although charities that receive a positive rating have higher levels of donor support than those receiving a negative rating, both positively and negatively rated nonprofits receive a higher level of direct donations than unrated nonprofits. Finally, we find that nonprofits with consistently good ratings receive higher donations than those with mixed or consistently negative ratings, indicating the donor community values consistency across the three rating agencies.

Features and Ethical Considerations Associated With Living Kidney and Liver Transplantations in South Korea

When the Organ Transplantation Act came into effect in 2000 in South Korea, living organ donations were legalized and the Korean Network for Organ Sharing (KONOS) had a duty to approve the application of donation. The number of living organ donors has increased and the waiting time of recipients has been steady or decreased. The Organ Transplantation Act mainly focuses on the informed consent process of donations, so unrelated directed donations are permitted unless there is a suspicion of organ trafficking. But the annual reports show that directed donations of unrelated and related donors may have an ethical concern about organ sales. The donations of family members show another ethical concern. The numbers of ABO-incompatible transplantations have steadily increased since 2008, and lineal descendants, including minors, comprised 61% of living liver donors in 2012. Addressing the unethical practices without inhibiting living organ donations is the current task in South Korea. Private agencies have actively operated the living organ donations programs. The web-based computerized organ exchange program has been cooperatively run by hospital-based organizations. The strict legal regulations that could decrease living organ donations are hard to adopt. In the current situation, the functions of the official system need to be more developed. A national organ exchange program run by KONOS could be an option which could reduce ABO-incompatible transplantations and relieve the ethical concern of organ sales in unrelated directed donations.

Multiple Information Signals in the Market for Charitable Donations

We find robust evidence which indicates that nonprofit donors incorporate third party rating information into their decision to give. Specifically, using a sample of over 3,800 unique nonprofit organizations rated by the three largest charity rating organizations and over 12,000 unrated control firms, we find that rated organizations have significantly higher direct donations than unrated charities. Given our ability to simultaneously test ratings from all three ratings agencies, we are also able to identify an incremental increase in donations accruing to organizations that receive multiple ratings. Additionally, although organizations that receive a positive assessment are associated with a higher level of public support relative to organizations receiving a negative assessment, our results indicate that both positive and negative rated organizations in fact receive a higher level of direct donations relative to unrated organizations. Finally, we find that the market values consistency across the three rating agencies, supporting the notion that noisy signals are valued less by donors.

Bruker proudly contributes to IYCR

Bruker congratulates the IUCR to the proclamation of the International Year of Crystallography (IYCR). As one of the world's leading analytical instrumentation companies, Bruker enthusiastically supports the IYCr activities to increase public awareness of the science of crystallography with a variety of activity. In addition to a direct donation to the IUCR our customers participate in the IYCR's Openlab initiative with state-of-the-art instrument in Pakistan, South Africa, United Arab Emirates and Vietnam. During the entire year Bruker supports meetings and conferences and organizes workshops and user meetings to inspire new blood as well as old hands. In countries with a small base of installed instruments Bruker contributes to the OpenLab initiative loaning a complete for the entire year 2014. Education and research at sites in Ivory Coast, South Africa, Morocco, Indonesia & Brazil benefit from this single crystal X-ray diffraction solution. The system is covered by a free-of-charge service contract and warranty. Personnel from each site receive training prior to the arrival of the instrument and get unlimited support by Bruker's service desk. Bruker is happy to contribute with knowledge, instrumentation and sponsorship to the success of the IYCr all over the planet. We are convinced that the combined efforts of the global crystallographic community demonstrate the importance of crystallography in most technological developments and increase interest in this interdisciplinary method. The talk will provide an summary on the events held, the impact achieved and provide an outlook on activities planned for the remaining IYCR.

Living Kidney Donors and Their Recipients: Who Wants to Know What?

