Enantioselective Additions of Aryltitanium Tris(isopropoxide) to Ketones: Structure of [(i‐PrO)2Ti{μ‐(S)‐BINOLate}(μ‐O‐i‐Pr)TiPh(O‐i‐Pr)2], Study of Mechanistic and Stereochemical Insights

Aryl addition reactions of ArTi(O‐i‐Pr)₃ to aromatic, heteroaromatic, or α,β‐unsaturated ketones are described, producing tertiary alcohols in good to excellent enantioselectivities of up to 97% ee. The structure of the dititanium complex [(i‐PrO)₂Ti{μ‐(S)‐BINOLate}(μ‐O‐i‐Pr)TiPh(O‐i‐Pr)₂] [(S)‐ 4 ] that simultaneously bears a chiral directing ligand and a nucleophile is reported. Complex (S)‐ 4 possesses a pocket structure and has been illustrated as the key active species for addition reactions of both aldehydes and ketones. Mechanistic and stereochemical insights concerning addition reactions of organometallic reagents to organic carbonyls are rationalized based on the pocket structure and pocket size of (S)‐ 4 .     

Effects of molding conditions on the electromagnetic interference performance of conductive ABS parts

Polymers filled with conducting fibers to prevent electromagnetic interference (EMI) performance have recently received great attention due to the requirements of 3C (computer, communication, and consumer electronics) products. In the present article, the effect of fiber content and processing parameters, including melt temperature, mold temperature, and injection velocity, on the electromagnetic interference shielding effectiveness (SE) in injection molded ABS polymer composites filled with conductive stainless steel fiber (SSF) was investigated. The influence of fiber orientation and distribution resulting from fiber content and molding conditions on EMI performance was also examined. It was found from measured results that fiber content plays a significant role in influencing part EMI SE performance. SE value can reach the highest values of approximately 40 dB and 60 dB at 1000 MHz frequency for fiber content 7 wt % and 14 wt %, respectively, under the best choice of molding conditions. Higher melt and mold temperature would increase shielding effectiveness due to a more uniform and random fiber orientation. However, higher injection velocity leading to highly‐orientated and less uniform distribution of fiber reduces shielding effectiveness. Among all molding parameters, melt temperature affects SE performance most significantly. Its influence slightly decreases as fiber content increases. Injection speed plays a secondary importance in affecting SE values, and its influence increases as fiber content increases. Upon examination of fiber distribution via optical microscope and subsequent image analysis, it was found that the fiber becomes more densely and random distributed toward the last melt‐filled region, whereas fiber exhibits less concentration around the middle way of the flow path. This can be attributed to the combined effects of fountain flow, frozen layer thickness, and gapwise melt front velocity. The results indicate that molding conditions, instead of fiber content alone, are very important on the SE performance for injection molded SSF filled ABS composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1072–1080, 2005     

Easy Access to 1‐Amino and 1‐Carbon Substituted Isoquinolines via Cobalt‐Catalyzed C?H/N?O Bond Activation

A green atom‐economical method for the synthesis of highly functionalized 1‐amino and 1‐carbon substituted isoquinolines from the reaction of N′‐hydroxybenzimidamides and aryl ketoximes, respectively, with alkynes via pentamethylcyclopentadienylcobalt(III)‐catalyzed C H/N O bond activation is described. The external oxidant‐free annulation reaction uses the =NOH moiety in N′‐hydroxybenzimidamides or N‐aromatic ketone oximes as the directing group and internal oxidant. This first row transition metal‐catalyzed annulation serves as an efficient alternative for the synthesis of isoquinolines, as water is the only by‐product and expensive noble metals such as rhodium(III), iridium(III), palladium(II), and ruthenium(II) are not required. The reaction proceeds via C H activation, alkyne insertion, reductive elimination, and N O activation.

     

Exploring Pharmacological Functions of Alternatively Spliced Variants of the Mu Opioid Receptor Gene,Oprm1, via Gene-Targeted Animal Models

The mu opioid receptor has a distinct place in the opioid receptor family, since it mediates the actions of most opioids used clinically (e.g., morphine and fentanyl), as well as drugs of abuse (e.g., heroin). The single-copy mu opioid receptor gene, OPRM1, goes through extensive alternative pre-mRNA splicing to generate numerous splice variants that are conserved from rodents to humans. These OPRM1 splice variants can be classified into three structurally distinct types: (1) full-length 7 transmembrane (TM) carboxyl (C)-terminal variants; (2) truncated 6TM variants; and (3) single TM variants. Distinct pharmacological functions of these splice variants have been demonstrated by both in vitro and in vivo studies, particularly by using several unique gene-targeted mouse models. These studies provide new insights into our understanding of the complex actions of mu opioids with regard to OPRM1 alternative splicing. This review provides an overview of the studies that used these gene-targeted mouse models for exploring the functional importance of Oprm1 splice variants.     

