Catalytic direct hydrocarboxylation of styrenes with CO2 and H2.

A three-component hydrocarboxylation of an olefin with CO2 and H2 could be regarded as a dream reaction, since it would provide a straightforward approach for the synthesis of aliphatic carboxylic acids in perfect atom economy. However, this transformation has not been realized in a direct manner under mild conditions, because boosting the carboxylation with thermodynamically stable CO2 while suppressing the rapid hydrogenation of olefin remains a challenging task. Here, we report a rhodium-catalysed reductive hydrocarboxylation of styrene derivatives with CO2 and H2 under mild conditions, in which H2 served as the terminal reductant. In this approach, the carboxylation process was largely accelerated by visible light irradiation, which was proved both experimentally and by computational studies. Hydrocarboxylation of various kinds of styrene derivatives was achieved in good yields without additional base under ambient pressure of CO2/H2 at room temperature. Mechanistic investigations revealed that use of a cationic rhodium complex was critical to achieve high hydrocarboxylation selectivity.

Resonance acoustic microbalance with naked-embedded quartz (RAMNE-Q) biosensor fabricated by microelectromechanical-system process.

A resonance acoustic microbalance with a naked-embedded quartz (RAMNE-Q) is realized by a microfabrication method, aiming at broader applications of quartz-crystal microbalance (QCM) biosensors. The RAMNE-Q biosensor consists of three layers; a silicon layer with an engraved microchannel and sandwiching glass layers. The naked AT-cut quartz resonator of 9.3 or 28.5 µm thick is located in the microchannel and supported by the silicon micropillars and semicircular walls without fixing, and it is encapsulated by the rigid body. Cupper antennas are used for generating and receiving electromagnetic fields to excite and detect the shear vibration of the quartz oscillator during the solution flow, thereby achieving the noncontact measurement of the resonance frequency. Because of the isolated resonator, the Q factor is high enough (about 1500 at 170-180 MHz) even in the flowing solution. We succeeded in detecting 1 ng/ml human immunoglobulin G in phosphate-buffered-saline solution via Staphylococcus aureus protein A immobilized nonspecifically on the quartz surfaces, demonstrating the high sensitivity and high signal-to-noise ratio of the RAMNE-Q biosensor. It does not require electrodes and is a replacement-free biosensor, and its reusability is confirmed.