Thalappil Pradeep

Bio: Thalappil Pradeep is an academic researcher from Indian Institute of Technology Madras. The author has contributed to research in topics: Cluster (physics) & Mass spectrometry. The author has an hindex of 76, co-authored 581 publications receiving 24664 citations. Previous affiliations of Thalappil Pradeep include DST Systems & Lawrence Berkeley National Laboratory.

Extraction of Silver by Glucose.

Abstract: Unprecedented silver ion leaching, in the range of 0.7 ppm was seen when metallic silver was heated in water at 70 °C in presence of simple carbohydrates, such as glucose, making it a green method of silver extraction. Extraction was facilitated by the presence of anions, such as carbonate and phosphate. Studies confirm a two-step mechanism of silver release, first forming silver ions at the metal surface and later complexation of ionic silver with glucose; such complexes have been detected by mass spectrometry. Extraction leads to microscopic roughening of the surface making it Raman active with an enhancement factor of 5×108.

Light-Activated Intercluster Conversion of an Atomically Precise Silver Nanocluster.

Abstract: Noble metal nanoclusters protected with carboranes, a 12-vertex, nearly icosahedral boron-carbon framework system, have received immense attention due to their different physicochemical properties. We have synthesized ortho-carborane-1,2-dithiol (CBDT) and triphenylphosphine (TPP) coprotected [Ag42(CBDT)15(TPP)4]2- (shortly Ag42) using a ligand-exchange induced structural transformation reaction starting from [Ag18H16(TPP)10]2+ (shortly Ag18). The formation of Ag42 was confirmed using UV-vis absorption spectroscopy, mass spectrometry, transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and multinuclear magnetic resonance spectroscopy. Multiple UV-vis optical absorption features, which exhibit characteristic patterns, confirmed its molecular nature. Ag42 is the highest nuclearity silver nanocluster protected with carboranes reported so far. Although these clusters are thermally stable up to 200 °C in their solid state, light-irradiation of its solutions in dichloromethane results in its structural conversion to [Ag14(CBDT)6(TPP)6] (shortly Ag14). Single crystal X-ray diffraction of Ag14 exhibits Ag8-Ag6 core-shell structure of this nanocluster. Other spectroscopic and microscopic studies also confirm the formation of Ag14. Time-dependent mass spectrometry revealed that this light-activated intercluster conversion went through two sets of intermediate clusters. The first set of intermediates, [Ag37(CBDT)12(TPP)4]3- and [Ag35(CBDT)8(TPP)4]2- were formed after 8 h of light irradiation, and the second set comprised of [Ag30(CBDT)8(TPP)4]2-, [Ag26(CBDT)11(TPP)4]2-, and [Ag26(CBDT)7(TPP)7]2- were formed after 16 h of irradiation. After 24 h, the conversion to Ag14 was complete. Density functional theory calculations reveal that the kernel-centered excited state molecular orbitals of Ag42 are responsible for light-activated transformation. Interestingly, Ag42 showed near-infrared emission at 980 nm (1.26 eV) with a lifetime of >1.5 μs, indicating phosphorescence, while Ag14 shows red luminescence at 626 nm (1.98 eV) with a lifetime of 550 ps, indicating fluorescence. Femtosecond and nanosecond transient absorption showed the transitions between their electronic energy levels and associated carrier dynamics. Formation of the stable excited states of Ag42 is shown to be responsible for the core transformation.

Reactive ion scattering from surfaces bearing isomeric chlorinated adsorbates

Abstract: The value of low-energy ionic collisions for selective surface analysis is shown by the fact that reactive scattering allows differentiation of isomeric chemisorbates. Reactions of Cr•+ and Cr-containing cations at chlorobenzyl mercaptan (CBM) monolayers on Au surfaces show different reaction products, depending on the position of chlorine substitution in the phenyl ring. The chlorine atom abstraction product, CrCl+, is observed at 45-eV collision in 4-CBM and is completely absent in 2-CBM at the same energy. The sensitivity of reactive ion scattering to the isomeric adsorbate is further demonstrated by the fact that the peak corresponding to Cr•+ addition and Cl loss via Cl−C bond cleavage, C7H6SCr+, is large in the monolayer formed from 4-CBM, but weak in the 2-CBM monolayer, suggesting that the chlorine is below the first layer of atoms in the latter case. The inverse intensity relationship applies for the dehydrohalogenation product C7H5Cr+ where the Cl atom at the ortho position in 2-CBM facilitates ...

