Gas Phase Synthesis of the Elusive Trisilacyclopropyl Radical (Si3H5) via Unimolecular Decomposition of Chemically Activated Doublet Trisilapropyl Radicals (Si3H7).

The gas phase reaction of the simplest silicon-bearing radical silylidyne (SiH; X2Π) with disilane (Si2H6; X1A1g) was investigated in a crossed molecular beams machine. Combined with electronic structure calculations, our data reveal the synthesis of the previously elusive trisilacyclopropyl radical (Si3H5)-the isovalent counterpart of the cyclopropyl radical (C3H5)-along with molecular hydrogen via indirect scattering dynamics through long-lived, acyclic trisilapropyl (i-Si3H7) collision complex(es). Possible hydrogen-atom roaming on the doublet surface proceeds to molecular hydrogen loss accompanied by ring closure. The chemical dynamics are quite distinct from the isovalent methylidyne (CH)-ethane (C2H6) reaction, which leads to propylene (C3H6) radical plus atomic hydrogen but not to cyclopropyl (C3H5) radical plus molecular hydrogen. The identification of the trisilacyclopropyl radical (Si3H5) opens up preparative pathways for an unusual gas phase chemistry of previously inaccessible ring-strained (inorgano)silicon molecules as a result of single-collision events.

The Elusive Ketene (H2 CCO) Channel in the Infrared Multiphoton Dissociation of Solid 1,3,5-Trinitro-1,3,5-Triazinane (RDX).

Understanding of the fundamental mechanisms involved in the decomposition of 1,3,5-trinitro-1,3,5-triazinane (RDX) still represents a major challenge for the energetic materials and physical (organic) chemistry communities mainly because multiple competing dissociation channels are likely involved and previous detection methods of the products are not isomer selective. In this study we exploited a microsecond pulsed infrared laser to decompose thin RDX films at 5 K under mild conditions to limit the fragmentation channels. The subliming decomposition products during the temperature programed desorption phase are detected using isomer selective single photoionization time-of-flight mass spectrometry (PI-ReTOF-MS). This technique enables us to assign a product signal at m/z=42 to ketene (H2 CCO), but not to diazomethane (H2 CNN; 42 amu) as speculated previously. Electronic structure calculations support our experimental observations and unravel the decomposition mechanisms of RDX leading eventually to the elusive ketene (H2 CCO) via an exotic, four-membered ring intermediate. This study highlights the necessity to exploit isomer-selective detection schemes to probe the true decomposition products of nitramine-based energetic materials.

Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition-Dehydrocyclization: The Third Way.

Polycyclic aromatic hydrocarbons (PAHs) represent the link between resonance-stabilized free radicals and carbonaceous nanoparticles generated in incomplete combustion processes and in circumstellar envelopes of carbon rich asymptotic giant branch (AGB) stars. Although these PAHs resemble building blocks of complex carbonaceous nanostructures, their fundamental formation mechanisms have remained elusive. By exploring these reaction mechanisms of the phenyl radical with biphenyl/naphthalene theoretically and experimentally, we provide compelling evidence on a novel phenyl-addition/dehydrocyclization (PAC) pathway leading to prototype PAHs: triphenylene and fluoranthene. PAC operates efficiently at high temperatures leading through rapid molecular mass growth processes to complex aromatic structures, which are difficult to synthesize by traditional pathways such as hydrogen-abstraction/acetylene-addition. The elucidation of the fundamental reactions leading to PAHs is necessary to facilitate an understanding of the origin and evolution of the molecular universe and of carbon in our galaxy.

A study on the enzymatic properties and reuse of cellulase immobilized with carbon nanotubes and sodium alginate.

Cellulase has many potential applications in ethanol production, extraction of medicinal ingredients, food, brewing, oil exploration, environmental protection. However, the widespread use of cellulase is limited by its relatively high production costs and low biological activity. Therefore, we studied the enzymatic properties and reusability of cellulase immobilized on multiwalled carbon nanotubes and sodium alginate for the first time. The results showed that the optimum temperature and pH of immobilized cellulase was 40 °C and 3.0, respectively. After 1 month of storage at 4 °C, the enzyme activity of immobilized cellulase dropped to 71.2% of the baseline. Immobilized cellulase was proved to be reusable and maintained ~ 70% of its activity after 7 cycles of repeated use. Versus free cellulase, the immobilized cellulase showed good thermal stability, pH resistance, storage stability and reusability, which could be beneficial in large-scale industrial manufacturing processes.

A vacuum ultraviolet photoionization study on the formation of methanimine (CH2NH) and ethylenediamine (NH2CH2CH2NH2) in low temperature interstellar model ices exposed to ionizing radiation.

