Molecular structure of Lantadene-B&C, triterpenoids ofantana camara, red variety: Lantadene-B, 22β-angeloyloxy-3-oxoolean-12-en-28-oic acid; Lantadene-C, 22 β-(S)-2′-methyl butanoyloxy-3-oxoolean-12-en-28-oic acid

(I)Lantadene-B: C35H52O5,M r =552.80, MonoclinicC2,a=25.65(1),b=6.819(9),c=18.75(1) Å,beta=100.61(9),V=3223(5) Å3,Z=4,D x =1.14 g cm–3 CuKagr (lambda=1.5418A),mgr=5.5 cm–1,F(000)=1208,R=0.118,wR=0.132 for 1527 observed reflections withF o ge2sgr(F o ). (II)Lantadene-C: C35H54O5·CH3OH,Mr=586.85, Monoclinic,P21,a=9.822(3),b=10.909(3),c=16.120(8)Å,beta=99.82(4),V=1702(1)Å3,Z=2,D x =1.145 g cm–3, MoKagr (lambda=0.7107Å), mgr=0.708 cm–1 F(000)=644,R=0.098, wR=0.094 for 1073 observed reflections. The rings A, B, C, D, and E aretrans, trans, trans, cis fused and are in chair, chair, sofa, half-chair, chair conformations, respectively, in both the structures. In the unit cell the molecules are stabilized by O-HctdotO hydrogen bonds in both the structures, however an additional C-HctdotO interaction is observed in the case of Lantadene-C.

Bridgehead substitution of 1-methoxybicyclo[2.2.2]oct 5-en-2-one derivatives: towards the synthesis of (±)-allo-cedrol [khusiol]1

Preparation of the key intermediates, 11 and 21, required for the synthesis of (+/-)-allo-cedrol (khusiol) is reported by a novel methodology involving the substitution at the bridgehead position of 1-methoxybicyclo[2.2.2]oct-5-en-2-one derivatives

Direct conversion of 13-beta-alkylgonatetraenes into 13-beta-alkylgon-4-en-3-ones

Birch reduction of 8,9-didehydroestradiol-17 beta 3-methyl ether 1 or 9(11)-didehydroestradiol-17 beta 3-methyl ether 2 followed by acid hydrolysis results in a mixture of 19-nortestosterone 8 and 19-nor-9 beta, 10 alpha-testosterone 9 in varying amounts. However, reduction of their acetates with sodium or lithium, tert-butyl alcohol in liquid ammonia and in the presence of aniline affords exclusively 19-nortestosterone. Similarly, 18a-homo-19-nortestosterone 12 is prepared from the acetate of 18a-homoestradiol-17 beta 3-methyl ether, 10.

Performance Analysis of User Selected Subband Channel Quality Indicator Feedback Scheme of LTE

Frequency-domain scheduling and rate adaptation have helped next generation orthogonal frequency division multiple access (OFDMA) based wireless cellular systems such as Long Term Evolution (LTE) achieve significantly higher spectral efficiencies. To overcome the severe uplink feedback bandwidth constraints, LTE uses several techniques to reduce the feedback required by a frequency-domain scheduler about the channel state information of all subcarriers of all users. In this paper, we analyze the throughput achieved by the User Selected Subband feedback scheme of LTE. In it, a user feeds back only the indices of the best M subbands and a single 4-bit estimate of the average rate achievable over all selected M subbands. In addition, we compare the performance with the subband-level feedback scheme of LTE, and highlight the role of the scheduler by comparing the performances of the unfair greedy scheduler and the proportional fair (PF) scheduler. Our analysis sheds several insights into the working of the feedback reduction techniques used in LTE.

Composite material and piezoelectric coefficient uncertainty effects on structural health monitoring using feedback control gains as damage indicators

This article addresses uncertainty effect on the health monitoring of a smart structure using control gain shifts as damage indicators. A finite element model of the smart composite plate with surface-bonded piezoelectric sensors and actuators is formulated using first-order shear deformation theory and a matrix crack model is integrated into the finite element model. A constant gain velocity/position feedback control algorithm is used to provide active damping to the structure. Numerical results show that the response of the structure is changed due to matrix cracks and this change can be compensated by actively tuning the feedback controller. This change in control gain can be used as a damage indicator for structural health monitoring. Monte Carlo simulation is conducted to study the effect of material uncertainty on the damage indicator by considering composite material properties and piezoelectric coefficients as independent random variables. It is found that the change in position feedback control gain is a robust damage indicator.

Synthesis of chiral bicyclo[2.2.2]oct-5-en-2-ones via an intramolecular alkylation reaction

Generation of the thermodynamic dienolate of 9-bromocarvone derivatives 5, 7 and 11 furnished the chiral bicycle[2.2.2] octenones 6, 8 and 9 and 12 and 13 containing a bridgehead methyl group via an intramolecular alkylation reaction. In an analogous manner intramolecular alkylation reaction of the bromo enones 15a-e, obtained from carvone 2 by 1,3-alkylative enone transposition (-->14) followed by a regiospecific bromoetherification reaction, furnished the bicyclo[2.2.2]oct-5-en-2-ones 16a-e and 17a-e.