Background: Kidney recipients are informed whether their donor (living or deceased) is high risk for HIV/AIDS, but otherwise are not provided any donor information. UNOS policy 12.2h authorizes only generic disclosure to living donors. Little is known about donor and recipient attitudes regarding disclosure in direct donations and exchanges or chains. Methods: Online survey link sent to ˜4200 members of National Kidney Foundation list-serv. Results: 396 individuals opened and 323 (7.7%) completed part or all of the survey. 160 self-identified as living or potential living donor and 76 as past or potential recipients of living or deceased donor kidney transplants. Donors were more likely to be female (80.3% v 57.3%, p<0.001) and younger (51.9% < 50 years v 23.7%, p<0.001). Over 80% of recipients and donors supported disclosure of health information about both the donor and the recipient. Recipients were more supportive of disclosing recipient psychiatric issues and recipient high-risk activities to donors (60.0% v 37.7%, p=0.001 and 58.3% v 38.1%, p = 0.004 respectively). Recipients were also more supportive of disclosure of donor history of drug use and high risk sexual activity than were donors (90.7 v 77.8%, p=0.017and 80.3 v 63.5%, p=0.009, respectively). About half thought it was permissible for donors and recipients to go on the Internet to learn more about the other, but only about 1/4 condoned contacting friends of the donor (24.7%) or recipient (26.4%). The majority of both donors and recipients did not think a transplanted kidney that functioned less than a year was of value; although surprisingly, donors were more supportive (40.0% v 23.3%, p=0.014). In chains and exchanges, 2/3 of donors and recipients thought the exchange donor should know if the recipient had a short life expectancy but less than 15% of recipients and donors supported disclosure of social issues like employment status, sexual orientation, and religion. Discussion: Donors and recipients support sharing of health information in direct and exchange transplants, but show lower levels of support for disclosure of psychosocial information (direct > exchanges). Further research is needed to determine if the current policies need revision.

Interaction of ascorbate with photosystem I

Ascorbate is one of the key participants of the antioxidant defense in plants. In this work, we have investigated the interaction of ascorbate with the chloroplast electron transport chain and isolated photosystem I (PSI), using the EPR method for monitoring the oxidized centers [Formula: see text] and ascorbate free radicals. Inhibitor analysis of the light-induced redox transients of P700 in spinach thylakoids has demonstrated that ascorbate efficiently donates electrons to [Formula: see text] via plastocyanin. Inhibitors (DCMU and stigmatellin), which block electron transport between photosystem II and Pc, did not disturb the ascorbate capacity for electron donation to [Formula: see text]. Otherwise, inactivation of Pc with CN(-) ions inhibited electron flow from ascorbate to [Formula: see text]. This proves that the main route of electron flow from ascorbate to [Formula: see text] runs through Pc, bypassing the plastoquinone (PQ) pool and the cytochrome b 6 f complex. In contrast to Pc-mediated pathway, direct donation of electrons from ascorbate to [Formula: see text] is a rather slow process. Oxidized ascorbate species act as alternative oxidants for PSI, which intercept electrons directly from the terminal electron acceptors of PSI, thereby stimulating photooxidation of P700. We investigated the interaction of ascorbate with PSI complexes isolated from the wild type cells and the MenB deletion strain of cyanobacterium Synechocystis sp. PCC 6803. In the MenB mutant, PSI contains PQ in the quinone-binding A1-site, which can be substituted by high-potential electron carrier 2,3-dichloro-1,4-naphthoquinone (Cl2NQ). In PSI from the MenB mutant with Cl2NQ in the A1-site, the outflow of electrons from PSI is impeded due to the uphill electron transfer from A1 to the iron-sulfur cluster FX and further to the terminal clusters FA/FB, which manifests itself as a decrease in a steady-state level of [Formula: see text]. The addition of ascorbate promoted photooxidation of P700 due to stimulation of electron outflow from PSI to oxidized ascorbate species. Thus, accepting electrons from PSI and donating them to [Formula: see text], ascorbate can mediate cyclic electron transport around PSI. The physiological significance of ascorbate-mediated electron transport is discussed.

Points mean prizes: priority points, preferential status and directed organ donation in Israel

The introduction of Israel’s new Organ Transplantation Act in 2010 has enabled the development of a unique priority point system aimed at motivating individual’s to donate their organ. The priority point system rewards those who are willing to donate an organ with preferential status and an increased chance of receiving a donor organ, should they come to be in need of one. Preliminary evidence suggests it has considerable public support among Israelis, who appear willing to redress the challenge posed by those who are willing to accept an organ but not willing to donate. Since the Act’s introduction Israel has witnessed record numbers signing donor cards and there has been a significant increase in the actual numbers of transplants.One aspect of the new Israeli system that has hitherto not much been considered is its tendency towards a communitarian model of organ donation and the implications this change in emphasis may have for the existing ‘opt-in’ model based upon autonomy and consent. Gil Siegel draws our attention to this aspect when he sets out his defence of a proposal he refers to as ‘directed organ donation to other registered donors’, which encourages community responsibility without affecting the established commitment to consent and individual freedom.This commentary provides a brief overview of the new Act and its priority point system. It also examines Siegel’s proposal and considers the implications it may have for equity and justice, personal choice and dispositional authority. It is argued that although the proposal brings with it several inevitable hurdles for policy makers these are not insurmountable. Rather, its extraordinary potential to save life and avoid suffering should prompt urgent action at policy level. If such a scheme was successfully implemented in Israel it would represent a landmark change in organ donation and allocation policy, and set an example from which we all could learn.

