Visible Light-Induced Transition Metal Catalysis.

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which has led to the discovery of unprecedented transformations as well as the improvement of known reactions. In this subfield of photocatalysis, a transition metal complex serves a double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via a single catalytic cycle, thus contrasting the established dual photocatalysis in which an exogenous photosensitizer is employed. In addition, this approach often synergistically combines catalyst-substrate interaction with photoinduced process, a feature that is uncommon in conventional photoredox chemistry. This Review describes the early development and recent advances of this emerging field.

Recent Advances in Visible Light Induced Palladium Catalysis.

Visible light-induced Pd catalysis has emerged as a promising subfield of photocatalysis. The hybrid nature of Pd radical species has enabled a wide array of radical-based transformations otherwise challenging or unknown via conventional Pd chemistry. In parallel to the ongoing pursuit of alternative, readily available radical precursors, notable discoveries have demonstrated that photoexcitation can alter not only oxidative addition but also other elementary steps. This Minireview highlights the recent progress in this area.

Enhanced Excited-State Hydricity of Pd-H Allows for Unusual Head-to-Tail Hydroalkenylation of Alkenes.

Photoinduced enhancement of hydricity of palladium hydride species enables unprecedented hydride addition-like ("hydridic") hydropalladation of electron-deficient alkenes, which allows for chemoselective head-to-tail cross-hydroalkenylation of electron-deficient and electron-rich alkenes. This mild and general protocol works with a wide range of densely functionalized and complex alkenes. Notably, this approach also allows for highly challenging cross-dimerization of electronically diverse vinyl arenes and heteroarenes.

Effect of Tryptic Digestion on Sensitivity and Specificity in MALDI-TOF-Based Molecular Diagnostics through Machine Learning.

The digestion of protein into peptide fragments reduces the size and complexity of protein molecules. Peptide fragments can be analyzed with higher sensitivity (often > 102 fold) and resolution using MALDI-TOF mass spectrometers, leading to improved pattern recognition by common machine learning algorithms. In turn, enhanced sensitivity and specificity for bacterial sorting and/or disease diagnosis may be obtained. To test this hypothesis, four exemplar case studies have been pursued in which samples are sorted into dichotomous groups by machine learning (ML) software based on MALDI-TOF spectra. Samples were analyzed in 'intact' mode in which the proteins present in the sample were not digested with protease prior to MALDI-TOF analysis and separately after the standard overnight tryptic digestion of the same samples. For each case, sensitivity (sens), specificity (spc), and the Youdin index (J) were used to assess the ML model performance. The proteolytic digestion of samples prior to MALDI-TOF analysis substantially enhanced the sensitivity and specificity of dichotomous sorting. Two exceptions were when substantial differences in chemical composition between the samples were present and, in such cases, both 'intact' and 'digested' protocols performed similarly. The results suggest proteolytic digestion prior to analysis can improve sorting in MALDI/ML-based workflows and may enable improved biomarker discovery. However, when samples are easily distinguishable protein digestion is not necessary to obtain useful diagnostic results.

Visible-Light-Induced Palladium-Catalyzed Generation of Aryl Radicals from Aryl Triflates.

A mild visible-light-induced Pd-catalyzed intramolecular C-H arylation of amides is reported. The method operates by cleavage of a C(sp2 )-O bond, leading to hybrid aryl Pd-radical intermediates. The following 1,5-hydrogen atom translocation, intramolecular cyclization, and rearomatization steps lead to valuable oxindole and isoindoline-1-one motifs. Notably, this method provides access to products with readily enolizable functional groups that are incompatible with traditional Pd-catalyzed conditions.

Aliphatic Radical Relay Heck Reaction at Unactivated C(sp3 )-H Sites of Alcohols.

The Mizoroki-Heck reaction is one of the most efficient methods for alkenylation of aryl, vinyl, and alkyl halides. Given its innate nature, this protocol requires the employment of compounds possessing a halogen atom at the site of functionalization. However, the accessibility of organic molecules possessing a halogen atom at a particular site in aliphatic systems is extremely limited. Thus, a protocol that allows a Heck reaction to occur at a specific nonfunctionalized C(sp3 )-H site is desirable. Reported here is a radical relay Heck reaction which allows selective remote alkenylation of aliphatic alcohols at unactivated ß-, γ-, and δ-C(sp3 )-H sites. The use of an easily installed/removed Si-based auxiliary enables selective I-atom/radical translocation events at remote C-H sites followed by the Heck reaction. Notably, the reaction proceeds smoothly under mild visible-light-mediated conditions at room temperature, producing highly modifiable and valuable alkenol products from readily available alcohols feedstocks.

