Filtering by
- Resource Type: Text
![129505-Thumbnail Image.png](https://d1rbsgppyrdqq4.cloudfront.net/s3fs-public/styles/width_400/public/2021-04/129505-Thumbnail%20Image.png?versionId=2bAJE3cCNwXA9UHy2uzquZX7G7Sb2Acd&X-Amz-Content-Sha256=UNSIGNED-PAYLOAD&X-Amz-Algorithm=AWS4-HMAC-SHA256&X-Amz-Credential=AKIASBVQ3ZQ42ZLA5CUJ/20240619/us-west-2/s3/aws4_request&X-Amz-Date=20240619T023920Z&X-Amz-SignedHeaders=host&X-Amz-Expires=120&X-Amz-Signature=4e6108fe7c3a20d53e2565ac072662c5af91a3cb740a20f2c93e84c4a2d7489f&itok=-PY5GNFS)
Attempts to prepare low-valent molybdenum complexes that feature a pentadentate 2,6-bis(imino)pyridine (or pyridine diimine, PDI) chelate allowed for the isolation of two different products. Refluxing Mo(CO)6 with the pyridine-substituted PDI ligand, PyEtPDI, resulted in carbonyl ligand substitution and formation of the respective bis(ligand) compound (PyEtPDI)2Mo (1). This complex was investigated by single-crystal X-ray diffraction, and density functional theory calculations indicated that 1 possesses a Mo(0) center that back-bonds into the π*-orbitals of the unreduced PDI ligands. Heating an equimolar solution of Mo(CO)[subscript 6] and the phosphine-substituted PDI ligand, Ph2PPrPDI, to 120 °C allowed for the preparation of (Ph2PPrPDI)Mo(CO) (2), which is supported by a κ5-N,N,N,P,P-Ph2PPrPDI chelate. Notably, 1 and 2 have been found to catalyze the hydrosilylation of benzaldehyde at 90 °C, and the optimization of 2-catalyzed aldehyde hydrosilylation at this temperature afforded turnover frequencies of up to 330 h–1. Considering additional experimental observations, the potential mechanism of 2-mediated carbonyl hydrosilylation is discussed.
![129547-Thumbnail Image.png](https://d1rbsgppyrdqq4.cloudfront.net/s3fs-public/styles/width_400/public/2021-04/129547-Thumbnail%20Image.png?versionId=ExEo01TkV37eRCEhM2.OIOIdWkc4rR1N&X-Amz-Content-Sha256=UNSIGNED-PAYLOAD&X-Amz-Algorithm=AWS4-HMAC-SHA256&X-Amz-Credential=AKIASBVQ3ZQ42ZLA5CUJ/20240619/us-west-2/s3/aws4_request&X-Amz-Date=20240619T023920Z&X-Amz-SignedHeaders=host&X-Amz-Expires=120&X-Amz-Signature=147ad0aeedc953b4b2edd52e46489efd4eb730d2f0844067242f38f150ffc066&itok=lQJZ1BWw)
A brief review of manganese-catalyzed hydrosilylation is presented along with a personal account of how the design for the highly active catalyst, (Ph2PPrPDI)Mn, was conceived. The reductive transformations achieved using this catalyst are described and put into further context by comparing the observed activities with those attained for leading late first-row transition-metal catalysts.
![128201-Thumbnail Image.png](https://d1rbsgppyrdqq4.cloudfront.net/s3fs-public/styles/width_400/public/2021-04/128201-Thumbnail%20Image.png?versionId=FyuHcUFQ1kxgafw1QZf0CSsz_cGqJvWK&X-Amz-Content-Sha256=UNSIGNED-PAYLOAD&X-Amz-Algorithm=AWS4-HMAC-SHA256&X-Amz-Credential=AKIASBVQ3ZQ42ZLA5CUJ/20240619/us-west-2/s3/aws4_request&X-Amz-Date=20240619T023921Z&X-Amz-SignedHeaders=host&X-Amz-Expires=120&X-Amz-Signature=2ed94411e24779ca3c5149f1d68139b75ef4a550caf24af7faf44a573063579f&itok=DK6RogPB)
Manual therapy has long been a component of physical rehabilitation programs, especially to treat those in pain. The mechanisms of manual therapy, however, are not fully understood, and it has been suggested that its pain modulatory effects are of neurophysiological origin and may be mediated by the descending modulatory circuit. Therefore, the purpose of this review is to examine the neurophysiological response to different types of manual therapy, in order to better understand the neurophysiological mechanisms behind each therapy’s analgesic effects. It is concluded that different forms of manual therapy elicit analgesic effects via different mechanisms, and nearly all therapies appear to be at least partially mediated by descending modulation. Additionally, future avenues of mechanistic research pertaining to manual therapy are discussed.
