Sequential Deoxygenation of CO and NO via Redox-Control of a Pyridinediimine Ligand with a Hemilabile Phosphine.

The deoxygenation of environmental pollutants CO and NO to form value-added products is reported. CO reduction with subsequent CO release and NO conversion to NO are achieved via the starting complex Fe(PDI)Cl (). contains the redox-active pyridinediimine (PDI) ligand with a hemilabile phosphine located in the secondary coordination sphere.

Open-source Software Sustainability Models: Initial White Paper From the Informatics Technology for Cancer Research Sustainability and Industry Partnership Working Group.

Background: The National Cancer Institute Informatics Technology for Cancer Research (ITCR) program provides a series of funding mechanisms to create an ecosystem of open-source software (OSS) that serves the needs of cancer research. As the ITCR ecosystem substantially grows, it faces the challenge of the long-term sustainability of the software being developed by ITCR grantees. To address this challenge, the ITCR sustainability and industry partnership working group (SIP-WG) was convened in 2019.

NO Coupling by Nonclassical Dinuclear Dinitrosyliron Complexes to Form NO Dictated by Hemilability.

Selective coupling of NO by a nonclassical dinuclear dinitrosyliron complex (D-DNIC) to form NO is reported. The coupling is facilitated by the pyridinediimine (PDI) ligand scaffold, which enables the necessary denticity changes to produce mixed-valent, electron-deficient tethered DNICs. One-electron oxidation of the [{Fe(NO)}] complex Fe(PDI)(NO) () results in NO coupling to form NO via the mixed-valent {[Fe(NO)]} species, which possesses an electron-deficient four-coordinate {Fe(NO)} site, crucial in N-N bond formation.

Introduction to Artificial Intelligence and Machine Learning for Pathology.

Context.—: Recent developments in machine learning have stimulated intense interest in software that may augment or replace human experts. Machine learning may impact pathology practice by offering new capabilities in analysis, interpretation, and outcomes prediction using images and other data.

Complete denitrification of nitrate and nitrite to N gas by samarium(II) iodide.

The reduction of nitrogen oxides (NxOyn-) to dinitrogen gas by samarium(ii) iodide is reported. The polyoxoanions nitrate (NO3-) and nitrite (NO2-), as well as nitrous oxide (N2O) and nitric oxide (NO) were all shown to react with stoichiometric amounts of SmI2 in THF for the complete denitrification to N2.

Harnessing the active site triad: merging hemilability, proton responsivity, and ligand-based redox-activity.

Metalloenzymes catalyze many important reactions by managing the proton and electron flux at the enzyme active site. The motifs utilized to facilitate these transformations include hemilabile, redox-active, and so called proton responsive sites. Given the importance of incorporating and understanding these motifs in the area of coordination chemistry and catalysis, we highlight recent milestones in the field.

Hemilabile Proton Relays and Redox Activity Lead to {FeNO} and Significant Rate Enhancements in NO Reduction.

Incorporation of the triad of redox activity, hemilability, and proton responsivity into a single ligand scaffold is reported. Due to this triad, the complexes Fe(PDI)(CO) (3) and Fe(PDI)(CO) (4) display 40-fold enhancements in the initial rate of NO reduction, with respect to Fe(PDI)(CO) (7). Utilizing the proper sterics and p K of the pendant base(s) to introduce hemilability into our ligand scaffolds, we report unusual {FeNO} mononitrosyl iron complexes (MNICs) as intermediates in the NO reduction reaction.

Career Paths of Pathology Informatics Fellowship Alumni.

Background: The alumni of today's Pathology Informatics and Clinical Informatics fellowships fill diverse roles in academia, large health systems, and industry. The evolving training tracks and curriculum of Pathology Informatics fellowships have been well documented. However, less attention has been given to the posttraining experiences of graduates from informatics training programs.

Uncoupled Redox-Inactive Lewis Acids in the Secondary Coordination Sphere Entice Ligand-Based Nitrite Reduction.

Metal complexes composed of redox-active pyridinediimine (PDI) ligands are capable of forming ligand-centered radicals. In this Forum article, we demonstrate that integration of these types of redox-active sites with bioinspired secondary coordination sphere motifs produce direduced complexes, where the reduction potential of the ligand-based redox sites is uncoupled from the secondary coordination sphere. The utility of such ligand design was explored by encapsulating redox-inactive Lewis acidic cations via installation of a pendant benzo-15-crown-5 in the secondary coordination sphere of a series of Fe(PDI) complexes.

