Regio- and enantioselective intermolecular rhodium-catalyzed [2+2+2] carbocyclization reactions of 1,6-enynes with methyl arylpropiolates

Transition metal-catalyzed [m+n+o] carbocyclization reactions provide powerful methods for the construction of complex polycyclic systems that are generally not accessible through classical pericyclic reactions. We have developed the first regio- and enantioselective crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon- and heteroatom-tethered 1,6-enynes with unsymmetrical 1,2-disubstituted alkynes. This study clearly delineates the ligand requirements for obtaining excellent regio- and enantioselectivity. Furthermore, the ability to utilize various electron-withdrawing groups, and to introduce quaternary carbon stereogenic centers, provides the level of versatility necessary for its application to target-directed synthesis. Additional studies on the development and application of this novel methodology to the total synthesis of natural products are currently underway.     

Ab initio calculation of molar volumes: Comparison with experiment and use in solvation models

A simple and efficient procedure of calculating molecular volume (V_M) based on the Monte Carlo method is presented. The volume of a molecule is defined by the volume occupied by the 0.001-au electron density envelope. We have employed this method to compute the molecular volumes (V_M) of a large selection of organic molecules and compare them with the corresponding molar volumes (V_m) measured in the liquid state. A strong correlation is found to exist between the V_M and V_m values (V_M/V_m ≈ 0.75). Using this linear relationship, the calculated molecular volume may provide an estimate of the cavity-volume parameter in solvent-effect calculations. As a chemical application of molecular volume, we have investigated the conformational equilibrium of 1,2-difluoroethane in the liquid state using the self-consistent reaction field theory. © 1995 by John Wiley & Sons, Inc.     

Photochemical Degradation of the Plant Growth Regulator 2‐(1‐Naphthyl) acetamide in Aqueous Solution Upon UV Irradiation

The photochemical degradation of 2‐(1‐naphthyl) acetamide (NAD) in aqueous solution using simulated sunlight excitation as well as UV light within the 254–300 nm range was investigated to obtain an insight into the transformation mechanism that could occur under environmental conditions. Several photoproducts were identified using HPLC/MS/MS techniques. The degradation quantum yield was found to be independent of the excitation wavelength, but showed a dependence of oxygen concentration. This increased by a factor of approximately 3 from aerated to oxygen‐free solutions. There is a clear involvement of both triplet and singlet excited states in NAD photoreactivity. The participation of singlet oxygen as a significant route in NAD degradation was ruled out by comparison with the behavior using Rose Bengal as a photosensitizer. A mechanistic pathway implying hydroxylation process through NAD radical cation species as well as an oxidation reaction by molecular oxygen is proposed. The photochemical behavior of NAD appears to mainly involve the aromatic moieties without any participation of the amide side chain. Toxicity tests clearly show that the generated primary photoproducts are responsible for a significant increase in the toxicity. However, upon prolonged irradiation this toxicity tends to decrease.     

Low-cost Imaging of Fluorescent DNA in Agarose Gel Electrophoresis using Raspberry Pi cameras

Low-cost analytical solutions built around microcomputers like the Raspberry Pi help to facilitate laboratory investigations in resource limited venues. Here, three camera modules (V1.3 with and without filter, as well as NoIR) that work with this microcomputer were assessed for their suitability in imaging fluorescent DNA following agarose gel electrophoresis. Evaluation of their utility was based on signal-to-noise (SNR) and noise variance metrics that were developed. Experiments conducted with samples were subjected to Polymerase Chain Reaction (PCR), and the amplified products were separated using gel electrophoresis and stained with Midori green. Image analysis revealed the NoIR camera performed the best with SNR and noise variance values of 21.7 and 0.222 respectively. In experiments conducted using UV LED lighting to simulate ethidium bromide (EtBr) excitation, the NoIR and V1.3 with filter removed cameras showed comparable SNR values.

     

Minimalist and convenient mode changing off-axis digital holography

Basic issues in creating practical setups for off-axis digital holography involve having (i) convenient switch of imaging in the transmission and reflection modes, (ii) reduction in stray light reflection, (iii) immunity against environmental noise, and (iv) efficient usage of light output from the laser source. These exigencies are addressed using a free-space setup described here that applies a minimal number of optical components. Experimental results are presented to verify the approach.     

Triple shape memory effect in multiple crystalline polyurethanes

Remembering more than one permanent shape is an attractive research topic for shape memory materials (SMMs). In this paper, multiple crystalline shape memory polyurethanes (SMPUs) are prepared with PCL10000 and PTMG2900 by a three‐step polymerization method. DSC and WAXD results show that the obtained polyurethane contains, simultaneously and independently, two kinds of crystals. In addition, it is confirmed through DMA analysis that reversible soft phase and hard domains are formed in the PCL‐PTMG based SMPU system; and two‐step modulus decreases at low temperature range can be obtained in the SMPU with suitable mass proportion of PCL to PTMG, e.g., 1:7. Thus, shape memory effect (SME) can be achieved in this system. Moreover, it is found that the PTMG soft segment dominates the shape memory effect when the PCL mass is lower than that of PTMG; while the PCL soft segment dominates the SME when PCL mass is higher than that of PTMG; and a two‐step programing shape recovery can be achieved when the mass proportion of PCL/PTMG reaches a balance value, e.g., 3:5. Copyright © 2009 John Wiley & Sons, Ltd.     

Pre-visual detection of iron and phosphorus deficiency by transformed reflectance spectra

Reflectance spectroscopy and strategies for spectral analysis over the visible range from 380 to 780 nm were used to provide diagnostic information on iron (Fe) and phosphorus (P) status of Brassica chinensis L. var parachinensis (Bailey) grown under hydroponics conditions. Leaf reflectance (R) spectra were collected and normalized inner reflectance (NR(I)) spectra were calculated. The regression coefficients (B-matrix) and variable importance for projection (VIP) in partial least squares regression were used to determine important wavelengths that correlate with total chlorophyll (Chl) content. No single wavelength that showed good correlation with Chl content was found. Therefore, NR(I) was transformed into CIELAB color values, which simplified the whole visible spectrum into three values. Our results showed that upon Fe deprivation, plants entered into a deficiency state very rapidly, highlighting the importance of early diagnosis. The direct effect of Fe on leaf Chl content allowed CIELAB color values to be used for pre-visual detection of Fe deficiency 2 days before the appearance of visually distinguishable morphological changes. On the other hand, P-deprived plants showed a marked decline in cellular P levels but remained above critical threshold concentrations after 7 days. The Chl content was not affected by the leaf P content and CIELAB color values showed no difference with control plants.