![128213-Thumbnail Image.png](https://d1rbsgppyrdqq4.cloudfront.net/s3fs-public/styles/width_400/public/2021-04/128213-Thumbnail%20Image.png?versionId=wSBjonNYoTIU29XTSgDpm1ZA5IlTaMpy&X-Amz-Content-Sha256=UNSIGNED-PAYLOAD&X-Amz-Algorithm=AWS4-HMAC-SHA256&X-Amz-Credential=AKIASBVQ3ZQ42ZLA5CUJ/20240619/us-west-2/s3/aws4_request&X-Amz-Date=20240619T023921Z&X-Amz-SignedHeaders=host&X-Amz-Expires=120&X-Amz-Signature=e4c22892c16f8f5ac03981258df150b491dbfda18845e0f7079435847c934be7&itok=Cmw0dPU-)
The notable increase in biofuel usage by the road transportation sector in Brazil during recent years has significantly altered the vehicular fuel composition. Consequently, many uncertainties are currently found in particulate matter vehicular emission profiles. In an effort to better characterise the emitted particulate matter, measurements of aerosol physical and chemical properties were undertaken inside two tunnels located in the São Paulo Metropolitan Area (SPMA). The tunnels show very distinct fleet profiles: in the Jânio Quadros (JQ) tunnel, the vast majority of the circulating fleet are light duty vehicles (LDVs), fuelled on average with the same amount of ethanol as gasoline. In the Rodoanel (RA) tunnel, the particulate emission is dominated by heavy duty vehicles (HDVs) fuelled with diesel (5% biodiesel). In the JQ tunnel, PM2.5 concentration was on average 52 μg m-3, with the largest contribution of organic mass (OM, 42%), followed by elemental carbon (EC, 17%) and crustal elements (13%). Sulphate accounted for 7% of PM2.5 and the sum of other trace elements was 10%. In the RA tunnel, PM2.5 was on average 233 μg m-3, mostly composed of EC (52%) and OM (39%). Sulphate, crustal and the trace elements showed a minor contribution with 5%, 1%, and 1%, respectively. The average OC : EC ratio in the JQ tunnel was 1.59 ± 0.09, indicating an important contribution of EC despite the high ethanol fraction in the fuel composition. In the RA tunnel, the OC : EC ratio was 0.49 ± 0.12, consistent with previous measurements of diesel-fuelled HDVs. Besides bulk carbonaceous aerosol measurement, polycyclic aromatic hydrocarbons (PAHs) were quantified. The sum of the PAHs concentration was 56 ± 5 ng m-3 and 45 ± 9 ng m-3 in the RA and JQ tunnel, respectively. In the JQ tunnel, benzo(a)pyrene (BaP) ranged from 0.9 to 6.7 ng m-3 (0.02–0.1‰ of PM2.5)] whereas in the RA tunnel BaP ranged from 0.9 to 4.9 ng m-3 (0.004–0. 02‰ of PM2.5), indicating an important relative contribution of LDVs emission to atmospheric BaP.
![128196-Thumbnail Image.png](https://d1rbsgppyrdqq4.cloudfront.net/s3fs-public/styles/width_400/public/2021-04/128196-Thumbnail%20Image.png?versionId=QISQuS1lueo6pg39IREtnYhQtG_ig0k6&X-Amz-Content-Sha256=UNSIGNED-PAYLOAD&X-Amz-Algorithm=AWS4-HMAC-SHA256&X-Amz-Credential=AKIASBVQ3ZQ42ZLA5CUJ/20240619/us-west-2/s3/aws4_request&X-Amz-Date=20240619T014637Z&X-Amz-SignedHeaders=host&X-Amz-Expires=120&X-Amz-Signature=f48a9654e840758f195bddeab186f2ca7c1c480a112844240672fd9ba105ea1e&itok=GwJP5l-c)
About 2.5 × 106 snapshots on microcrystals of photoactive yellow protein (PYP) from a recent serial femtosecond crystallographic (SFX) experiment were reanalyzed to maximum resolution. The resolution is pushed to 1.46 Å, and a PYP structural model is refined at that resolution. The result is compared to other PYP models determined at atomic resolution around 1 Å and better at the synchrotron. By comparing subtleties such as individual isotropic temperature factors and hydrogen bond lengths, we were able to assess the quality of the SFX data at that resolution. We also show that the determination of anisotropic temperature factor ellipsoids starts to become feasible with the SFX data at resolutions better than 1.5 Å.