IDENTIFICATION OF TRANSFER FUNCTION MODELS FROM THE RELAY FEEDBACK TEST

A MIMO process is considered to be composed of several single-input-multi-output (SIMO) processes. In this article, a method for identifying such SIMO process is devised. To identify each SIMO process, a single run of relay feedback experiment on a particular input is required. For each of such experiments, models of FOPDT (First-Order-Plus-Dead-Time) or of SOPDT (Second-Order-Plus-Dead-Time) are identified. Estimation of the parameters is carried out one-by-one and does not involve least square minimization. Direct application of these SIMO identification to MIMO processes is thus illustrated. The accuracy of each estimated gain can be controlled within one single run of experiment. A sufficient condition for the experiments to ensure robustness of the resulting model is presented. Thus, this proposed method can be applied to some MIMO processes even they are ill-conditioned.     

Simulation of a mold‐cooling process for gas‐assisted injection molded parts designed with a top rib on the gas channel

The same CAE model used for the filling and packing stage in the gas‐assisted injection molding (GAIM) process simulation was also applied to simulate the cooling phase. This was made possible by using the line source method for modeling cooling channels. The cycle‐averaged and cyclic transient mold cavity surface temperature distribution within a steady cycle was calculated using the three‐dimensional modified boundary element technique similar to that used in conventional injection molding. The analysis results for GAIM plates of a semicircular gas channel design attached with a top rib are illustrated and discussed. It was found that the difference in cycle‐averaged mold wall temperatures may be as high as 10°C, and within a steady cycle, part temperatures may also vary by about 15°C. The conversion of the gas channel into equivalent circular pipe and further simplification into two‐node elements using the line source method not only affects the mold wall temperature calculation very slightly but also reduces the computer time by 93%. This indicates that it is feasible to achieve an integrated process simulation for GAIM under one CAE model, resulting in great computational efficiency for industrial application.     

Fabrication of superhydrophobic silica‐based surfaces with high transmittance by using polypropylene and tetraeyhoxysilane precursors

Preparation of superhydrophobic silica‐based surfaces via sol–gel process by adding polyethylene glycol (PEG) polymer into the precursor solution has been developed. Surface roughness of the films was obtained by removing the organic polymer at 500°C and then the hydrophobic groups bonded onto the films were obtained by self‐assembly modification with a monolayer. Characteristic properties of the as‐prepared films were analyzed by contact angle measurements, scanning electron microscopy, atomic force microscopy, UV–vis scanning spectrophotometer, and X‐ray photoelectron spectrophotometer. The experimental parameters were varied by the type of silane species, the R ratio, the hydrolysis time of the precursor solution, the molecular weight of PEG, the pH value of mixing solution, and the different reagents for modification. The results showed that optimum ratio of TEOS/H₂O/ethanol in the sol–gel process for precursor solution was set to 1/10/4. The better contact angles of the films can be obtained by the acid catalyst reaction, especially the pH value of mixing solution was adjusted to 0. When the as‐prepared rough films were modified with (tridecafluoro‐1,1,2,2‐tetrahydrooctyl) dimethylchlorosilane (TFCS), the contact angle of the film can be promoted to 150.4°, and the transmittance of the films in the visible light region was greater than 94.5%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Experimental determination of NH<Subscript>4</Subscript>NO<Subscript>3</Subscript>-KNO<Subscript>3</Subscript> binary phase diagram

The solid-state phase transitions in ammonium nitrate (AN)-potassium nitrate (KN) system, and the equilibrium AN-KN phase diagram have been determined by using differential scanning calorimetry and high-temperature in situ x-ray diffractometry. Sample preparation was performed in a special “dry room” with very low humidity. A single phase region (AN III) with no phase transitions to 373 K was observed in the composition range 5 to 20% KN; this is critical for use in air bag gas generators. The high-temperature KN phase (KN I) has a wide range of stability from 20 to 100 wt.% KN. There are one eutectic, two eutectoid, three peritectoid, and one congruent transformations in this phase diagram. Two new nonstoichiometric phases were found at lower temperatures in the mid-composition range between the AN and KN terminal solid solutions. Details of the phase equilibria are presented.     

Reversal of the Inflammatory Responses in Fabry Patient iPSC-Derived Cardiovascular Endothelial Cells by CRISPR/Cas9-Corrected Mutation

The late-onset type of Fabry disease (FD) with GLA IVS4 + 919G > A mutation has been shown to lead to cardiovascular dysfunctions. In order to eliminate variations in other aspects of the genetic background, we established the isogenic control of induced pluripotent stem cells (iPSCs) for the identification of the pathogenetic factors for FD phenotypes through CRISPR/Cas9 genomic editing. We adopted droplet digital PCR (ddPCR) to efficiently capture mutational events, thus enabling isolation of the corrected FD from FD-iPSCs. Both of these exhibited the characteristics of pluripotency and phenotypic plasticity, and they can be differentiated into endothelial cells (ECs). We demonstrated the phenotypic abnormalities in FD iPSC-derived ECs (FD-ECs), including intracellular Gb3 accumulation, autophagic flux impairment, and reactive oxygen species (ROS) production, and these abnormalities were rescued in isogenic control iPSC-derived ECs (corrected FD-ECs). Microarray profiling revealed that corrected FD-derived endothelial cells reversed the enrichment of genes in the pro-inflammatory pathway and validated the downregulation of NF-κB and the MAPK signaling pathway. Our findings highlighted the critical role of ECs in FD-associated vascular dysfunctions by establishing a reliable isogenic control and providing information on potential cellular targets to reduce the morbidity and mortality of FD patients with vascular complications.