Photogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units.

Light-driven strategies that enable the chemoselective activation of a specific bond in multifunctional systems are comparatively underexplored in comparison to transition-metal-based technologies, yet desirable when considering the controlled exploration of chemical space. With the current drive to discover next-generation therapeutics, reaction design that enables the strategic incorporation of an sp3 carbon center, containing multiple synthetic handles for the subsequent exploration of chemical space would be highly enabling. Here, we describe the photoactivation of ambiphilic C1 units to generate α-bimetalloid radicals using only a Lewis base and light source to directly activate the C-I bond. Interception of these transient radicals with various SOMOphiles enables the rapid synthesis of organic scaffolds containing synthetic handles (B, Si, and Ge) for subsequent orthogonal activation. In-depth theoretical and mechanistic studies reveal the prominent role of 2,6-lutidine in forming a photoactive charge transfer complex and in stabilizing in situ generated iodine radicals, as well as the influential role of the boron p-orbital in the activation/weakening of the C-I bond. This simple and efficient methodology enabled expedient access to functionalized 3D frameworks that can be further derivatized using available technologies for C-B and C-Si bond activation.

Direct Light-Enabled Access to α-Boryl Radicals: Application in the Stereodivergent Synthesis of Allyl Boronic Esters.

Operationally simple strategies to assemble boron containing organic frameworks are highly enabling in organic synthesis. While conventional retrosynthetic logic has engendered many platforms focusing on the direct formation of C-B bonds, α-boryl radicals have recently reemerged as versatile open-shell alternatives to access organoborons via adjacent C-C bond formation. Direct light-enabled α-activation is currently contingent on photo- or transition metal-catalysis activation to efficiently generate radical species. Here, we disclose a facile activation of α-halo boronic esters using only visible light and a simple Lewis base to enable homolytic scission. Intermolecular addition to styrenes facilitates the rapid construction of highly versatile E-allylic boronic esters. The simplicity of activation permits the strategic merger of this construct with selective energy transfer catalysis to enable the complimentary stereodivergent synthesis of Z-allylic boronic esters.

The Impact of Boron Hybridisation on Photocatalytic Processes.

Recently the fruitful merger of organoboron chemistry and photocatalysis has come to the forefront of organic synthesis, resulting in the development of new technologies to access complex (non)borylated frameworks. Central to the success of this combination is control of boron hybridisation. Contingent on the photoactivation mode, boron as its neutral planar form or tetrahedral boronate can be used to regulate reactivity. This Minireview highlights the current state of the art in photocatalytic processes utilising organoboron compounds, paying particular attention to the role of boron hybridisation for the target transformation.

Fibrous Extracellular Spheroids in an Endoscopic Ultrasound-Guided Pancreatic Fine Needle Aspiration Correlating to a Gyriform Pancreatic Endocrine Tumor with a Unique Cobblestone Pavement Growth Pattern.

Pancreatic neuroendocrine neoplasms (PanNENs) are uncommon tumors. Fine needle aspiration (FNA) samples from PanNENs are typically of high cellularity and lack necrosis. In cytology slides from these tumors, dyscohesive cells are usually reported with variably round to oval to plasmacytoid forms exhibiting coarsely granular chromatin and showing immunoreactivity for synaptophysin. We present an unusual, and to our knowledge not previously described, example of an FNA of a PanNEN with large extracellular fibrous spheroids containing intrinsic fibroblasts and rimmed by small to intermediate sized neoplastic epithelial cells with high nuclear cytoplasmic ratios. The cytomorphology of the PanNEN in this case was in some ways reminiscent of that expected in adenoid cystic carcinomas of the salivary glands that most often contain large extracellular globules of basement membrane material and a somewhat biphasic population of lesional cells. The cytomorphology in this case was found to correlate well with the resection specimen histomorphology of an exaggerated gyriform pattern of growth resulting in a unique cobblestone-pavement like microscopic appearance. Knowledge of this potential cytomorphology will aid the cytology community through recognition and reporting of this previously undescribed pattern in an uncommon disease.

Gaseous Emissions from Light-Duty Vehicles: Moving from NEDC to the New WLTP Test Procedure.

The Worldwide Harmonized Light Duty Test Procedure (WLTP), recently issued as GTR15 by UNECE-WP29, is designed to check the pollutant emission compliance of Light Duty Vehicles (LDVs) around the world and to establish the reference vehicle fuel consumption and CO2 performance. In the course of the development of WLTP, the Joint Research Center (JRC) of the European Commission has tested gaseous emissions of twenty-one Euro 4-6 gasoline and diesel vehicles, on both the current European type approval test procedure (NEDC) and the progressive versions of the WLTP. The results, which should be regarded just as an initial and qualitative indication of the trends, demonstrated minimal average differences between CO2 emissions over the NEDC and WLTP. On the other hand, CO2 emissions measured at JRC on the NEDC were on average 9% higher than the respective type approval values, therefore suggesting that for the tested vehicles, CO2 emissions over WLTP were almost 10% higher than the respective NEDC type approval values. That difference is likely to increase with application of the full WLTP test procedure. Measured THC emissions from most vehicles stayed below the legal emission limits and in general were lower under the WLTP compared to NEDC. Moving from NEDC to WLTP did not have much impact on NOx from gasoline vehicles and CO from diesel vehicles. On the contrary, NOx from diesel vehicles and CO from low-powered gasoline vehicles were significantly higher over the more dynamic WLTP and in several cases exceeded the emission limits. Results from this study can be considered indicative of emission patterns of modern technology vehicles and useful to both policy makers and vehicle manufacturers in developing future emission policy/technology strategies.

Assessment of on-road emissions of four Euro V diesel and CNG waste collection trucks for supporting air-quality improvement initiatives in the city of Milan.

This paper summarizes the results of an extensive experimental study aiming to evaluate the performance and pollutant emissions of diesel and CNG waste collection trucks under realistic and controlled operating conditions in order to support a fleet renewal initiative in the city of Milan. Four vehicles (1 diesel and 3 CNG) were tested in two phases using a portable emission measurement system. The first phase included real world operation in the city of Milan while the second involved controlled conditions in a closed track. Emissions recorded from the diesel truck were on average 2.4 kg/km for CO(2), 0.21 g/km for HC, 7.4 g/km for CO, 32.3 g/km for NO(x) and 46.4 mg/km for PM. For the CNG the values were 3.6 kg/km for CO(2), 2.19 g/km for HC, 15.8 g/km for CO, 4.38 g/km for NO(x) and 11.4 mg/km for PM. CNG vehicles presented an important advantage with regards to NO(x) and PM emissions but lack the efficiency of their diesel counterparts when it comes to CO, HC and particularly greenhouse gas emissions. This tradeoff needs to be carefully analyzed prior to deciding if a fleet should be shifted towards either technology. In addition it was shown that existing emission factors, used in Europe for environmental assessment studies, reflect well the operation for CNG but were not so accurate when it came to the diesel engine truck particularly for CO(2) and NO(x). With regard to NO(x), it was also shown that the limits imposed by current emission standards are not necessarily reflected in real world operation, under which the diesel vehicle presented almost 4 times higher emissions. Regarding CO(2), appropriate use of PEMS data and vehicle information allows for accurate emission monitoring through computer simulation.