η4‐HBCC‐σ,π‐Borataallyl Complexes of Ruthenium Comprising an Agostic Interaction

Thermolysis of [Cp*Ru(PPh₂(CH₂)PPh₂)BH₂(L₂)] 1 (Cp*=η⁵‐C₅Me₅; L=C₇H₄NS₂), with terminal alkynes led to the formation of η⁴‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)B{R‐C=CH₂}(L)₂] ( 2 a – c ) and η²‐vinylborane complexes [Cp*Ru(R‐C=CH₂)BH(L)₂] ( 3 a – c ) ( 2 a , 3 a : R=Ph; 2 b , 3 b : R=COOCH₃; 2 c , 3 c : R=p‐CH₃‐C₆H₄; L=C₇H₄NS₂) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a – c are linked by a unique η⁴‐interaction. Conversions of 1 into 3 a – c proceed through the formation of intermediates 2 a – c . Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ‐borane complex [Cp*RuCO(μ‐H)BH₂L] 4 (L=C₇H₄NS₂) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η⁴‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)BH{R‐C=CH₂}(L)] 5 and [Cp*Ru(μ‐H)BH{HC=CH‐R}(L)] 6 (R=COOCH₃; L=C₇H₄NS₂) by Markovnikov and anti‐Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η⁴‐σ,π‐borataallyl complex [Cp*Ru(μ‐H)BH{R‐C=CH‐R}(L)] 7 (R=COOCH₃; L=C₇H₄NS₂). An agostic interaction was also found to be present in 2 a – c and 5 – 7 , which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, ¹H, ¹¹B, ¹³C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b , 3 a – c and 5 – 7 . DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds.     

Ammonium Sulphate—Magnesium Promoted Selective Reduction of Aromatic Nitro Compounds

Various nitroarenes and 2,1,3-benznooxadiazole-1-oxides were selectively and rapidly reduces to their corresponding amino and diamino compounds respectively in high yields using (NH₄SO₄-Mg/A1/Bi, a new reduction system.     

Investigation of surface plasmon resonance using cylindrical dielectric-metal-dielectric (C-DMD) plasmonic configuration

In this paper we have proposed a technique based on image analysis of the surface plasmon excitation at the metal-dielectric interface of inside silver coated fused silica capillary glass tube. Chemical deposition technique has been used for the deposition of silver. Angular interrogation in Kretschmann-like configuration is realized by non-radial transverse illumination of this cylindrical dielectric-metal-dielectric (C-DMD) structure with a He–Ne laser source. Here the uniform film deposition of the inside surface of the capillary is not that crucial except within the transversely illuminated working area concerned. Moreover, the proposed technique has been validated experimentally for sensing different aqueous dielectric samples inserted inside the tube.     

Design and Characterization of a W-Band Folded-Waveguide Slow-Wave Structure

A single-section slow-wave structure for a W-band folded-waveguide traveling-wave tube with operating bandwidth of around 4% was designed for delivering the output power of 50 W at the operating voltage of 13.5 kV and operating beam current of 80 mA. The design was carried out using analytical formulations and 3D electromagnetic simulations. The beam-wave interaction analysis was carried out using large signal Lagrangian analysis and particle-in-cell simulation. The folded-waveguide slow-wave structure along with input-output couplers and RF windows were fabricated. Cold test measurements were carried out for dispersion characteristics of the slow-wave structure and voltage standing-wave ratio and insertion loss characteristics of the RF window. The measured cold circuit parameters show close agreement with the analysis.     

Dioxane Dibromide–Mediated Solvent‐Free Synthesis of Vicinal Dibromides

Structurally varied vicinal dibromides have been synthesized in high yield and good purity through highly stereoselective anti‐addition of bromine across the olefinic linkages using dioxane dibromide (DD) under solvent‐free conditions.     

A diversity oriented synthesis of d-erythro-sphingosine and siblings

An efficient building block-based synthetic protocol has been developed for the synthesis of 3-ketosphingoids with various chain lengths using cross metathesis of a Garner’s aldehyde-derived α,β-unsaturated ketone as the key step. Stereoselective reduction of the biomimetic precursors thus obtained provided d-erythro-sphingosine and truncated anaogues in good overall yields.     

Reaction of bis-Lactone in Rigid Polycycles with Alkyl Lithiums. Synthesis of Novel Oxa-Cace Compounds

Reaction of bis-lactone embodied in the rigid tircyclo [5.2.1.0^2,6] decane 5 with MeLi and t-BuLi produced the novel oxa-cage compounds 9 and 11 instead of the expected ketones 6.     

Coexistence and harvesting control policy in a food chain model with mutual defense of prey

A model is proposed to understand the dynamics in a food chain (one predator‐two prey). Unlike many approaches, we consider mutualism (for defense against predators) between the two groups of prey. We investigate the conditions for coexistence and exclusion. Unlike Elettreby's (2009) results, we show that prey can coexist in the absence of predators (as expected since there is no competition between prey). We also show the existence of Hopf bifurcation and limit cycle in the model, and numerically present bifurcation diagrams in terms of mutualism and harvesting. When the harvest is practiced for profit making, we provide the threshold effort value that determines the profitability of the harvest. We show that there is zero profit when the constant effort is applied. Below (resp. above) , there will always be gain (resp. loss). In the case of gain, we provide the optimal effort and optimal steady states that produce maximum profit and ensure coexistence. Recommendations for resource managers As a result of our investigation, we bring the following to the attention of management:

• 1. In the absence of predators, different groups of prey can coexist if they mutually help each other (no competition among them).
• 2. There is a maximal effort to invest in order to gain profit from the harvest. Above , the investment will result in a loss.
• 3. In the case of profit from harvest, policy makers should recommend the optimal effort to be applied and the optimal stock to harvest. This will guarantee maximum profit while ensuring sustainability of all species.

     

Artificial neural network‐based modeling of snow properties using field data and hyperspectral imagery

This study attempts to model snow wetness and snow density of Himalayan snow cover using a combination of Hyperspectral image processing and Artificial Neural Network (ANN). Initially, a total of 300 spectral signature measurements, synchronized with snow wetness and snow density, were collected in the field. The spectral reflectance of snow was then modeled as a function of snow properties using ANN. Four snow wetness and three snow density models were developed. A strong correlation was observed in near‐infrared and shortwave‐infrared region. The correlation analysis of ANN modeled snow density and snow wetness showed a strong linear relationship with field‐based data values ranging from 0.87–0.90 and 0.88–0.91, respectively. Our results indicate that an Artificial Intelligence (AI) approach, using a combination of Hyperspectral image processing and ANN, can be efficiently used to predict snow properties (wetness and density) in the Himalayan region. Recommendations for resource managers

• Snow properties, such as snow wetness and snow density are mainly investigated through field‐based survey but rugged terrains, difficult weather conditions, and logistics management issues establish remote sensing as an efficient alternative to monitor snow properties, especially in the mountain environment.
• Although Hyperspectral remote sensing is a powerful tool to conduct the quantitative analysis of the physical properties of snow, only a few studies have used hyperspectral data for the estimation of snow density and wetness in the Himalayan region. This could be because of the lack of synchronized snow properties data with field‐based spectral acquisitions.
• In combination with Hyperspectral image processing, Artificial Neural Network (ANN) can be a useful tool for effective snow modeling because of its ability to capture and represent complex input‐output relationships.
• Further research into understanding the applicability of neural networks to determine snow properties is required to obtain results from large snow cover areas of the Himalayan region.