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IN 2017, ACTOR COREY HAWKINS WAS filming a movie in Toronto when he got a call from the producers of the U. S. Open. The singer they had booked to [...]

RICKEY THOMPSON AND I ARE IN THE WOMEN'S SECTION OF THE VAN NUYS Goodwill, playing a game we call 'Is This '90s Fashion?'--and I am losing. I fish out a [...]

Polycyclic aryl naphthalene and tetralin dihydro arylnaphthalene lactone lignans possess anticancer and antibiotic activity. Related furo[3,4-c]pyranones, typified by the sequester-terpenoid isobolivianine, show similar antiproliferative bioactivity. Efficient syntheses of compounds featuring these polycyclic cores have proven challenging due to low yields and poor stereoselectivity. We report the synthesis of chiral cinnamyl but-2-enanoates and 3,3-diphenylallyl-but-2-enoates 1 as new Diels–Alder substrates. These compounds undergo [4 + 2]-cycloadditions to give furo[3,4-c]pyranones 2 in good yield (70%) and diastereoselectivity (7:1), together with naphthyl 3 and dihydronaphthyl tetralins 4 as minor products. Molecular structures and stereochemistries of the major products were verified using X-ray diffraction. Density functional theory calculations revealed that the cycloaddition process involves a bispericyclic/ambimodal process where there is a single transition state that leads to both intramolecular styryl Diels–Alder (ISDA) 3, 4 and intramolecular hetero Diels–Alder (IHDA) cycloadducts 2. With the elevated temperature conditions after cycloaddition, the resulting ISDA cycloadduct either undergoes [3,3]-sigmatropic rearrangement to the more stable major IHDA product or aromatization leading to the phenyltetralin.

Phosphines are extremely important ligands in organometallic chemistry, and their donor or acceptor ability can be measured through the Tolman electron parameter (TEP). Here, we describe the development of a TEP machine learning model (called TEPid) that provides nearly instantaneous calculation of experimentally calibrated CO vibrational stretch frequencies for (R)3P–Ni0(CO)3complexes. This machine learning model with an error of less than 1 cm–1(compared to density functional theory (DFT) calculated values) was developed using >4,000 DFT calculated (R)3P–Ni0(CO)3TEP values and 19 connectivity-based descriptors associated with SMILES strings. We also built a web-based interface to run the machine learning model where phosphine SMILES strings can be entered and TEP values returned. We applied this TEPid model to examine the donor and acceptor capabilities of phosphines in the large Kraken phosphine database. This showed that the Kraken database is skewed toward donor phosphines. In the same spirit of the Kraken database, we generated tens of thousands of new experimentally based phosphines that, when combined with Kraken phosphines, provide an electronically balanced ligand library.

I LOVE MY DAD, who lives in Tennessee, but we are about as dissimilar as two similar people can get. Same personality, but with totally different interests. I'd always wanted [...]

Reactions that result in the oxy-functionalization of sp2C–H bonds to give phenols are relatively rare. Here we report experiments and density functional theory (DFT) calculations that demonstrate selective C–H bond hydroxylation of nitroarenes to their corresponding mono-phenoxide as the exclusive product using OsO4in a highly basic solvent mixture of water, hydroxide, and pyridine. DFT calculations using a mixed explicit/continuum solvent approach indicate that there is likely a mixture of OsO4-hydroxide/pyridine ground-state structures that have competitive reactivity and that the mechanism involves the nucleophilic addition of an anionic metal-oxo species to the arene followed by a hydride transfer process that is different from the standard [3 + 2] mechanism often invoked for the OsO4oxidation of σ and π bonds. This work demonstrates the utility of using a strongly basic solvent for C–H bond oxidation reactions as this effectively converts any reactive phenolic product into the corresponding phenoxide, which is protected and essentially inert to further oxidation by the nucleophilic metal-oxo species.

i dated Elvis because I was trying to get even with Marlon Brando. I found somebody's lingerie in Marlon's house one time, and I was just devastated. Literally the next [...]

MAURICE SAUNDERS HAS a damn-near-perfect smile--so textbook, with teeth so linear, that it'd be grating if it weren't so approachable. You must be strategic about the smile you display on [...]

By 12 weeks post-birth intercourse resumes for most couples. Andy García, the new Father of the Bride, says yes "I'M ABOUT TO be the father of the bride times three", Andy García says about his summer plans. "I'm definitely more modern and more open", García says, comparing his and Billy's approaches to parenting. He plays Billy Herrera, a Miami architect and a rule-the-roost patriarch in the antiquated mold who strongly disapproves of his daughter's fiancé, a billionaire heir who, among other perceived transgressions, dared to propose without first seeking Billy's permission. [Extracted from the article]

Byline: Justin Kirkland EVER WONDER HOW--and what--your dog or cat does when you're gone? Is he blissfully snoozing? (We like to think so.) Nervously pacing? (Gosh, we hope not.) Or [...]