Synthesis of Atomically Precise Silver Clusters by Using the Miscibility Principle

Abstract: Invited for the cover of this issue is Thalappil Pradeep at the Indian Institute of Technology Madras, India. The cover image shows a schematic phase diagram of the three-component solvent system used for preparing monolayer-protected silver clusters. The different clusters obtained by keeping the reactants the same but adjusting the solvent system by moving to different regions of the phase diagram are shown in different colors.

I and i

Abstract: There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality. Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

Fast parallel algorithms for short-range molecular dynamics

Abstract: Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

疟原虫var基因转换速率变化导致抗原变异[英]／Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A

Abstract: 抗原变异可使得多种致病微生物易于逃避宿主免疫应答。表达在感染红细胞表面的恶性疟原虫红细胞表面蛋白1（PfPMP1）与感染红细胞、内皮细胞、树突状细胞以及胎盘的单个或多个受体作用，在黏附及免疫逃避中起关键的作用。每个单倍体基因组var基因家族编码约60种成员，通过启动转录不同的var基因变异体为抗原变异提供了分子基础。

Gold nanoparticles in chemical and biological sensing.

Abstract: Detection of chemical and biological agents plays a fundamental role in biomedical, forensic and environmental sciences1–4 as well as in anti bioterrorism applications.5–7 The development of highly sensitive, cost effective, miniature sensors is therefore in high demand which requires advanced technology coupled with fundamental knowledge in chemistry, biology and material sciences.8–13 In general, sensors feature two functional components: a recognition element to provide selective/specific binding with the target analytes and a transducer component for signaling the binding event. An efficient sensor relies heavily on these two essential components for the recognition process in terms of response time, signal to noise (S/N) ratio, selectivity and limits of detection (LOD).14,15 Therefore, designing sensors with higher efficacy depends on the development of novel materials to improve both the recognition and transduction processes. Nanomaterials feature unique physicochemical properties that can be of great utility in creating new recognition and transduction processes for chemical and biological sensors15–27 as well as improving the S/N ratio by miniaturization of the sensor elements.28 Gold nanoparticles (AuNPs) possess distinct physical and chemical attributes that make them excellent scaffolds for the fabrication of novel chemical and biological sensors (Figure 1).29–36 First, AuNPs can be synthesized in a straightforward manner and can be made highly stable. Second, they possess unique optoelectronic properties. Third, they provide high surface-to-volume ratio with excellent biocompatibility using appropriate ligands.30 Fourth, these properties of AuNPs can be readily tuned varying their size, shape and the surrounding chemical environment. For example, the binding event between recognition element and the analyte can alter physicochemical properties of transducer AuNPs, such as plasmon resonance absorption, conductivity, redox behavior, etc. that in turn can generate a detectable response signal. Finally, AuNPs offer a suitable platform for multi-functionalization with a wide range of organic or biological ligands for the selective binding and detection of small molecules and biological targets.30–32,36 Each of these attributes of AuNPs has allowed researchers to develop novel sensing strategies with improved sensitivity, stability and selectivity. In the last decade of research, the advent of AuNP as a sensory element provided us a broad spectrum of innovative approaches for the detection of metal ions, small molecules, proteins, nucleic acids, malignant cells, etc. in a rapid and efficient manner.37 Figure 1 Physical properties of AuNPs and schematic illustration of an AuNP-based detection system. In this current review, we have highlighted the several synthetic routes and properties of AuNPs that make them excellent probes for different sensing strategies. Furthermore, we will discuss various sensing strategies and major advances in the last two decades of research utilizing AuNPs in the detection of variety of target analytes including metal ions, organic molecules, proteins, nucleic acids, and microorganisms.