Microplastic Pollution: Chemical Characterization and Impact on Wildlife.

Microplastics are small pieces of plastic that are less than 5 mm in size and can be found in most environments, including the oceans, rivers, and air. These small plastic particles can have negative impacts on wildlife and the environment. In this review of the literature, we analyze the presence of microplastics in various species of wildlife, including fish, birds, and mammals. We describe a variety of analytical techniques, such as microscopy and spectrometry, which identify and quantify the microplastics in the samples. In addition, techniques of sample preparation are discussed. Summary results show that microplastics are present in all the wildlife species studied, with the highest concentrations often found in fish and birds. The literature suggests that microplastics are widely distributed in the environment and have the potential to affect a wide range of species. Further research is required to fully understand the impacts of microplastics on wildlife and the environment.

Diagnostic Screening of Bovine Mastitis Using MALDI-TOF MS Direct-Spotting of Milk and Machine Learning.

Novel strategies for diagnostic screening of animal and herd health are crucial to contain disease outbreaks, maintain animal health, and maximize production efficiency. Mastitis is an inflammation of the mammary gland in dairy cows, often resulting from infection from a microorganism. Mastitis outbreaks result in loss of production, degradation of milk quality, and the need to isolate and treat affected animals. In this work, we evaluate MALDI-TOF mass spectrometry as a diagnostic for the culture-less screening of mastitis state from raw milk samples collected from regional dairies. Since sample preparation requires only minutes per sample using microvolumes of reagents and no cell culture, the technique is promising for rapid sample turnaround and low-cost diagnosis. Machine learning algorithms have been used to detect patterns embedded within MALDI-TOF spectra using a training set of 226 raw milk samples. A separate scoring set of 100 raw milk samples has been used to assess the specificity (spc) and sensitivity (sens) of the approach. Of machine learning models tested, the gradient-boosted tree model gave global optimal results, with the Youden index of J = 0.7, sens = 0.89, and spc = 0.81 achieved for the given set of conditions. Random forest models also performed well, achieving J > 0.63, with sens = 0.83 and spc = 0.81. Naïve Bayes, generalized linear, fast large-margin, and deep learning models failed to produce diagnostic results that were as favorable. We conclude that MALDI-TOF MS combined with machine learning is an alternative diagnostic tool for detection of high somatic cell count (SCC) and subclinical mastitis in dairy herds.

Genomic Characterization of Fecal Escherichia coli Isolates with Reduced Susceptibility to Beta-Lactam Antimicrobials from Wild Hogs and Coyotes.

This study was carried out to determine the antimicrobial resistance (AMR) genes and mobile genetic elements of 16 Escherichia coli isolates-with reduced susceptibility to ceftazidime and imipenem-that were recovered from the fecal samples of coyotes and wild hogs from West Texas, USA. Whole-genome sequencing data analyses revealed distinct isolates with a unique sequence type and serotype designation. Among 16 isolates, 4 isolates were multidrug resistant, and 5 isolates harbored at least 1 beta-lactamase gene (blaCMY-2, blaCTX-M-55, or blaCTX-M-27) that confers resistance to beta-lactam antimicrobials. Several isolates carried genes conferring resistance to tetracyclines (tet(A), tet(B), and tet(C)), aminoglycosides (aac(3)-IId, ant(3″)-Ia, aph(3')-Ia, aph(3″)-lb, aadA5, and aph(6)-ld), sulfonamides (sul1, sul2, and sul3), amphenicol (floR), trimethoprim (dfrA1 and dfrA17), and macrolide, lincosamide, and streptogramin B (MLSB) agents (Inu(F), erm(B), and mph(A)). Nine isolates showed chromosomal mutations in the promoter region G of ampC beta-lactamase gene, while three isolates showed mutations in gyrA, parC, and parE quinolone resistance-determining regions, which confer resistance to quinolones. We also detected seven incompatibility plasmid groups, with incF being the most common. Different types of virulence genes were detected, including those that enhance bacterial fitness and pathogenicity. One blaCMY-2 positive isolate (O8:H28) from a wild hog was also a Shiga toxin-producing E. coli and was a carrier of the stx2A virulence toxin subtype. We report the detection of blaCMY-2, blaCTX-M-55, and blaCTX-M-27 beta-lactamase genes in E. coli from coyotes for the first time. This study demonstrates the importance of wildlife as reservoirs of important multi-drug-resistant bacteria and provides information for future comparative genomic analysis with the limited literature on antimicrobial resistance dynamics in wildlife such as coyotes.