Methylamine (CH3NH2) and methanimine (CH2NH) represent essential building blocks in the formation of amino acids in interstellar and cometary ices. In our study, by exploiting isomer selective detection of the reaction products via photoionization coupled with reflectron time of flight mass spectrometry (Re-TOF-MS), we elucidate the formation of methanimine and ethylenediamine (NH2CH2CH2NH2) in methylamine ices exposed to energetic electrons as a proxy for secondary electrons generated by energetic cosmic rays penetrating interstellar and cometary ices. Interestingly, the two products methanimine and ethylenediamine are isoelectronic to formaldehyde (H2CO) and ethylene glycol (HOCH2CH2OH), respectively. Their formation has been confirmed in interstellar ice analogs consisting of methanol (CH3OH) which is ioselectronic to methylamine. Both oxygen-bearing species formed in methanol have been detected in the interstellar medium (ISM), while for methanimine and ethylenediamine only methanimine has been identified so far. In comparison with the methanol ice products and our experimental findings, we predict that ethylenediamine should be detectable in these astronomical sources, where methylamine and methanimine are present.

[Effects of forest gap on seasonal dynamics of soil organic carbon and microbial biomass car- bon in Picea asperata forest in Miyaluo of Western Sichuan, Southwest China].

Effects of gap sizes (50, 100 and 150 m2) on seasonal dynamics of soil organic carbon (SOC) and microbial biomass carbon (MBC) in soil surface (0-15 cm) and subsurface (15-30 cm) were investigated in a 50-year old Picea asperata plantation in Miyaluo forest, Western Si- chuan, China. In the four seasons, the SOC and MBC contents were higher in the soil surface than in soil subsurface in the four treatments, and varied insignificantly in different seasons. Compared with the control, the SOC content increased by 35.4%, 21.2% and 10.3% in soil surface, and by 45.5%, 25.0% and 12.1% in soil subsurface with the forest gaps of 50, 100 and 150 m2, respectively. The MBC content increased by 26.7%, 16.7%, 11.3% and 24.4%, 12.6%, 7.3% in soil surface and subsurface, respectively. There were significant negative relationship between soil SOC content and the soil pH and moisture, and significant positive relationship between soil SOC content and soil temperature. Significant effects of SOC content, soil pH, soil temperature, soil moisture on MBC content were observed, suggesting that forest gaps could significantly affect envi- ronmental conditions, and increasing gaps could reduce microbial activity and decomposition rate and decrease soil SOC and MBC contents.

[Study on display of acupuncture meridian based on electric signal transfer characteristics].

OBJECTIVE: To analyze the real-time effects of electroacupuncture (EA) stimulation by means of multiport network theory and measurement of the electric signals transfer coefficient, so as to explore a way for determining the running course of acupuncture meridian and for characterizing its physiological activities in the living body. METHODS: The body was modeled as a complex inhomogeneous 3-dimensions multi-port network, and the meridians were assumed to be "the most smoothly channels for signal transmission". Experiments were performed in 12 beheaded toads whose forelimbs and hindlimbs were divided into proportional coordinates. A concentric electrode with a conical tip was inserted into the toad leg for electrical stimulation of the local muscle, and another electrode alike was inserted into different spots of the limbs to detect the spreading signals in a 3-dimensional scanning mode. Following detecting the response electric voltage values of various spots and calculating their transfer coefficients, the spots which acquired a maximum signal value were considered to be the "acupoints". The imaginary connective lines passing the "acupoints" were regarded as the running courses of acupuncture meridians. RESULTS: A total of twelve 3-dimensional curves were detected based on the connected lines of electric signal transfer function extremum spots 2 mm beneath the skin of the ipsilateral fore- and hind-limbs of 12 spinal toads. CONCLUSION: The present study initially validates the feasibility of electric signal transfer coefficient measurement for displaying the running course of acupuncture meridian in the toad fore- and hindlimbs.

[Study on signal transmission characteristics of meridian based on electrical network theory and experiments].

Study on features of acupoints with resistance test in the past half century is reviewed in this article. Mechanism and technology of the method are introduced as well as its shortcomings. The determination method of signal transmission along meridians with the combination of electrical network theories and practice is advanced. And the result of a series experiments on one meridian at the superficial part of the body are given as well. Thus, it is concluded that the signals of the point-in/point-out and the signals along a non-meridian path with the same distance are significantly different, which gives a verification of the feasibility of the method by using electrical network theories to set out characteristics of signal transmission along meridians dynamically.