Synthetic Approaches to Star‐Shaped Molecules with 1,3,5‐Trisubstituted Aromatic Cores

Herein, we summarize the synthetic approaches that have been developed for the synthesis of star‐shaped molecules. Typically, to design such highly functionalized molecules, simple building blocks are first assembled through trimerization reactions, starting from commercially available starting materials. Then, these building blocks are synthetically manipulated to generate extended star‐shaped molecules. We also discuss the syntheses of star‐shaped molecules that contain 2,4,6‐trisubstituted 1,3,5‐triazine or 1,3,5‐trisubstituted benzene rings as a central core and diverse substituted styrene, phenyl, and fluorene derivatives at their periphery, which endows these molecules with extended conjugation. A variety of metal‐catalyzed reactions, such as Suzuki, Buchwald–Hartwig, Sonogashira, Heck, and Negishi cross‐coupling reactions, as well as metathesis, have been employed to functionalize a range of star‐shaped molecules. The methods described herein will be helpful for designing a wide range of intricate compounds that are highly valuable in the fields of supramolecular chemistry and materials science. Owing to space limitations, we will not cover all of the publications on this topic. Instead, we will focus on examples that were reported by our research group and other relevant recent literature. Apart from the trimerization sequence, this Minireview has been structured based on the key reactions that were used to prepare the star‐shaped molecules and other higher analogues. Finally, some examples that do not fit into this classification are discussed.     

Synthesis of coumarin based Knoevenagel-Ugi adducts by a sequential one pot five-component reaction and their biological evaluation as anti-bacterial agents

An efficient multicomponent synthesis of Ugi compounds comprising coumarin backbone has been achieved by employing one pot five component sequential Knoevenagel-Ugi reaction. This method offers the advantages of easy handling procedure, atom economy, mild reaction conditions and good yields of products. A molecular library was synthesized by changing the substituents on two of the independent starting materials. The synthesized compounds were also tested for anti-microbial activities and were found to be moderate to good anti-bacterial agents.     

添加钙基膨润土对猪粪堆肥中水溶性有机物光谱特征的影响

为了探究添加钙基膨润土(CB)对猪粪好氧堆肥过程中水溶性有机物(DOC)动态变化的影响,向猪粪和木屑混合物料中添加不同质量比的CB,采用自制的强制通风好氧发酵装置,进行了为期60天的好氧堆肥试验。定期采集堆肥样品并进行冷冻干燥,通过紫外-可见光谱(UV-Vis),傅里叶变换红外光谱(FTIR)和荧光光谱(FS)相结合的方法,对堆肥样品中DOC光谱特征的变化进行研究。结果表明,在堆肥过程中DOC呈降低趋势,且随着CB添加量的增多,DOC的降解率为49.11%~62.92%;堆肥DOC相应的UV-Vis和FS光谱分析显示,类腐殖质的特征峰强度不断升高,而碳水化合物、类蛋白的特征峰强度逐渐降低;且与对照相比,添加钙基膨润土使类腐殖质特征峰的强度增大,峰位置红移。堆肥结束时,相较于对照,添加CB处理的光谱特征参数SUVA₂₅₄,SUVA₂₈₀和腐殖化系数分别增加了16.51%~47.72%,8.58%~44.02%和23.16%~88.22%,且5%添加比例最佳,这被FTIR解析峰密度进一步证实;相关性分析显示,SUVA₂₅₄与堆肥腐熟度呈极显著相关,可指示堆肥腐熟度。综上所述,随着堆肥的进行,有机物由非腐殖质向腐殖质转化,DOC的分子质量及芳构化程度逐渐增加,且添加CB对这一过程具有促进作用,并以5%添加比例最佳。     

Detection of excess crystalline As in GaAs: Nation oxide overlayers by Raman scattering

Laser Raman spectroscopy was employed as a non-destructive probe for the detection and monitoring of crystalline arsenic in the native oxide films formed during heating of GaAs in air at various temperatures. Spectroscopy of oxide films formed after successive heating and etching treatments could confirm the location of arsenic to be near the top of the GaAs: native oxide overlayer.     