Ligand-based reduction of nitrate to nitric oxide utilizing a proton-responsive secondary coordination sphere.

Utilizing the proton-responsive pyridinediimine ligand [(2,6-PrCH)(N[double bond, length as m-dash]CMe)(N(Pr)CH)(N[double bond, length as m-dash]CMe)CHN] (didpa), the ligand-based reduction of nitrate (NO) to nitric oxide (NO) was achieved. The bioinspired [Fe(Hdidpa)(CO)] was shown to react with tetrabutylammonium nitrate to form the dinitrosyl iron complex [Fe(didpa)(NO)]. The didpa scaffold was shown to provide two electrons for the net reduction of NO to NO in 43% yield.

The feasibility and effectiveness of Catch It, an innovative CBT smartphone app.

Background: The widespread use of smartphones makes effective therapies such as cognitive-behavioural therapy (CBT) potentially accessible to large numbers of people.

Aims: This paper reports the usage data of the first trial of Catch It, a new CBT smartphone app.

Method: Uptake and usage rates, fidelity of user responses to CBT principles, and impact on reported negative and positive moods were assessed.

Nitrite reduction by a pyridinediimine complex with a proton-responsive secondary coordination sphere.

The proton-responsive pyridinediimine ligand, (DEA)PDI (where (DEA)PDI = [(2,6-(i)PrC6H3)(N[double bond, length as m-dash]CMe)(N(Et)2C2H4)(N[double bond, length as m-dash]CMe)C5H3N]) was utilized for the reduction of NO2(-) to NO. Nitrite reduction is facilitated by the protonated secondary coordination sphere coupled with the ligand-based redox-active sites of [Fe(H(DEA)PDI)(CO)2](+) and results in the formation of the {Fe(NO)2}(9) DNIC, [Fe((DEA)PDI)(NO)2](+).

Stabilization of a Zn(ii) hydrosulfido complex utilizing a hydrogen-bond accepting ligand.

Hydrogen sulfide (H2S) has gained recent attention as an important biological analyte that interacts with bioinorganic targets. Despite this importance, stable H2S or HS(-) adducts of bioinorganic metal complexes remain rare due to the redox activity of sulfide and its propensity to form insoluble metal sulfides. We report here reversible coordination of HS(-) to Zn(didpa)Cl2, which is enabled by an intramolecular hydrogen bond between the zinc hydrosulfido product and the pendant tertiary amine of the didpa ligand.

Perceptions of pathology informatics by non-informaticist pathologists and trainees.

Background: Although pathology informatics (PI) is essential to modern pathology practice, the field is often poorly understood. Pathologists who have received little to no exposure to informatics, either in training or in practice, may not recognize the roles that informatics serves in pathology. The purpose of this study was to characterize perceptions of PI by noninformatics-oriented pathologists and to do so at two large centers with differing informatics environments.

Square planar Cu(I) stabilized by a pyridinediimine ligand.

A set of distorted square planar Cu(I) complexes were synthesized and characterized utilizing the sterically encumbering pyridinediimine ligand, (iPr)PDI (where (iPr)PDI = 2,6-(2,6-(i)Pr2C6H3N=CMe)2C5H3N). The oxidation state of the Cu center(s) were elucidated to be Cu(I) with a neutral PDI ligand system based on structural, spectroscopic, and computational data.

Prediction of primary breast cancer size and T-stage using micro-computed tomography in lumpectomy specimens.

Background: Histopathology is the only accepted method to measure and stage the breast tumor size. However, there is a need to find another method to measure and stage the tumor size when the pathological assessment is not available. Micro-computed tomography.

Pyridinediimine Iron Complexes with Pendant Redox-Inactive Metals Located in the Secondary Coordination Sphere.

A series of pyridinediimine (PDI) iron complexes that contain a pendant 15-crown-5 located in the secondary coordination sphere were synthesized and characterized. The complex Fe((15c5)PDI)(CO)2 (2) was shown in both the solid state and solution to encapsulate redox-inactive metal ions. Modest shifts in the reduction potential of the metal-ligand scaffold were observed upon encapsulation of either Na(+) or Li(+).

Probing the Protonation State and the Redox-Active Sites of Pendant Base Iron(II) and Zinc(II) Pyridinediimine Complexes.