Which foods are good for your body, and which are the opposite? If you're like us, you find it impossible to keep track, because the diets and data keep changing [...]

Cobalt(I) complexes supported by a series of PCcarbeneP pincer ligands of varying donicity, differing in the aryl group linking the phosphine arms with the anchoring carbon donor, are described. Addition of the proligands to cobalt bromide results in the formation of a series of cobalt(II) tetrahedral complexes, Ln-1, which serve as excellent precursors to the corresponding PCalkylP and PCcarbeneP complexes. The square-planar cobalt PCcarbeneP complexes L2R-3-X(X = Cl, Br) are readily synthesized by addition of a bulky aryloxide radical to the corresponding PCalkylP complex L1-2-Br, via addition of L2Rto ClCo(PPh3)3in the presence of trityl radical, or by addition of NaHBEt3and trityl radical to isolated L2R-1. For the L2NMe2PCcarbeneP complexes, salt metathesis reactions with CsOH·H2O, LiCH2TMS, or LiNH2result in the corresponding hydroxo, alkyl, and amine complexes L2NMe2-3-R(R = OH, CH2TMS, NH2). Reaction of L2NMe2-3-OHwith benzoic acid affords the κ2-O2CPh derivative The nature of the carbene bond in either ligand platform and the effects of the X-type capping ligand on the Co═C bond are explored using CASSCF and CASPT2 calculations and show that triplet structures are relatively more stable for the less electron donating ligand L1while singlet Co(I) carbenes dominate for the more electron rich L2derivatives. For L2NMe2complexes, the effect of the transligand X was also probed. π donors imbue the carbene with singlet character, while the strongly σ donating alkyl derivative exhibits significant triplet character.

- K. S. 3 HAIL to the CHIP No matter how many snacks you lay out in your party spread, if potato chips are in the mix, potato chips will win. - JUSTIN KIRKLAND 8 BECOME the Emperor of ICE CREAM… SANDWICHES IT'S-ITS are where IT'S AT I'm told that if you grew up in northern California, It's-Its are as common as, say, Klondike Bars. COLUMNS We could almost reach out and touch that disco ball on a velvet stick, couldn't we?. [Extracted from the article]

In the pursuit of smelling good, there's no shame in looking for some inspiration. Imagine smelling rich and famous--the nostril equivalent of tasting the world's finest wine. Like describing wine, [...]

We describe the preparation of the cis-bis(η1,η2-2,2-dimethylpent-4-en-1-yl)rhodate(I) anion, cis-[Rh(CH2CMe2CH2CH═CH2)2]−, and the interaction of this species with Li+both in solution and in the solid state. For the lithium(diethyl ether) salt [Li(Et2O)][Rh(CH2CMe2CH2CH═CH2)2], VT-NMR and 1H{7Li} NOE NMR studies in toluene-d8show that the Li+cation is in close proximity to the dz2orbital of rhodium. In the solid-state structure of the lithium(12-crown-4) salt [Li(12-crown-4)2][Li{Rh(CH2CMe2CH2CH═CH2)2}2], one lithium atom is surrounded by two [Rh(CH2CMe2CH2CH═CH2)2]−anions, and in this assembly there are two unusually short Rh–Li distances of 2.48 Å. DFT calculations, natural energy decomposition, and ETS-NOCV analysis suggest that there is a weak dative interaction between the 4dz2orbitals on the Rh centers and the 2pzorbital of the Li+cation. The charge-transfer term between Rh and Li+contributes only about the 1/5 of the total interaction energy, however, and the principal driving force for the proximity of Rh and Li in compounds 1and 2is that Li+is electrostatically attracted to negative charges on the dialkylrhodiate anions.

IN 2017, ACTOR COREY HAWKINS WAS filming a movie in Toronto when he got a call from the producers of the U. S. Open. FEATURES PRECEDING PAGES, from left: Jacket ($3,745), T-shirt ($795), and trousers ($1,075) by Dolce & Gabbana; sunglasses ($490) by Rhude. He didn't know it at the time, but among the 23,000 people in the stands sat Lin-Manuel Miranda, and Hawkins's performance was an informal audition for the film adaptation of the playwright's breakout musical, In the Heights. [Extracted from the article]

Open governance requirements are designed to improve accountability, which implies that transparent governments are more trustworthy stewards of their publicly invested power. However, transparency may also reduce institutional effectiveness and inhibit political compromise, diminishing the capacity to manage resources responsibly. We assess empirical support for these competing perspectives in the context of American state legislatures, many of which have become exempt from state sunshine laws in recent decades. We leverage variation in the timing of these legislative exemptions to identify the effect of removing transparency in a crucial governing institution on investors’ risk perceptions of states’ general obligation bonds. Our analysis of these data during the period 1995–2010 suggests that removing legislative transparency reducesstate credit risk. We conclude that while openness in government may be normatively desirable, shielding legislative proceedings from public view may actually be better for states’ debt repayment capacity, improving their overall fiscal health.