Pyrophosphate synthesis in iron mineral films and membranes simulating prebiotic submarine hydrothermal precipitates

Cells use three main ways of generating energy currency to drive metabolism: (i) conversion of adenosine diphosphate (ADP) to adenosine triphosphate (ATP) by the proton motive force through the rotor-stator ATP synthase; (ii) the synthesis of inorganic phosphate∼phosphate bonds via proton (or sodium) pyrophosphate synthase; or (iii) substrate-level phosphorylation through the direct donation from an active phosphoryl donor. A mechanism to produce a pyrophosphate bond as “energy currency” in prebiotic systems is one of the most important considerations for origin of life research. Baltscheffsky (1996) suggests that inorganic pyrophosphate (P2O74-; PPi) may have preceded ATP/ADP as an energy storage molecule in earliest life, produced by an H+ pyrophosphatase. Here we test the hypothesis that PPi could be synthesized in inorganic precipitates simulating hydrothermal chimney structures transected by thermal and/or ionic gradients. Appreciable yields of PPi were obtained via substrate phosphorylation by acetyl phosphate within the iron sulfide/silicate precipitates at temperatures expected for an alkaline hydrothermal system.

Political interaction in the senate: estimating a political “spatial” weights matrix and an application to lobbying behavior

Many motivations exist that cause legislators to behave strategically when voting. These include logrolling, towing the party line, or political favor trading. However, it has proven difficult in the existing literature to uncover the magnitude of the interaction among politicians. This paper takes a “spatial” approach to the problem, using a spatial autoregressive model to not only uncover the magnitude of interactions, but also the direction of the interactions. In contrast to most applications of spatial econometrics, I allow the elements of the spatial weights matrix to be estimated as parameters. The political spatial weights matrix is calculated for 96 senators in the 110th U.S. Congress. Furthermore, in a marginal effects simulation, I calculate the overall effect on voting from “flipping” a senator’s vote, allowing flipped votes to have a cascading effect. I apply these measures to study political fundraising, mildly suggesting that political interest groups direct donations to senators with the most influence.

L-edge X-ray absorption spectroscopy and DFT calculations on Cu2O2 species: direct electrophilic aromatic attack by side-on peroxo bridged dicopper(II) complexes.

The hydroxylation of aromatic substrates catalyzed by coupled binuclear copper enzymes has been observed with side-on-peroxo-dicopper(II) (P) and bis-μ-oxo-dicopper(III) (O) model complexes. The substrate-bound-O intermediate in [Cu(II)2(DBED)2(O)2](2+) (DBED = N,N'-di-tert-butyl-ethylenediamine) was shown to perform aromatic hydroxylation. For the [Cu(II)2(NO2-XYL)(O2)](2+) complex, only a P species was spectroscopically observed. However, it was not clear whether this O-O bond cleaves to proceed through an O-type structure along the reaction coordinate for hydroxylation of the aromatic xylyl linker. Accurate evaluation of these reaction coordinates requires reasonable quantitative descriptions of the electronic structures of the P and O species. We have performed Cu L-edge XAS on two well-characterized P and O species to experimentally quantify the Cu 3d character in their ground state wave functions. The lower per-hole Cu character (40 ± 6%) corresponding to higher covalency in the O species compared to the P species (52 ± 4%) reflects a stronger bonding interaction of the bis-μ-oxo core with the Cu(III) centers. DFT calculations show that 10-20% Hartree-Fock (HF) mixing for P and ~38% for O species are required to reproduce the Cu-O bonding; for the P species this HF mixing is also required for an antiferromagnetically coupled description of the two Cu(II) centers. B3LYP (with 20% HF) was, therefore, used to calculate the hydroxylation reaction coordinate of P in [Cu(II)2(NO2-XYL)(O2)](2+). These experimentally calibrated calculations indicate that the electrophilic attack on the aromatic ring does not involve formation of a Cu(III)2(O(2-))2 species. Rather, there is direct electron donation from the aromatic ring into the peroxo σ* orbital of the Cu(II)2(O2(2-)) species, leading to concerted C-O bond formation with O-O bond cleavage. Thus, species P is capable of direct hydroxylation of aromatic substrates without the intermediacy of an O-type species.