No abstract

Direct (utilize easily available and abundant precursors) and selective (both chemo- and regio-) aliphatic C–H functionalization is an attractive mean with which to streamline chemical synthesis. With many possible sites of reaction, traditional methods often need an adjacent polar directing group nearby to achieve high regio- and chemoselectivity and are often restricted to a single site of functionalization. Here we report a remote aliphatic C–H thiolation process with predictable and switchable regioselectivity through NiH-catalysed migratory hydrothiolation of two feedstock chemicals (alkenes/alkynes and thiols). This mild reaction avoids the preparation of electrophilic thiolation reagents and is highly selective to thiols over other nucleophilic groups, such as alcohols, acids, amines, and amides. Mechanistic studies show that the reaction occurs through the formation of an RS-Bpin intermediate, and THF as the solvent plays an important role in the regeneration of NiH species.

This study addresses the need to reduce the risk of clogging when preparing samples for cell concentration, i.e., the CaSki Cell-lines (epidermoid cervical carcinoma cells). Aiming to develop a non-clogging microconcentrator, we proposed a new counter-flow concentration unit characterized by the directions of penetrating flows being at an obtuse angle to the main flow, due to employment of streamlined turbine blade-like micropillars. Based on the optimization results of the counter-flow unit profile, a fractal arrangement for the counter-flow concentration unit was developed. A counter-flow microconcentrator chip was then designed and fabricated, with both the processing layer and collecting layer arranged in terms of the honeycomb structure. Visualized experiments using CaSki cell samples on the microconcentrator chip demonstrated that no cell-clogging phenomena occurred during the test and that no cells were found in the final filtrate. The test results show an excellent concentration performance for the microconcentrator chip, while a concentrating ratio of [4 with the flow rate being below 1.0 ml/min. As only geometrical structure is employed in the passive device, the counter-flow microconcentrator can be easily integrated into advanced microfluidic systems. Owing to the merit of non-clogging and continuous processing ability, the counter-flow microconcentrator is not only suitable for the sample preparation within biomedical field, but also applicable in water-particle separation.

• Our knowledge of ozone (O 3 ) effects on dynamic stomatal response is still limited.• Determinants of O 3 -induced stomatal sluggishness were examined in deciduous tree species in open-top chambers.• Ozone exposure slowed closing of stomata after leaf cutting.• Stomatal sluggishness was well explained by stomatal O 3 flux per net photosynthesis.• Stomatal sluggishness depended both on ozone flux and on the capacity for detoxification or repair. a b s t r a c t a r t i c l e i n f o Our knowledge of ozone effects on dynamic stomatal response is still limited, especially in Asian tree species. We thus examined ozone effects on steady-state leaf gas exchange and stomatal dynamics in three common tree species of China (Ailanthus altissima, Fraxinus chinensis and Platanus orientalis). Seedlings were grown and were exposed to three levels of ozone in open-top chambers (42, 69, 100 nmol mol −1 daylight average, from 09:00 to 18:00). At steady-state, ozone exposure induced an uncoupling of photosynthesis and stomatal conductance, as the former decreased while the latter did not. Dynamic stomatal response was investigated by cutting the leaf petiole after a steady-state stomatal conductance was reached. Ozone exposure increased stomatal sluggishness, i.e., slowed stomatal response after leaf cutting, in the following order of sensitivity, F. chinensis N A. altissima N P. orientalis. A restriction of stomatal ozone flux reduced the ozone-induced sluggishness in P. orientalis. The ozone-induced impairment of stomatal control was better explained by stomatal ozone flux per net photosynthesis rather than by stomatal ozone flux only. This suggests that ozone injury to stomatal control depends both on the amount of ozone entering a leaf and on the capacity for biochemical detoxification or repair. Leaf mass per area and the density of stomata did not affect stomatal sluggishness.