Utilizing the pyridinediimine ligand [(2,6-(i)PrC6H3)N═CMe)(N((i)Pr)2C2H4)N═CMe)C5H3N] (didpa), the zinc(II) and iron(II) complexes Zn(didpa)Cl2 (1), Fe(didpa)Cl2 (2), [Zn(Hdidpa)Cl2][PF6] (3), [Fe(Hdidpa)Cl2][PF6] (4), Zn(didpa)Br2 (5), and [Zn(Hdidpa)Br2][PF6] (6), Fe(didpa)(CO)2 (7), and [Fe(Hdidpa)(CO)2][PF6] (8) were synthesized and characterized. These complexes allowed for the study of the secondary coordination sphere pendant base and the redox-activity of the didpa ligand scaffold. The protonated didpa ligand is capable of forming metal halogen hydrogen bonds (MHHBs) in complexes 3, 4, and 6.

Whole slide imaging for human epidermal growth factor receptor 2 immunohistochemistry interpretation: Accuracy, Precision, and reproducibility studies for digital manual and paired glass slide manual interpretation.

Background: The use of digital whole slide imaging for human epidermal growth factor receptor 2 (HER2) immunohistochemistry (IHC) could create improvements in workflow and performance, allowing for central archiving of specimens, distributed and remote interpretation, and the potential for additional computerized automation.

Procedures: The accuracy, precision, and reproducibility of manual digital interpretation for HER2 IHC were determined by comparison to manual glass slide interpretation. Inter- and intra-pathologist reproducibility and precision between the glass slide and digital interpretations of HER2 IHC were determined in 5 studies using DAKO HercepTest-stained breast cancer slides with the Philips Digital Pathology System.

Computational Pathology: A Path Ahead.

Context: We define the scope and needs within the new discipline of computational pathology, a discipline critical to the future of both the practice of pathology and, more broadly, medical practice in general.

Objective: To define the scope and needs of computational pathology.

Data Sources: A meeting was convened in Boston, Massachusetts, in July 2014 prior to the annual Association of Pathology Chairs meeting, and it was attended by a variety of pathologists, including individuals highly invested in pathology informatics as well as chairs of pathology departments.

Longitudinal engagement of pathology residents: a proposed approach for informatics training.

Objectives: The intersecting of pathology training and practice and the utilization of information technology has become an increasingly common occurrence, and the most effective means of teaching residents informatics during these invaluable years has yet to be firmly established.

Methods: In offering the idea of longitudinal engagement that stresses early and extended trainee involvement, we attempt to provide a different manner of helping address some of the leading time-limited issues surrounding education in informatics.

Results: The proposed model is intended to allow building off a base of fundamentals reached through introductory didactics, exposure to and active participation in departmental and hospital-wide administrative bodies, refining of initial skills gained through frequent mentoring and coaching, and combining these cumulative knowledge and experiential underpinnings with graduated responsibility in a particular area of expertise.

The ongoing evolution of the core curriculum of a clinical fellowship in pathology informatics.

The Partners HealthCare system's Clinical Fellowship in Pathology Informatics (Boston, MA, USA) faces ongoing challenges to the delivery of its core curriculum in the forms of: (1) New classes of fellows annually with new and varying educational needs and increasingly fractured, enterprise-wide commitments; (2) taxing electronic health record (EHR) and laboratory information system (LIS) implementations; and (3) increasing interest in the subspecialty at the academic medical centers (AMCs) in what is a large health care network. In response to these challenges, the fellowship has modified its existing didactic sessions and piloted both a network-wide pathology informatics lecture series and regular "learning laboratories". Didactic sessions, which had previously included more formal discussions of the four divisions of the core curriculum: Information fundamentals, information systems, workflow and process, and governance and management, now focus on group discussions concerning the fellows' ongoing projects, updates on the enterprise-wide EHR and LIS implementations, and directed questions about weekly readings.

Pathology informatics fellowship training: Focus on molecular pathology.

Background: Pathology informatics is both emerging as a distinct subspecialty and simultaneously becoming deeply integrated within the breadth of pathology practice. As specialists, pathology informaticians need a broad skill set, including aptitude with information fundamentals, information systems, workflow and process, and governance and management. Currently, many of those seeking training in pathology informatics additionally choose training in a second subspecialty.