![128816-Thumbnail Image.png](https://d1rbsgppyrdqq4.cloudfront.net/s3fs-public/styles/width_400/public/2021-04/128816-Thumbnail%20Image.png?versionId=rfhmZVbHa1VlFIuLonCyVUU2Q0TzADiT&X-Amz-Content-Sha256=UNSIGNED-PAYLOAD&X-Amz-Algorithm=AWS4-HMAC-SHA256&X-Amz-Credential=AKIASBVQ3ZQ42ZLA5CUJ/20240619/us-west-2/s3/aws4_request&X-Amz-Date=20240619T020027Z&X-Amz-SignedHeaders=host&X-Amz-Expires=120&X-Amz-Signature=554d4ef78361b8072487a106cc513f003bdc6620f64d61192324c616c713077a&itok=EkEHH5C3)
To address the need to study frozen clinical specimens using next-generation RNA, DNA, chromatin immunoprecipitation (ChIP) sequencing and protein analyses, we developed a biobank work flow to prospectively collect biospecimens from patients with renal cell carcinoma (RCC). We describe our standard operating procedures and work flow to annotate pathologic results and clinical outcomes. We report quality control outcomes and nucleic acid yields of our RCC submissions (N=16) to The Cancer Genome Atlas (TCGA) project, as well as newer discovery platforms, by describing mass spectrometry analysis of albumin oxidation in plasma and 6 ChIP sequencing libraries generated from nephrectomy specimens after histone H3 lysine 36 trimethylation (H3K36me3) immunoprecipitation. From June 1, 2010, through January 1, 2013, we enrolled 328 patients with RCC. Our mean (SD) TCGA RNA integrity numbers (RINs) were 8.1 (0.8) for papillary RCC, with a 12.5% overall rate of sample disqualification for RIN <7. Banked plasma had significantly less albumin oxidation (by mass spectrometry analysis) than plasma kept at 25°C (P<.001). For ChIP sequencing, the FastQC score for average read quality was at least 30 for 91% to 95% of paired-end reads. In parallel, we analyzed frozen tissue by RNA sequencing; after genome alignment, only 0.2% to 0.4% of total reads failed the default quality check steps of Bowtie2, which was comparable to the disqualification ratio (0.1%) of the 786-O RCC cell line that was prepared under optimal RNA isolation conditions. The overall correlation coefficients for gene expression between Mayo Clinic vs TCGA tissues ranged from 0.75 to 0.82. These data support the generation of high-quality nucleic acids for genomic analyses from banked RCC. Importantly, the protocol does not interfere with routine clinical care. Collections over defined time points during disease treatment further enhance collaborative efforts to integrate genomic information with outcomes.
![136176-Thumbnail Image.png](https://d1rbsgppyrdqq4.cloudfront.net/s3fs-public/styles/width_400/public/2021-05/136176-Thumbnail%20Image.png?versionId=cD5DfbOroARhPfCzrU0F62FLo_Ce3A8p&X-Amz-Content-Sha256=UNSIGNED-PAYLOAD&X-Amz-Algorithm=AWS4-HMAC-SHA256&X-Amz-Credential=AKIASBVQ3ZQ42ZLA5CUJ/20240619/us-west-2/s3/aws4_request&X-Amz-Date=20240619T020539Z&X-Amz-SignedHeaders=host&X-Amz-Expires=120&X-Amz-Signature=dac30216e271e6bf4a68a37e1a7c91ee2b9a4d402151fabc38452b98e15bb46f&itok=8uHAFejQ)
![136177-Thumbnail Image.png](https://d1rbsgppyrdqq4.cloudfront.net/s3fs-public/styles/width_400/public/2021-05/136177-Thumbnail%20Image.png?versionId=_S0sBgdRRd.fRlOR4v4qLOSuHkULTiaq&X-Amz-Content-Sha256=UNSIGNED-PAYLOAD&X-Amz-Algorithm=AWS4-HMAC-SHA256&X-Amz-Credential=AKIASBVQ3ZQ42ZLA5CUJ/20240619/us-west-2/s3/aws4_request&X-Amz-Date=20240619T021628Z&X-Amz-SignedHeaders=host&X-Amz-Expires=120&X-Amz-Signature=40c2165c2a06c5950b139539185d847f7068dd317a4f8718826c75305bd1eb53&itok=inFAj-xo)