General and Selective Metal-Free Radical α-C-H Borylation of Aliphatic Amines.

Despite recent developments, selective C(sp3)-H borylation of feedstock amines remains a formidable challenge. Herein, we have developed a general, mild, and photoinduced transition metal- and strong base-free method for α-C(sp3)-H borylation of amines. This protocol features a regioselective 1,5-hydrogen atom transfer process to access key α-aminoalkyl radical intermediate using commercially available easy-to-install/remove iodobenzoyl radical translocating group. Remarkably, this general, efficient, and operationally simple method allows activation of primary and secondary α-C-H sites of a broad range of acyclic and cyclic amines toward highly regio- and diastereoselective synthesis of valuable α-aminoboronates. Utility of this protocol has been demonstrated by its employment in late-stage borylation of structurally complex amines and formal C-H arylation reaction of amines. Thus, it is expected that this operationally simple, general, and practical method will find broad application in organic synthesis and drug discovery.

Comparative effect of papaya (Carica papaya) leaves' extract and Toltrazuril on growth performance, hematological parameter, and protozoal load in Sonali chickens infected by mixed Eimeria spp.

OBJECTIVE: Anticoccidial drugs may lead to the development of drug resistance and drug residues. Herbal extracts could be an attractive alternative. This research was undertaken to evaluate the anticoccidial outcome of Carica papaya compared with the anticoccidial drug (Toltazuril) in Sonali chickens. MATERIALS AND METHODS: A total of 80 Sonali chickens were evenly and equally allocated into four groups, namely T 1 (non-infected control), T 2 (infected control), T 3 (treated with C. papaya), and T 4 (treated with Toltrazuril). All groups were experimentally infected with oocysts of mixed Eimeria spp. orally except T 1, and the mixed Eimeria spp. oocyst load (OL), body weight (BW) gain, and hematological parameters were calculated. RESULTS: In the findings, the highest OL reduction rate in T 4 was 100%, while the T 3 was 83.44%. Nevertheless, BW differed significantly (p < 0.01) among the different groups, while the daily BW gain was higher in T 3 amounting to 8.10 gm. In the case of hematological parameter, total erythrocyte count (TEC), hemoglobin (Hb), packed cell volume (PCV), and erythrocyte sedimentation rate in different groups were almost the same and were also statistically insignificant (p > 0.05) barring total leukocyte count resulting as significant (p < 0.05) at day 30. Additionally, the results of Pearson's correlation in T 3 at day 30 indicated a strong significant (p < 0.01) negative correlation between OL and BW (r = -0.780) with the following regression equation: y = -0.16*x + 433.665. Moreover, the correlation of TEC, PCV, and Hb with OL was significantly (p < 0.01) negative, r = -0.786, r = -0.752 and r = -0.633, where the regression equations were y = -0.03*x + 4.51, y = -0.03*x + 27.42, and y = -0.04*x + 11.40, respectively. CONCLUSION: Long-term use of C. papaya leaves' extracts effectively controls coccidiosis in Sonali chickens and can act as an effective growth promoter.

C-H functionalization reactions enabled by hydrogen atom transfer to carbon-centered radicals.

Selective functionalization of ubiquitous unactivated C-H bonds is a continuous quest for synthetic organic chemists. In addition to transition metal catalysis, which typically operates under a two-electron manifold, a recent renaissance in the radical approach relying on the hydrogen atom transfer (HAT) process has led to tremendous growth in the area. Despite several challenges, protocols proceeding via HAT are highly sought after as they allow for relatively easy activation of inert C-H bonds under mild conditions leading to a broader scope and higher functional group tolerance and sometimes complementary reactivity over methods relying on traditional transition metal catalysis. A number of methods operating via heteroatom-based HAT have been extensively reported over the past few years, while methods employing more challenging carbon analogues have been less explored. Recent developments of mild methodologies for generation of various carbon-centered radical species enabled their utilization in the HAT process, which, in turn, led to the development of remote C(sp3)-H functionalization reactions of alcohols, amines, amides and related compounds. This review covers mostly recent advances in C-H functionalization reactions involving the HAT step to carbon-centered radicals.