FEATURES 20 LIVES, 20 PERSPECTIVES NUMBERS REVEAL ESSENTIAL truths, but they don't provide much comfort. With 3.9 million confirmed cases and 270,000 deaths* in 187 countries on every continent but Antarctica, the coronavirus pandemic has already altered daily life beyond recognition. THE AUTOCRAT WHISPERER FIONNUALA NÍ AOLÁIN UN SPECIAL RAPPORTEUR ON COUNTERTERRORISM & HUMAN RIGHTS Minneapolis 70 TO 90%: Percentage of Americans willing to yield certain freedoms to support public measures to slow the virus One of my big concerns is the potential for the abuse of power by authoritarians that rises in parallel with the pandemic under the guise of responding to a global health crisis. THE FUNERAL DIRECTOR STEPHEN KEMP OWNER, KEMP FUNERAL HOME & CREMATION SERVICES Southfield, Michigan AFRICAN-AMERICANS MAKE UP: 14 percent of Michigan's population 41 percent of its coronavirus-related deaths FUNERAL DIRECTORS ARE community people. [Extracted from the article]

Using data on the content of debate associated with votes in the UK House of Commons from 1992–2015, this article examines how government party MPs employ language in legislative speech when they vote against the party line. We find a robust statistical association between dissent on votes and the use of first‐person pronouns, simpler language, and giving longer speeches. Using a random forest algorithm for classification, we find that these language covariates are predictive of rebellion. The use of simpler, first‐person language has implications for political representation and offers new insight into how MPs use votes to distinguish themselves from their party, perhaps reflecting attempts to connect with constituents.

Zr metallocenes have significant potential to be highly tunable polyethylene catalysts through modification of the aromatic ligand framework. Here we report the development of multiple machine learning models using a large library (>700 systems) of DFT-calculated zirconocene properties and barriers for ethylene polymerization. We show that very accurate machine learning models are possible for HOMO–LUMO gaps of precatalysts but the performance significantly depends on the machine learning algorithm and type of featurization, such as fingerprints, Coulomb matrices, smooth overlap of atomic positions, or persistence images. Surprisingly, the description of the bonding hapticity, the number of direct connections between Zr and the ligand aromatic carbons, only has a moderate influence on the performance of most models. Despite robust models for HOMO–LUMO gaps, these types of machine learning models based on structure connectivity type features perform poorly in predicting ethylene migratory insertion barrier heights. Therefore, we developed several relatively robust and accurate machine learning models for barrier heights that are based on quantum-chemical descriptors (QCDs). The quantitative accuracy of these models depends on which potential energy surface structure QCDs were harvested from. This revealed a Hammett-type principle to naturally emerge showing that QCDs from the π-coordination complexes provide much better descriptions of the transition states than other potential-energy structures. Feature importance analysis of the QCDs provides several fundamental principles that influence zirconocene catalyst reactivity.

The article evaluates perfume Tom Ford Beau de Jour offered by Tom Ford, Corpus Natural Deodorant offered by J75 Inc. and fragrance candle Malin+Goetz Cannabis Earthy offered by Malin + Goetz.

PHOSPHORUS BOMBS can kill, but they saved retired Colonel Tony Nadal's life. Pinned down during a 1965 battle in Vietnam, Nadal (then a captain) led his unit to safety behind [...]

Scholars of social networks often rely on summary statistics to measure and compare the structures of their networks of interest. However, measuring the uncertainty inherent in these summaries can be challenging, thus making hypothesis testing for network summaries difficult. Computational and nonparametric procedures can overcome these difficulties by allowing researchers to generate reference distributions for comparison directly from their data. In this research, I demonstrate the use of nonparametric hypothesis testing in networks using the popular network summary statistic network modularity. I provide a method based on permutation testing for assessing whether a particular network modularity score is larger than a researcher might expect due to random chance. I then create a simulation study of network modularity and its simulated reference distribution that I propose. Finally, I provide an empirical example of this technique using cosponsorship networks from U.S. state legislatures. [ABSTRACT FROM PUBLISHER]

The article discusses the role of wealth in legislative redistricting processes in the the state legislatures of California and North Carolina. The author utilizes logistic regression analysis of census block group exchanges between legislative districts to argue that income was a significant factor in the redrawing of legislative majority political party districts in California and North Carolina. According to the article, the Democratic Party controlled the state legislatures in both states following the 2000 U.S. census.

The article assesses the relation between political action committees (PACs) and U.S. state policies. It is said that lobbying activity on debated policy issues is related to the number of PACs in a state, as well as political donations to PACs. A statistical test using health care policy factors such as state Medicaid spending, the elderly as a percentage of state population, and the amount of health legislation proposed in a given state is utilized to discern factors relevant to the formation of PACs and the number of lobbying registrations.

I found somebody's lingerie in Marlon's house one time, and I was just devastated. FEATURES rita moreno i dated Elvis because I was trying to get even with Marlon Brando. [Extracted from the article]