Isomerisation of 4-aryl-4-methylhex-5-en-2-ones to 5-aryl-4-methylhex-5-en-2-ones by an intramolecular ene-retro ene reaction sequence

Acid-catalysed thermal rearrangement of 4-aryl-4-methylhex-5-en-2-ones (products of the Claisen rearrangement of beta-methylcinnamyl alcohols and 2-methoxypropene) to isomeric 5-aryl-4-methylhex-5-en-2-ones via an intramolecular ene reaction of the enol tautomer followed by a retro ene reaction of the resultant acetylcyclopropane is described. Formation of the known diketone 13 via the ozonolysis of the rearrangement product 10, confirmed the structures of the rearranged enones, whereas formation of the enone 15 containing an extra methyl group on the styrene double bond confirmed the proposed mechanism. Finally, the rearrangement has been extended to the formal synthesis of beta-cuparenone 20 via the enones 22 and 23.

Nonlinear dynamics and chaotic motions in feedback-controlled two- and three-degree-of-freedom robots

The dynamics of a feedback-controlled rigid robot is most commonly described by a set of nonlinear ordinary differential equations. In this paper we analyze these equations, representing the feedback-controlled motion of two- and three-degrees-of-freedom rigid robots with revolute (R) and prismatic (P) joints in the absence of compliance, friction, and potential energy, for the possibility of chaotic motions. We first study the unforced or inertial motions of the robots, and show that when the Gaussian or Riemannian curvature of the configuration space of a robot is negative, the robot equations can exhibit chaos. If the curvature is zero or positive, then the robot equations cannot exhibit chaos. We show that among the two-degrees-of-freedom robots, the PP and the PR robot have zero Gaussian curvature while the RP and RR robots have negative Gaussian curvatures. For the three-degrees-of-freedom robots, we analyze the two well-known RRP and RRR configurations of the Stanford arm and the PUMA manipulator respectively, and derive the conditions for negative curvature and possible chaotic motions. The criteria of negative curvature cannot be used for the forced or feedback-controlled motions. For the forced motion, we resort to the well-known numerical techniques and compute chaos maps, Poincare maps, and bifurcation diagrams. Numerical results are presented for the two-degrees-of-freedom RP and RR robots, and we show that these robot equations can exhibit chaos for low controller gains and for large underestimated models. From the bifurcation diagrams, the route to chaos appears to be through period doubling.

Role of feedback in mammalian vision: a new hypothesis and a computational model

This paper presents a novel hypothesis on the function of massive feedback pathways in mammalian visual systems. We propose that the cortical feature detectors compete not for the right to represent the output at a point, but for exclusive rights to abstract and represent part of the underlying input. Feedback can do this very naturally. A computational model that implements the above idea for the problem of line detection is presented and based on that we suggest a functional role for the thalamo-cortical loop during perception of lines. We show that the model successfully tackles the so called Cross problem. Based on some recent experimental results, we discuss the biological plausibility of our model. We also comment on the relevance of our hypothesis (on the role of feedback) to general sensory information processing and recognition. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Spiroannulation of a cyclopentane ring. Synthesis of spiro[4.n](n+5)alk-2-en-1-ones

A methodology based on Claisen rearrangement-Wacker oxidation and intramolecular aldol condensation strategy starting from cyclic ketones leading to spiro[4.n](n+5)alk-2-en-1-ones has been developed. Thus one-pot Claisen rearrangement of the alkyl alcohols 6a-c furnished the aldehydes 8a-c, which on regiospecific oxidation using Wacker conditions generated the keto-aldehydes 9a-c. Finally, intramolecular aldol condensation transformed the keto-aldehydes 9a-c into spiroannulated products 10a-c.

A comparison of the DNMR behaviour of methyl 5,6-bis(2-methoxyphenyl)-1,4-dimethyl-7-oxobicyclo[2.2.1]hept-5-en-2-endo-carboxylate and its 7-oxa analogue

Methyl 5,6-Bis(2-methoxyphenyt)-1,4-dimethyl-7-oxobicyclo[2.2.1]hept-5-en-2-endo-carboxylate, a moderately crowded norbornenone ester, exhibits complex VT-DNMR behaviour. A similar behaviour is not seen in its 7-oxa analogue, showing that conformational transmission from position 7 has a crucial influence on the distance parameters that govern the dynamic processes involving the substituents on the bicycloheptene framework.

Haptic Feedback for Injecting Biological Cells using Miniature Compliant Mechanisms

We present a real-time haptics-aided injection technique for biological cells using miniature compliant mechanisms. Our system consists of a haptic robot operated by a human hand, an XYZ stage for micro-positioning, a camera for image capture, and a polydimethylsiloxane (PDMS) miniature compliant device that serves the dual purpose of an injecting tool and a force-sensor. In contrast to existing haptics-based micromanipulation techniques where an external force sensor is used, we use visually captured displacements of the compliant mechanism to compute the applied and reaction forces. The human hand can feel the magnified manipulation force through the haptic device in real-time while the motion of the human hand is replicated on the mechanism side. The images are captured using a camera at the rate of 30 frames per second for extracting the displacement data. This is used to compute the forces at the rate of 30 Hz. The force computed in this manner is sent at the rate of 1000 Hz to ensure stable haptic interaction. The haptic cell-manipulation system was tested by injecting into a zebrafish egg cell after validating the technique at a size larger than that of the cell.