A second order uniformly convergent numerical scheme for parameterized singularly perturbed delay differential problems

In this work, we propose a hybrid difference scheme for solving parameterized singularly perturbed delay differential problems. A unified error analysis framework for the proposed hybrid scheme is given that allows to conclude uniform convergence of \(\mathcal {O}(N^{-2}\ln ^{2} N)\) on Shishkin meshes and \(\mathcal {O}(N^{-2})\) on Bakhvalov meshes, where N is the number of mesh intervals in the domain. Numerical results are included to confirm the theoretical estimates.     

Enhanced dielectric properties of polyethylene glycol (PEG) modified BaTiO<Subscript>3</Subscript> (BT)-poly(vinylidene fluoride) (PVDF) composites

To improve the compatibility between the ceramic particle and polymer matrix, the surface modifier polyethylene glycol (PEG) was used for the modification of BaTiO₃ (BT) particles as fillers in the poly(vinylidene fluoride) (PVDF) matrix via solution casting techniques. The structural analysis of the composite characterized by X-ray diffraction confirms the tetragonal structure. The results showed that the PEG modified BT-PVDF composites had a higher dielectric constant (≈192) and relatively lower dielectric loss value at 1000 Hz. The Nyquist plot suggests the contribution of only bulk effect present in the composites. The AC electrical conductivity studies obey Jonscher’s universal power law by fitting AC conductivity data which reveals the potential utility of the composites for ideal capacitor and microscopic reasons for this improvement were presented. Furthermore, the remnant polarization was significantly improved and maximum polarization was observed for PEG modified BT-PVDF composites.     

Coordination diversity in palladium(II)-picolinamide ligand complexes: structural and quantum chemical studies

The separation of different metal ions can be successfully accomplished by using picolinamide-based ligands. We herein report the first X-ray structure of picolinamide-based ligands of the type C₅H₄NCONR₂ (where R=ⁱC₃H₇ (L1) and ⁱC₄H₉ (L2)) and C₅H₄NCONHR (R=^tC₄H₉ (L3)) with palladium(II) ion. We have synthesized and characterized the structures of two palladium complexes, [PdCl₂(L1)₂] (1) and [PdCl₂L3] (3). In 1, ligand L1 forms a 2?:?1 complex with palladium(II) chloride, whereas in 3, the ligand L3 forms a 1?:?1 complex. Further, in 1, the ligand L1 acts as a monodentate ligand and is bound only through pyridyl-N atom, whereas in 3, the ligand L3 acts as a bidentate chelating ligand and is bound through both the pyridyl-N and amido-O atoms to the Pd(II) center. Electronic structure calculations are carried out to understand the experimental coordination diversity in the Pd complexes. Our calculations clearly suggest that a combination of steric hindrance of the ligand and the electronic effect of metal ions may modulate the coordination preferences.     

A study on seasonal variability of <Superscript>222</Superscript>Rn–<Superscript>220</Superscript>Rn parameters in dwellings around a thermal power plant,India

A novel ethylene diamine tetraacetic acid derivative of 4-nitroimidazole (EDTA-4-EtNHNM) was successfully synthesized as a carrier molecule and it was radiolabeled with ^99mTc in high yield to obtain ^99mTc-EDTA-4-EtNHNM, which was hydrophilic and had good in vitro stability. The tumor cell experiment and the biodistribution study in mice bearing S180 tumor showed that this complex exhibited a hypoxic selectivity and had high accumulation in tumor tissue with major clearance through urinary tract. High tumor uptake and tumor/muscle ratio of the complex suggests promise towards further evaluation.     

More fun & games with rings,strings & rods

The formation of polyrotaxanes of type 1 by “statistical” threading¹ will be described. Examples will include polymerization in the presence of macrocycles and threading of preformed polymers and macrocycles. An analysis of the structural and experimental factors involved in the threading process will be presented. The solution and solid state behavior of the polyrotaxanes will be discussed, including situations in which T_g can be controlled by macrocycles that are compatible with the backbone and situations where the threaded macrocycles crystallize. The preparation of polyrotaxanes of type 3 by threading of polymacrocycles 2 with linear polymers and the resultant changes in physical properties will also be described.