Sustainable life cycles of natural-precursor-derived nanocarbons

Sustainable societal and economic development relies on novel nanotechnologies that offer maximum efficiency at minimal environmental cost. Yet, it is very challenging to apply green chemistry approaches across the entire life cycle of nanotech products, from design and nanomaterial synthesis to utilization and disposal. Recently, novel, efficient methods based on nonequilibrium reactive plasma chemistries that minimize the process steps and dramatically reduce the use of expensive and hazardous reagents have been applied to low-cost natural and waste sources to produce value-added nanomaterials with a wide range of applications. This review discusses the distinctive effects of nonequilibrium reactive chemistries and how these effects can aid and advance the integration of sustainable chemistry into each stage of nanotech product life. Examples of the use of enabling plasma-based technologies in sustainable production and degradation of nanotech products are discussed—from selection of precursors derived from natural resources and their conversion into functional building units, to methods for green synthesis of useful naturally degradable carbon-based nanomaterials, to device operation and eventual disintegration into naturally degradable yet potentially reusable byproducts.

Thermal Expansivities and Temperature Coefficients of Refractive Indices for Molten Salts

An empirical relation for temperature–independent molar polarization is suggested. When this relation was used, the thermal expansivity was estimated correctly from refractive index data.

Applications of the Vilsmeier reaction. 13. Vilsmeier approach to polycyclic aromatic hydrocarbons

The Synthesis of three typical polycyclic hydrocarbons (PAH) has been described, wherein the Vilsmeier reaction plays a major role. Vilsmeier reaction of the tetraloll gives the dihydronaphthaldehyde 2 which on cyclodehydration gives the dihydroarene 3. Ita dehydrogenation affords 3-methoxybenz[a]anthracene (4). Vilsmeier reaction on the dimethoxydihydronaphthalene 5 gives the versatile dimethoxydihydronaphthaldehyde 6 which has been converted to the dimethoxybenzo[c]fluorene 7 by direct cyclodehydration and the fulvene 10 by cyclodehydration of allylic alcohol 8 derived from 6 followed by dehydrogenation. The saturated alcohol 12 corresponding to 8 undergoes cyclodehydration to give the dimethoxyhexahydrobenzo[c]phenanthrene (13). Some of the advantages of the Vilsmeier approach to PAH have been pointed out.

On the Maximum Cloud Zone and the ITCZ over Indian, Longitudes during the Southwest Monsoon

An investigation is presented of the daily variation of the maximum cloud zone (MCZ) and the 7W mb trough in the Northern Hemisphere over the Indian longitudes 70–90°E during April–October for 1973–77. It is found that during June–September there are two favorable locations for a MCZ over these longitudes–on a majority of days the MCZ is present in the monsoon zone north of 15°N, and often a secondary MCZ occurs in the equatorial region (0–10°N). The monsoon MCZ gets established by northward movement of the MCZ occurring over the equatorial Indian ocean in April and May. The secondary MCZ appears intermittently, and is characterized by long spells of persistence only when the monsoon MCZ is absent. In each of the seasons studied, the MCZ temporarily disappeared from the mean summer monsoon location (15–28°N) about four weeks after it was established near the beginning of July. It is reestablished by the northward movement of the secondary MCZ, which becomes active during the absence of the monsoon MCZ, in a manner strikingly similar to that observed in the spring to summer transition. A break in monsoon conditions prevails just prior to the temporary disappearance of the monsoon MCZ. Thus we conclude that the monsoon MCZ cannot survive for longer than a month without reestablishment by the secondary MCZ. Possible underlying mechanisms are also discussed.

Oxidations of thio ketones by singlet and triplet oxygen

Oxidation of di-tert-butyl thioketone (1) and 2,2,4,4-tetramethylcyclobutylth ioketone (2) by singlet oxygen yields the corresponding sulfine and ketone; in the case of 1 the sulfine is the major product, whereas in 2 it is the ketone. 1,2,3-Dioxathietane has been suggested as the precursor for the ketones, and the zwitterionic/diradid peroxide is believed to be a common primary intermediate for both sulfine and ketone. Steric influence is felt both during primary interaction between singlet oxygen and thioketone and during the partitioning of the peroxide intermediate. Steric interaction is suggested as the reason for variations in the product distribution between 1 and 2. Singlet oxygen is also generated through energy transfer from the triplet state of thioketones. These excited states also directly react with oxygen to yield ketone.

Synthesis of Thioesters from Carboxylic Acids via Acyloxyphosphonium Intermediates with Benzyltriethylammonium Tetrathiomolybdate as the Sulfur Transfer Reagent

An efficient protocol is reported for the synthesis of thioesters from carboxylic acids with use of acyloxy phosphonium salts as intermediates and benzyltriethylammonium tetrathiomolybdate as the sulfur transfer reagent.

Invariance group properties and exact solutions of equations describing time-dependent free surface flows under gravity

Using the method of infinitesimal transformations, a 6-parameter family of exact solutions describing nonlinear sheared flows with a free surface are found. These solutions are a hybrid between the earlier self-propagating simple wave solutions of Freeman, and decaying solutions of Sachdev. Simple wave solutions are also derived via the method of infinitesimal transformations. Incomplete beta functions seem to characterize these (nonlinear) sheared flows in the absence of critical levels.

Pressure-induced first-order transition in layered crystalline semiconductor GeSe to a metallic phase

The electrical resistivity of layerd crystalline GeSe has been investigated up to a pressure of 100 kbar and down to liquid-nitrogen temperature by use of a Bridgman anvil device. A pressure-induced first-order phase transition has been observed in single-crystal GeSe near 6 GPa. The high-pressure phase is found to be quenchable and an x-ray diffraction study of the quenched material reveals that it has the face-centered-cubic structure. Resistivity measurements as a function of pressure and temperature suggest that the high-pressure phase is metallic.